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ArticleNovember 27, 2013

Synthesis, Characterization, and Electronic Structure of Single-Crystal SnS, Sn₂S₃, and SnS₂
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Chemistry of Materials

Cite this: Chem. Mater. 2013, 25, 24, 4908–4916

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https://doi.org/10.1021/cm403046m

Published November 27, 2013

Abstract

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Tin sulfide is being widely investigated as an earth-abundant light harvesting material, but recorded efficiencies for SnS fall far below theoretical limits. We describe the synthesis and characterization of the single-crystal tin sulfides (SnS, SnS₂, and Sn₂S₃) through chemical vapor transport, and combine electronic structure calculations with time-resolved microwave conductivity measurements to shed light on the underlying electrical properties of each material. We show that the coexistence of the Sn(II) and Sn(IV) oxidation states would limit the performance of SnS in photovoltaic devices due to the valence band alignment of the respective phases and the “asymmetry” in the underlying point defect behavior. Furthermore, our results suggest that Sn₂S₃, in addition to SnS, is a candidate material for low-cost thin-film solar cells.

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Introduction

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In order for photovoltaic (PV) technology to provide a significant fraction of the world’s energy demands, devices must be composed of cheap and abundant materials. (1) Tin monosulfide (SnS) is increasingly being investigated as a photoconverter because it is neither scarce, expensive, nor toxic, (2) unlike commercially available cadmium telluride (CdTe) or copper–indium–gallium–diselenide (CIGS). (3) It is also a binary component of the popular copper–zinc−tin–sulfide (CZTS) absorber system. (4)

SnS exhibits almost ideal electronic properties for PV applications, including a higher optical absorption coefficient than CdTe, (5, 6) and an effective onset of optical absorption that coincides with the optimum band gap for maximum efficiency according to the Shockley–Queisser limit within the AM 1.5 solar spectrum. (7-11) As a result, a theoretical conversion efficiency of 24% for SnS single-junction devices is predicted from Prince–Loferski diagrams. (8, 12-14) SnS also does not require extrinsic doping because of intrinsic p-type conductivity brought about by the formation of tin vacancies. (15) All of this suggests that the application of SnS in thin film photovoltaics could lead to devices with low cost and high market penetration. (16) In practice, however, the highest certified light-to-electricity conversion efficiency of SnS devices is still only 2.0%, (17) despite the first SnS PV device being reported in 1997 with a 0.5% efficiency. (18)

The poor performance of SnS solar cells to date could be related to a number of materials issues including: (i) low quality single phase materials, i.e. single phase SnS with defect and carrier concentrations and/or morphology that is not optimal. (ii) Device architecture, i.e. the commonly used electrical contacts and buffer layer materials are unsuitable for high conversion efficiencies. (19, 20) (iii) Mixed phases, i.e., the presence of alternate SnS polytypes, Sn₂S₃ or SnS₂, may be detrimental to the photovoltaic performance. (21, 22) The first issue could be avoidable under suitable synthesis conditions, (23-25) and the second could be investigated by varying the materials used as electrical contacts. (19, 20) We address the third outstanding issue in this work, investigating the three distinct stoichiometries of tin sulfide and the properties of each.

As a heavier element in Group 14 of the Periodic Table, Sn has two accessible oxidation states: divalent (electronic configuration [Kr]4d¹⁰5s²5p⁰) and tetravalent (electronic configuration [Kr]4d¹⁰5s⁰5p⁰). The thermodynamic balance between these two oxidation states is subtle, and both Sn(II) and Sn(IV) compounds are known to exist. SnS and SnS₂ are formed from a single oxidation state, while Sn₂S₃ is a multivalent compound, which can be described as Sn(II)Sn(IV)S₃. The lower oxidation state is associated with a Sn lone pair, (26) which is the origin of the structural distortion found in the ground-state orthorhombic phase of SnS (Figure 1). (27)

In terms of conductivity, a reducible cation (i.e., tetravalent Sn) is generally associated with electron conduction (n-type), while an oxidizable cation (i.e., divalent Sn) is associated with hole conduction (p-type). Indeed, SnS₂ and Sn₂S₃ have been reported to be n-type semiconductors, whereas SnS exhibits p-type behavior. (28-31) It has been observed that a 15% deviation from ideal stoichiometry is sufficient to change the conduction of SnS from p- to n-type, (32) and it is thought that with appropriate control of the stoichiometry, a p–n junction can be formed from just tin and sulfur. (33, 34) These factors re-enforce the hypothesis that deviations from ideal stoichiometry could be the cause of poor device performances recorded thus far.

Figure 1. Ground-state crystal structures of the three phases of tin (gray) sulfide (yellow): (a) SnS, (b) SnS₂, and (c) Sn₂S₃.

There is confusion in the literature with respect to the assignment of distinct phases and the presence of alternate stoichiometries that cannot necessarily be discerned by common diffraction methods. (27, 32, 34) Indeed, as we will discuss, fundamental properties such as color, band gap, and the origin of free-carriers are still under debate and the current treatment of these materials is clearly not amenable to high performance applications. To understand the behavior of these materials in thin-films and nanoparticles, it is important to isolate the separate phases and to consider the distinct properties of each. (31)

We approach the problem by combining high-quality experiment and computation. The targeted synthesis of SnS, SnS₂, and Sn₂S₃ by chemical vapor transport (CVT) is used to produce macroscopic crystals, which have been characterized in terms of structure, morphology, and conductivity. The electronic structure and defect chemistry of the three materials have been modeled using density functional theory (DFT). Several inconsistencies are found with respect to phase-assignments and materials properties in the literature. Our results provide a platform to achieving sustainable light harvesting devices from Sn and S.

Methods

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Chemical Vapor Transport

Single crystals of tin sulfide have been grown previously by the Bridgman method (31) and chemical vapor transport, (35) and thin films formed by many different deposition methods. (24, 32, 36-42) CVT was first proposed by Schäfer as a way to vaporise metals at lower temperatures by forming a volatile chemical intermediate. (43) For tin, iodine has been shown as an optimum carrier agent, (44) which has also been successfully applied to CZTS single crystals. (45)

The crystal growth apparatus consists of a horizontal tubular furnace (Elite Thermal Systems Ltd.) with four independently controlled zones within the furnace. The temperature components were chosen after calibration with a thermocouple drawn along inside of the furnace, such that the desired gradient was obtained across the length of the ampule (further details can be found in ref 45).

Tin (>99% powder, Aldrich) and stoichiometric amounts of sulfur (>99.999% pieces, Puratronic, hand crushed with an agate pestle and mortar) were placed in silica ampules that are 15 cm in length and 2 cm in diameter. Iodine (99.999% pieces, Aldrich) was placed in the same ampule, in quantities corresponding to the 5 mg cm^–3 as recommended by Nitsche et al. to deliver the solid more slowly than the rate of crystal growth. (44) This ampule was then evacuated under the effect of liquid nitrogen in order to prevent the I₂ from evaporating under vacuum. Prior to ampule evacuation, all components were exposed to air and the associated content thereof, which represents a potential source of impurities, for example, oxidation or the inclusion of moisture. A schematic representation of the experimental system, and the chemical processes that this induces, is shown in Figure 2.

Composition and Structural Characterization

The crystal structure for each of the phases was confirmed with X-ray Diffraction (XRD). Single-crystal XRD was performed on a Xcalibur, Atlas, Geminiultra X-ray diffractometer, for a Cu Kα radiation source. Powder-diffraction measurements were performed on a Bruker D8-Advance machine for a Cu Kα radiation source.

To assess the stoichiometries and morphology, a low-vacuum, high-performance JEOL-JSM-6610LV scanning electron microscope (SEM) fitted with an Oxford Instruments X-Max 800 mm energy-dispersive spectrometer (EDS) was used for multiple point-scans of the single crystals. The crystals were unpolished and unsputtered, but were washed with chloroform to remove any residual iodine from the CVT method.

Figure 2. Schematic of the CVT process, with red showing higher and blue showing cooler temperatures. The crystals are in yellow and the solid components black. Tin migrates as tin iodide toward the cooler end of the ampule, where Sn–S stoichiometries form and release the iodine. I₂ diffuses back toward the tin to create a cycle.

Time-Resolved Microwave Conductivity

In pulse-radiolysis time-resolved microwave conductivity experiments (PR-TRMC), charges are generated in the sample by irradiation with high-energy electrons. The SnS, SnS₂, and Sn₂S₃ samples consisted of micrometer-sized crystallites that were diluted approximately ten times by mixing them with polymethylmethacrylate (PMMA) powder. To measure the conductivity, we inserted the sample into a microwave conductivity cell with the dimensions of a rectangular K_a band microwave waveguide. The Sn_xS_y samples were irradiated with nanosecond electron pulses of 3 MeV. The incident high-energy electrons undergo scattering within the sample and transfer energy by inducing ionisations. In this way a close to uniform distribution of positive charges (holes) and (secondary, ternary etc.) electrons is produced. The penetration depth of 3 MeV electrons is approximately 1.5 cm, which exceeds the thickness of the microwave cavity (0.5 cm), hence, the incident 3 MeV electrons pass through the sample and charging does not occur. After the nanosecond electron pulse, the change in conductivity of the sample is probed as a function of time by monitoring the attenuation of reflected microwave power (frequency range between 28 and 38 GHz, maximum electric field strength in the sample 10 V/m). The fractional change in microwave power reflected by the cell (ΔP/P) is directly proportional to the change in conductivity, Δ σ by

(1)in which A is the sensitivity factor, n is the concentration of charges, and μ their mobility. The initial value of n, can be deduced using dosimetry measurements combined with an approximation of the average energy required to generate one electron–hole pair. Knowledge of n allows quantification of μ. A more detailed description of the PR-TRMC method can be found elsewhere. (46, 47)

Computational Methods

The bulk phases of SnS, SnS₂, and Sn₂S₃ were simulated using Kohn–Sham DFT (48, 49) within the plane-wave project-augmented wave formalism as implemented in the Vienna ab initio simulation package (VASP). (50, 51) Electron exchange and correlation were described with the semilocal generalized gradient approximation (GGA) within the functional of Perdew, Burke and Ernzerhof optimized for solids (PBEsol). (52) The shallow core 4d states of Sn were explicitly treated as valence electrons. A plane-wave basis set (400 eV kinetic energy cutoff) was employed with well converged k-point sampling. To provide a quantitative prediction of the band gaps, hybrid-DFT was employed, incorporating 25% screened Hartree–Fock exchange to produce the HSE06 functional. (53)

All calculations were performed in closed-shell configurations (restricted spin), with geometry relaxations undertaken using the Broyden–Fletcher–Goldfarb–Shanno algorithm and a force convergence criterion tolerance in all cases of at least 0.01 eV/Å. (54) The equilibrium crystal structures and thermochemical data at this level of theory have previously been reported with good agreement with available experiment. (27)

The formation enthalpy of intrinsic point defects, tin and sulfur vacancies, was calculated using the supercell approach within the FHI-AIMS package, (55) and a previously reported method. (27) Lattice expansions of (2 × 4 × 4), (4 × 4 × 2), and (2 × 4 × 1) were used for SnS, SnS₂, and Sn₂S₃ respectively. k-point sampling of at least 2 × 2 × 2 was performed, consistent with the lengths of the reciprocal lattice vectors. The defect formation energies were calculated with respect to the elemental standard states (Sn metal and solid S₈).

Results

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Thermodynamics of Sn–I Transport

To guide the synthesis of the Sn–S phases by iodide vapor transport and help understand the underlying growth processes, a thermodynamic model of the relevant reactions was calculated. The stability region for each compound was found by minimizing the sum of the chemical potentials of the possible species on each side of the chemical equations as a function of the temperature, as taken from the database of Knacke et al. (56) We refer to previous work for detailed derivation of the equilibrium temperature ranges of stability for the species involved (e.g., iodine in the form of either atomic I or I₂). (57) The following reactions are assumed to be taking place (x, y, w ∈

; 1 ≤ x ≤ 2; 1 ≤ y ≤ 8; 0 ≤ w ≤ 1):

•	SnS(s) + (4/x – 2(1 – w)/x) I_x(g) + 1/y S_y(g) → SnI_2(w+1)(g) + 2/yS_y(g)
•	SnS₂(s) + 24/xI_x(g) → 6SnI_2(w+1)(g) + 12/yS_y(g) + 6(2 + 2w)/xI_x(g)
•	3Sn₂S₃(s) + 24/xI_x(g) + 3/yS_y(g) → 6SnI_2(w+1)(g) + 12/yS_y(g) + 6(2 + 2w)/xI_x(g)

The Gibbs free energies of reaction as a function of the temperature are shown for each process in Figure 3.

Assuming thermodynamic equilibrium among the species in reactions 1–3 above, we can conclude that the equilibria involved in the transport of SnS, Sn₂S₃, and SnS₂ via tin iodide vapor are remarkably different. Therefore we foresee no thermodynamic hindrance to the effective separation of the crystallized phases given careful synthetic control.

Figure 3. Standard Gibbs free energies of the reactions involved in the tin iodide formation for the vapor transport of SnS, Sn₂S₃, and SnS₂ as a function of the temperature.

Single-Crystal Growth

The CVT conditions required to synthesize SnS, SnS₂, and Sn₂S₃ are listed in Table 1, corresponding to the stoichiometric amounts of solid reagents.

The reaction conditions agree well with the work of others, (35, 44) but have the intriguing implication that in order to obtain phase pure SnS, rapid cooling may be necessary to escape the temperature window needed to synthesize Sn₂S₃ and/or SnS₂. Indeed rapid quenching of SnS below 650 °C was a practice observed by Lambros et al. in their isolation of “almost perfect” crystals. (58)

In our case, it was found that during the experiment for the synthesis of SnS₂, i.e., with highest sulfur load, both SnS₂ yellow flakes and Sn₂S₃ black needles were both obtained but were spatially separated within the ampule, with Sn₂S₃ being closer to the hotter side of the vessel compared to SnS₂. These findings are noteworthy because they agree with the thermochemical model derived in the previous section. The Gibbs free energy curves for the formation of tin iodide vapor from Sn₂S₃ and SnS₂ in Figure 3 show that the stability of SnS₂ against iodide formation is lower in the higher temperature side of the gradient applied, which is why this phase is expected to crystallize closer to the cold side of the reaction vessel. Conversely, the opposite argument can be applied for Sn₂S₃.

Stoichiometry and Structure Identification

The crystal structures of each material were confirmed using XRD. For Sn₂S₃ and SnS₂ single-crystal diffraction was possible, which confirmed the ground-state Pnma structure of Sn₂S₃ with structural parameters in agreement with previous reports. (59) For SnS₂ an extended R3̅ polytype was identified, which is closely related to the known ground state P3̅m1 phase but with an AAB layer stacking. (60) The ill-defined morphology of bulk SnS, resulting from the rapid cooling process from above its melting temperature, was not conducive to single-crystal diffraction; however, powder diffraction of a ground sample resulted in the expected Pnma phase. (61) To provide further evidence of the phase identities, we performed EDS analysis on our samples with results that are in agreement with the structural assignment (Table 2).

From XRD and EDS analysis, the phase assignment of the three materials is clear, with dark gray SnS, black needles of Sn₂S₃, and yellow flakes of SnS₂. However, this assignment is in contradiction to previous studies. Nitsche et al. reported their black needlelike crystals as SnS when following the same procedure we isolated Sn₂S₃. (44) Price et al. described yellow plates of Sn₂S₃ and black needles of SnS₂, the opposite of what we observe here. (62) Many more report on the tunability of SnS properties with different Sn:S ratio, when our results indicate that this is more likely to be a mechanical mixture of obtained phases rather than a homogeneous transition. (63, 64)

Transport Properties

As previously discussed SnS is a natural p-type material with hole mediated transport. Reported conductivities range from 10^–5 to 0.07 Ω ^–1 cm^–1, (65, 66) carrier concentrations from 10¹⁵ to 10¹⁸ cm^–3, and hole mobilities from 4 to 139 cm² V^–1 s^–1. (65, 67-69)

SnS₂ is an intrinsic n-type material. Reported conductivities range from 10^–7 to 0.90 Ω ^–1 cm^–1, (67, 70) carrier concentrations from 10¹³ to 10¹⁷ cm^–3, and electron mobilities from 15 to 52 cm² V^–1 s^–1. (67, 71)

Table 1. Reaction Conditions Used to Synthesize the Phases of Tin Sulfide Using CVT^a

phase	temperature gradient (°C)	mass of tin (g)	mass of sulfur (g)	time (days)
SnS	850–950	1.579	0.427	10
SnS₂	600–850	1.691	0.897	12
Sn₂S₃	500–650	1.781	0.723	10

In all reactions, approximately 250 mg of iodine was used as a carrier agent.

Table 2. Elemental Composition of Single Crystals Obtained As Atomic Percent Using Energy-Dispersive Spectroscopy and Their Macroscopic Appearance

Sn₂S₃ has also been reported as an intrinsic n-type material with conductivities ranging from 10^–5 to 10^–3 Ω ^–1, (29, 30) carrier concentrations around 10¹⁵ cm^–3, (30) with no information available for charge carrier mobilities. (67)

All of these factors, listed in Table 3, will be crucial for optimization of the device applications of tin sulfide.

Microwave Conductivity

For photovoltaic applications, the charge carrier drift length is an important parameter, the value of which is given by the square root of the product of the lifetime of the light-induced charge carriers (τ) and their mobility (μ). To obtain these values for the tin sulfides, we performed pulse-radiolysis time-resolved microwave conductivity measurements.

Formation of mobile charges induces a rise in the electrical conductivity, which results in increased microwave absorption. The reduced amount of microwave power is detected on a nanosecond time scale as shown for SnS₂ and Sn₂S₃ in Figure 4. For SnS, the high dark conductivity of our crystals, i.e., the conductivity in absence of a pulse, does not allow microwave measurements using this setup.

During the pulse, the signal rapidly increases because of the formation of mobile charge carriers (Fgure 4). The maximum signal size can be converted into a mobility using eq 1 as given in the experimental section, yielding for both materials a value of the order of 150 cm² V^–1 s^–1. These are comparable to the highest values reported in the literature for these materials. Directly after the pulse, a fast decay is observable for both semiconductors; however, the decays are very different. The decay can be explained by the immobilization of charge carriers due to, for example, electron trapping. Alternatively recombination of charge carriers also leads to a reduction in signal size. For Sn₂S₃, the signal decays to almost zero within a period of less than 50 ns. In contrast, the decay for SnS₂ is far slower and extends into the microsecond time scale.

Figure 4. Normalized pulse radiolysis TRMC traces recorded for SnS₂ and Sn₂S₃ using a pulsed 3 MeV electron beam.

Table 3. Reported Electron Transport Properties for the Tin Sulfides, Collected from Various Sources

phase	conductivity (Ω^–1 cm^–1)	carrier concentration (cm^–3)	mobilities (cm² V^–1 s^–1)
SnS	0.077, (72) 0.069, (65) 0.05, (63) 0.033, (68) 0.030, (69) 6 × 10^–5, 5.3 × 10^–5, (66) 4 × 10^–5^, (73)	1–3 × 10¹⁸, (15) 1.16 × 10¹⁷, (65) 1 × 10¹⁷, (74) 1.5 × 10¹⁶, (24) 1.2 × 10¹⁵, (72) 1 × 10¹⁵^, (68, 69)	400–500, (72) 385, (74) 139, (69) 130, (68) 90, (15, 67) 15.3, (24) 3.73 (65)
SnS₂	0.90, (67) 1.3 × 10^–2, (29) 2.4 × 10^–5, (71) 3.9 × 10^–7^, (70)	2 × 10¹⁷, (67) 1 × 10¹³^, (71)	51.5, (67) 15 (71)
Sn₂S₃	4.4 × 10^–3, (30) 2.5 × 10^–5^, (29)	9.42 × 10¹⁴^, (30)	“little information available” (67)

Figure 5. Dose-normalized change in conductivity for SnS₂ and Sn₂S₃. The x-axis shows time in nanoseconds and the y-axis shows the fractional change in microwave power reflected by the cell divided by the integrated beam charge per pulse (Q) in nano-Coulombs.

The origin of the decay can be studied in more detail by changing the dose of the electron beam and comparing the dose normalized TRMC traces as shown in Figure 5. For SnS₂, the signal decreases more rapidly as the dose increases. This is a clear sign of charge-carrier recombination according to second-order electron–hole kinetics. For Sn₂S₃, the decay is independent of the dose, indicating that trapping or recombination is a first-order process.

At the lowest pulse of 2 ns, for SnS₂, lifetime (τ_1/2) is 50 ns and mobility (μ) is around 150 V^–1 s^–1, giving a mobility lifetime product of 7.5 × 10^–6 cm² V^–1. For Sn₂S₃, τ_1/2 ≈ 5 ns and mobility is around 150 V^–1 s^–1, giving a mobility lifetime product 7.5 × 10^–7 cm² V^–1. These values are somewhat lower than those found for other materials, e.g., 7 ×10^–5 cm² V^–1 for CdTe. (75)

The signal for SnS₂ did decay to zero after a very long time (as shown in the Supporting Information). The long lifetimes can be attributed to the fact that the mobilities in different directions of the lattice vary by 4 orders of magnitude. (76) This large anisotropy in mobility is attributed to the two-dimensional sheet like structures of the lattice in SnS₂ crystals. Interaction of the high energetic electrons of the accelerator pulse with the material induces the formation of charges over different sheets. Because the charge transport perpendicular to the sheets is slow, recombination of opposite charges is retarded.

The Einstein–Smoluchowski relation relates charge diffusion coefficient D to

(2)where μ is mobility, k_B is the Boltzmann constant, T is temperature, and q is the electrical charge. Using the measured values of 150 cm² V^–1 s^–1 and 298 K for T, the charge diffusion coefficient is found to be 3.85 cm² s^–1 for both samples.

For SnS, an important conclusion can be made from the absence of TRMC data. The promotion of electrons into higher energy states, necessary for the TRMC method, is also responsible for the splitting of the quasi Fermi levels, which dictates the open-circuit voltage in photovoltaic devices. (77) The background conductivity is a potential contributor to the poor V_oc observed to date. (17) As such, SnS devices might benefit from reducing the intrinsic conductivity through control of the growth conditions or extrinsic doping, as demonstrated with Sb recently. (25)

Defect Theory

To understand the microscopic origin of the conductivity in these undoped materials, we computed the energies associated with plausible defect reactions for each material at the DFT level of electronic structure methods. Defect concentrations were calculated following the law of mass action, under the assumption of thermal equilibrium at the growth temperature. (78) In SnS (SnS₂), a fully ionized tin vacancy would generate two (four) positive charge carriers (i.e., holes) and one sulfur vacancy would generate two negative charge carriers (i.e., electrons). These are expected to be the dominant native point defects.

As shown in Table 4, we corroborate the dependency of conductivity on defect stabilities and by extension predict typical charge carrier concentrations for each phase. The Sn vacancy has the lowest formation energy and highest concentration in SnS, which is consistent with that being the dominant acceptor defect. The S vacancy (in SnS) was thought to potentially act as an electron trap, but it has been shown that the sulfur vacancies themselves do not compensate for the p-type contribution of tin vacancies (due to defect levels deep in the band gap). (23)

For SnS₂, the S vacancy dominates, which is consistent with its observed n-type behavior from charge balancing considerations . For Sn₂S₃, our results agree with observed behavior and go further to elucidate the intermediate behavior of Sn₂S₃, as a species containing both Sn(II) and Sn(IV) oxidation states. For SnS and SnS₂ the dominance of tin and sulfur vacancies, respectively, is unambiguous, which manifests as the observed longer carrier lifetimes and a second-order decay behavior for SnS₂. In Sn₂S₃, the formation energies of the two vacancy defects are very close in energy, which indicates that carrier concentrations should be sensitive to the growth or annealing conditions, and furthermore, the major carrier type might be subject to change. This prediction also explains the rapid recombination behavior shown in the previous section: the high concentration of donor sites can effectively compensate the n-type carriers and vice versa.

Electronic Structure

Because thin-film SnS samples typically show lower levels of conductivity than our crystals, we further explore the possibility that other phases could be present in “tin monosulfide” samples and films, corroborated by the persistent observation of “brown” films in literature and the wide variety of properties observed (see Tables 3 and 6). (79, 80) Besides this, the fact that tin monosulfide and sesquisulfide have the same space group and similar XRD diffraction patterns means it is possible that the disappointing performance of SnS is due to an intrinsic alloy or mechanical mixture with Sn₂S₃. As mentioned in the introduction, it has been suggested that sulfur-rich conditions would be needed to avoid this occurrence, but such conditions alone were not sufficient to prevent off-stoichiometric phases of FeS₂ forming; another material that has so far failed to deliver as a PV absorber layer. (81)

The physical appearance of the single crystals suggests band gaps close to the IR region of the spectrum for SnS and Sn₂S₃ and a larger gap closer to the UV region for SnS₂ (i.e., yellow). Previous experimental measurements of the band gaps for each material are collected in Table 6. The values are wide-ranging: 1.08–1.70 eV for SnS, 1.82–2.41 eV for SnS₂, and 0.95–2.20 eV for Sn₂S₃. In addition to the form of materials, variation can also be attributed to fitting process, where the optical absorption spectrum is subject to a linear fit according to an idealized parabolic band dispersion. Of note are the number of fits to dipole forbidden transitions for fundamental band gaps. Formally, these can occur only in centrosymmetric structures, (82) which does not correspond to any of the common tin sulfide phases. The results of our band structure calculations are included in Table 5. These are calculated at the experimental lattice constants to avoid any errors from the underlying structure.

Table 4. Point Defect Formation Energies and Concentrations Calculated under Sulfur-Rich Conditions (Atomic Exchange with a Resevoir of α-S) for the Neutral Defects at the Respective Synthesis Temperatures^a

phase	space group	species	defect energy (eV)	concentration (cm^–3)	type
SnS	Pnma	V_Sn	0.68	2.28 × 10¹⁹	acceptor
	Pnma	V_S	2.17	6.57 × 10¹²
SnS₂	P3̅m1	V_Sn	3.16	2.54 × 10⁰⁴
	P3̅m1	V_S	1.80	2.21 × 10¹²	donor
Sn₂S₃	Pnma	V_Sn(1)	1.17	7.08 × 10¹⁴	acceptor
	Pnma	V_Sn(2)	2.68	2.04 × 10⁰⁵
	Pnma	V_S(1)	1.67	7.72 × 10¹¹
	Pnma	V_S(2)	1.38	5.13 × 10¹³	donor
	Pnma	V_S(3)	1.77	1.63 × 10¹¹

Multiple inequivalent sites for defect formation are distinguished with numerical subscripts. The dominant defects are indicated by their type.

Table 5. Calculated Fundamental Band Gaps of the Tin Sulfides Using the HSE06 Technique

phase	E_g (eV)
SnS	1.11 (indirect)
SnS₂	2.24 (indirect)
Sn₂S₃	1.09 (indirect)

Recent papers have reported calculated band gaps of SnS using G₀W₀ many-body perturbation theory based on local density approximation (LDA) structures or wave functions. (23, 83) Our result of 1.11 eV would correspond to a room temperature band gap of 0.98 eV following the method outlined by Malone et al. (58, 83) This value agrees well with the experimental observations of Zainal et al. (84)

The calculated valence band maxima, conduction band minima and vacuum potentials allow us construct a natural band offset diagram for each of the tin sulfide phases, which is shown in Figure 6. The procedure is detailed in ref 19, where electrostatic alignment is performed using the nonpolar (100) surface of SnS, a reconstructed (001) surface of Sn₂S₃, and a reconstructed (001) surface of SnS₂.

Figure 6. Calculated band offset diagram, using the HSE06 functional, for each of the three tin sulfide phases using a vacuum alignment procedure and that of CZTS for reference. (92)

The lowest ionization potential is found for SnS (Figure 6), with a monotonic increase from Sn₂S₃ to SnS₂. Similarly, the electron affinity increases from 3.59 eV for SnS, to 4.24 eV for SnS₂, and 5.02 eV for Sn₂S₃. The calculations predict that the SnS/Sn₂S₃ and Sn₂S₃/SnS₂ interfaces would form p–n junctions of Type II nature, driving the separation of electrons and holes. However, the alignment between SnS and SnS₂ is of Type IIb, i.e., spontaneous electron and hole transfer would occur toward SnS. (93) With respect to SnS solar cells, a dispersion of these secondary phases (reported by multiple authors) (42, 62, 94-96) could decrease the open circuit voltage by mitigating the desired rectifying behavior across the cell. This could explain the limiting properties seen in devices as small-scale secondary phases and point defects have shown to be of macroscopic importance for Cu₂ZnSnS₄ (CZTS) cells. (97) Also of importance is the relatively low ionization potential of SnS compared to other photo absorbers (e.g., CZTS), which suggests that commonly used contacts such as molybdenum might not allow the effective separation of charges necessary for PV performance. The importance of appropriate contacts for SnS based solar cells has recently been highlighted. (19)

Table 6. Reported Optical Band Gaps of the Tin Sulfides from Thin-Film and Single Crystal Samples^a

phase	reported optical E_g (eV)
SnS	0.9 −1.1 (indirect); (84) 1.08 (indirect); (15) 1.27 (allowed indirect); (85) 1.32 (direct), (65, 69) 1.43 (direct); (41) 1.70 (direct); (34, 66) 1.79 (direct) (86)
SnS₂	1.82 (forbidden indirect); (70) 2.07 (indirect); (87) 2.2 (forbidden indirect); (29) 2.41 (no further details) (88)
Sn₂S₃	0.95 eV (forbidden direct); (89) 1.05 (forbidden direct); (29) 1.16 (forbidden direct); (90) 1.6–1.9 (79) 2 (direct); (30) 2.2 (indirect) (91)

The type of band gap used in the fitting process is shown in parentheses.

Discussion and Conclusions

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Detailed examination of the tin sulfides has shown that the intrinsic material properties of the individual phases do not pose any insurmountable obstacles to the realization of their potential in respective photovoltaic or photochemical applications. Our characterization leads to the conclusion that the three stoichiometries of tin sulfide have been isolated and the identification of suitable methods allows for bulk production of phase-pure crystals.

Results obtained for SnS could provide an explanation as to the absence of high-efficiency PV devices with SnS as an absorber layer. Usually, the reported short circuit current is acceptable, yet the open circuit voltage is low. Indeed, due to a high background conductivity, the splitting of the quasi Fermi level will be difficult under illumination, and this will contribute to a low V_oc (typically lower than 200 mV). Careful control of the Sn:S stoichiometry is required to ensure that the concentration of Sn vacancies is sufficiently low; however, experimentally a low Sn content could also correspond to the formation of the alternative S-rich phases.

Our results for SnS₂ confirm that this material could be a good n-type buffer layer in thin-film solar cells, and could be quite thick, as the drift length of the electron carriers is sufficiently long. However, SnS₂ would form a metallic type IIb heterojunction with SnS that would be detrimental to a SnS/SnS₂ photovoltaic device as no depletion layer would form, although this may be overcome by tuning the morphology (e.g., dipoles) at the interface.

Finally, for Sn₂S₃, we confirm that it does not suffer from the same behavior as SnS (i.e., no large density of carriers in the dark), yet its carrier mobility is high (larger than amorphous silicon for example), (98) and its band gap is also attractive, more so than, for example, FeS₂. (99) The nature of Sn₂S₃ means that its presence in SnS films would inhibit transport physics, as a Type II junction would form between the two; similarly, any SnS present in an Sn₂S₃ sample would act as a hole trap and also limit performance. Because of the similarity in structural and vibrational (Raman/IR) properties of the various phases of tin sulfide, in order to assign the presence of Sn(II) and Sn(IV) in thin-film samples, characterization tools such as XPS and EXAFS could play an important role in the future.

In conclusion, we have synthesized single crystals of SnS, Sn₂S₃, and SnS₂ and investigated their electronic structure. The different semiconducting behavior of each phase can be explained from the underlying defect chemistry: p-type SnS (low energy Sn vacancies), n-type SnS₂ (low-energy S vacancies), and mixed-type Sn₂S₃ (accessible Sn and S vacancies). On the basis of analysis of the valence band alignments, we show that if phase pure samples are not obtained, and either of the other two known phases are present, then these would also be detrimental to transport properties and subsequently lower the photovoltaic device performance.

Supporting Information

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Full X-ray crystallographic data for the three phases discussed in this paper and additional TRMC results for SnS₂. This material is available free of charge via the Internet at http://pubs.acs.org/.

cm403046m_si_001.pdf (316.44 kb)

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Author Information

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Corresponding Author
- Aron Walsh - Centre for Sustainable Chemical Technologies, Department of Chemistry, University of Bath, Bath, United Kingdom; Email: [email protected]
Authors
- Lee A. Burton - Centre for Sustainable Chemical Technologies, Department of Chemistry, University of Bath, Bath, United Kingdom
- Diego Colombara - Laboratory for Energy Materials, Université du Luxembourg, 41, rue du Brill, L-4422 Belvaux, Luxembourg
- Ruben D. Abellon - Opto-Electronic Materials Section, Department of Chemical Engineering, Faculty of Applied Sciences, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands
- Ferdinand C. Grozema - Opto-Electronic Materials Section, Department of Chemical Engineering, Faculty of Applied Sciences, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands
- Laurence M. Peter - Centre for Sustainable Chemical Technologies, Department of Chemistry, University of Bath, Bath, United Kingdom
- Tom J. Savenije - Opto-Electronic Materials Section, Department of Chemical Engineering, Faculty of Applied Sciences, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands
- Gilles Dennler - Department Energy and the Environment, IMRA Europe SAS, 220 rue Albert Caquot, BP213, F-06904 Sophia Antipolis Cedex, France
Notes
The authors declare no competing financial interest.

Acknowledgment

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The authors thank C. R. Bowen, C. H. Hendon, and K. C. Molloy (Bath) for useful discussions; P. Jones for glass-blowing expertise; and C. Woodhall for XRD measurements. A.W. acknowledges support from the Royal Society University Research Fellowship scheme and L.A.B. is funded by the EPSRC (Grant number EP/G03768X/1, EP/J017361/1 and EP/I019693/1). D.C. and L.M.P. acknowledge EPSRC funding through the Supergen grant (Photovoltaic Materials for the 21st Century EP/F029624/1). Access to the HECToR supercomputer was facilitated through membership of the HPC Materials Chemistry Consortium, which is funded by EPSRC (Grant EP/F067496). Images of chemical structure were made using VESTA software. (100)

References

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This article references 100 other publications.

1
Wadia, C.; Alivisatos, A. P.; Kammen, D. M. Energy Environ. Sci. 2009, 43, 2072– 2077
Google Scholar
There is no corresponding record for this reference.
2
Peter, L. M. Philos. Trans. R. Soc. London, Ser. A 2011, 369, 1840– 1856
Google Scholar
2
Towards sustainable photovoltaics: the search for new materials
Peter, L. M.
Philosophical Transactions of the Royal Society, A: Mathematical, Physical & Engineering Sciences (2011), 369 (1942), 1840-1856CODEN: PTRMAD; ISSN:1364-503X. (Royal Society)
A review. The opportunities for photovoltaic (PV) solar energy conversion are reviewed in the context of projected world energy demands for the twenty-first century. Conventional single-crystal silicon solar cells are facing increasingly strong competition from thin-film solar cells based primarily on polycryst. absorber materials, such as cadmium telluride (CdTe) and copper indium gallium diselenide (CIGS). However, if PVs are to make a significant contribution to satisfy global energy requirements, issues of sustainability and cost will need to be addressed with increased urgency. There is a clear need to expand the range of materials and processes that is available for thin-film solar cell manuf., placing particular emphasis on low-energy processing and sustainable non-toxic raw materials. The potential of new materials is exemplified by copper zinc tin sulfide, which is emerging as a viable alternative to the more toxic CdTe and the more expensive CIGS absorber materials.
3
Scragg, J. J.; Dale, P. J.; Peter, L. M.; Zoppi, G.; Forbes, I. Physica Status Solidi (b) 2008, 245, 1772– 1778
Google Scholar
There is no corresponding record for this reference.
4
Chen, S.; Gong, X. G.; Walsh, A.; Wei, S. H. Appl. Phys. Lett. 2010, 96, 021902– 3
Google Scholar
4
Defect physics of the kesterite thin-film solar cell absorber Cu2ZnSnS4
Chen, Shiyou; Gong, X. G.; Walsh, Aron; Wei, Su-Huai
Applied Physics Letters (2010), 96 (2), 021902/1-021902/3CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)
Cu2ZnSnS4 is one of the most promising quaternary absorber materials for thin-film solar cells. Examn. of the thermodn. stability of this quaternary compd. reveals that the stable chem. potential region for the formation of stoichiometric compd. is small. Under these conditions, the dominant defect will be p-type CuZn antisite, which has an acceptor level deeper than the Cu vacancy. The dominant self-compensated defect pair in this quaternary compd. is [Cu-Zn+Zn+Cu]0, which gives various polytype structures of Cu2ZnSnS4. Probably to maximize the solar cell performance, growth of Cu2ZnSnS4 under Cu-poor/Zn-rich conditions will be optimal, if the pptn. of ZnS can be avoided by kinetic barriers. (c) 2010 American Institute of Physics.
5
Reddy, K. R.; Reddy, N. K.; Miles, R. Sol. Energy Mater. Sol. Cells 2006, 90, 3041– 3046
Google Scholar
There is no corresponding record for this reference.
6
Ferekides, C. S.; Balasubramanian, U.; Mamazza, R.; Viswanathan, V.; Zhao, H.; Morel, D. L. Sol. Energy 2004, 77, 823– 830
Google Scholar
6
CdTe thin film solar cells: device and technology issues
Ferekides, C. S.; Balasubramanian, U.; Mamazza, R.; Viswanathan, V.; Zhao, H.; Morel, D. L.
Solar Energy (2004), 77 (6), 823-830CODEN: SRENA4; ISSN:0038-092X. (Elsevier Ltd.)
A review of work on CdTe thin-film solar cells sponsored by the National Renewable Energy Lab. Thin film CdTe solar cells and modules are typically heterojunctions with CdS being the n-type partner, or window layer. The preferred configuration for CdTe solar cells is the superstrate structure. The cadmium chloride heat treatment, the back contact formation process, and the utilization of resistive buffer layers in tandem with a thin cadmium sulfide window layer, are important areas of research in thin film CdTe solar cells. Results for a vapor chloride heat treatment with high throughput characteristics, a dry back contact process, and a comparative study of resistive buffer layers and their effect on the performance of CdTe solar cells are presented.
7
Abou-Helal, M.; Boshta, M. J. Am. Sci. 2012, 8, 61– 63
Google Scholar
There is no corresponding record for this reference.
8
Reddy, K. R.; Reddy, P. P.; Datta, P.; Miles, R. Thin Solid Films 2002, 403–404, 116– 119
Google Scholar
There is no corresponding record for this reference.
9
Parenteau, M.; Carlone, C. Phys. Rev. B 1990, 41, 5227– 5234
Google Scholar
There is no corresponding record for this reference.
10
Anderson, J. S.; Morton, C. M. Proc. Russ. Soc. A 1945, 184, 873
Google Scholar
There is no corresponding record for this reference.
11
Shockley, W.; Queisser, H. J. J. Appl. Phys. 1961, 32, 510– 520
Google Scholar
11
Detailed balance limit of efficiency of p-n junction solar cells
Shockley, William; Queisser, Hans J.
Journal of Applied Physics (1961), 32 (), 510-19CODEN: JAPIAU; ISSN:0021-8979.
In order to find an upper theoretical limit for the efficiency of p-n junction solar energy converters, a limiting efficiency, called the detailed balance limit of efficiency, has been calcd. for an ideal case in which the only recombination mechanism of hole-electron pairs is radiative, as required by the principle of detailed balance. The efficiency is also calcd. for the case in which radiative recombination is only a fixed fraction fc of the total recombination, the rest being nonradiative. Efficiencies at the matched loads were calcd. with band gap and fc as parameters, the sun and cell being assumed to be black bodies with temps. of 6000°K. and 300°K., resp. The max. efficiency is 30% for an energy gap of 1.1 e.v. and fc = 1. Actual junctions do not obey the predicted current-voltage relation, and reasons for the difference and its relevance to efficiency are discussed.
12
Nair, M. T. S.; Nair, P. K. Semicond. Sci. Technol. 1991, 6, 132
Google Scholar
12
Simplified chemical deposition technique for good quality tin monosulfide thin films
Nair, M. T. S.; Nair, P. K.
Semiconductor Science and Technology (1991), 6 (2), 132-4CODEN: SSTEET; ISSN:0268-1242.
A chem. deposition technique, much simpler and more versatile than previously reported and capable of yielding good quality SnS films of thickness up to ≃1.2 μm under a choice of deposition conditions, is presented. The as-prepd. films are polycryst. with p-type dark cond. in the range 10-5-10-4 Ω-1cm-1 for the thicker (∼1 μm) films and showing a photocurrent to dark current ratio of 5-10 under 500 W m-2 tungsten halogen illumination. The optical transmittance and reflectance spectra and the photocurrent response curves of a series of SnS samples are explicitly presented to provide insight into possible applications of these films.
13
Prince, M. B. J. Appl. Phys. 1955, 26, 534– 540
Google Scholar
There is no corresponding record for this reference.
14
Loferski, J. J. J. Appl. Phys. 1956, 27, 777– 784
Google Scholar
14
Theoretical considerations governing the choice of the optimum semiconductor for photovoltaic solar energy conversion
Loferski, Joseph J.
Journal of Applied Physics (1956), 27 (), 777-84CODEN: JAPIAU; ISSN:0021-8979.
Diode reverse satn. current is computed from the published values of the semiconductor parameters of 3 intermetallic compounds, i.e., InP, GaAs, and CdTe, and it is shown that the efficiencies predicted for these materials are greater than those predicted for other materials which have been proposed, i.e., Si, CdS, Se, and AlSb.
15
Albers, W.; Haas, C.; J. Vink, H.; Wasscher, J. D. J. Appl. Phys. 1961, 32, 2220
Google Scholar
15
Investigations on SnS
Albers, W.; Haas, C.; Vink, H. J.; Wasscher, J. D.
Journal of Applied Physics (1961), 32 (), 2220-5CODEN: JAPIAU; ISSN:0021-8979.
The p, T, x diagram of the Sn-S system was detd., especially in the region of the compd. SnS. The pressure of S2 in equil. with SnS and a liquid phase was found to extend over several decades up to 25 mm. Hg at the "Sn-rich" side, whereas at the "S-rich" side the S2 pressures in equil. with solid SnS and a liquid phase lie between 25 mm. Hg and 100 mm. Hg. The existence region of solid SnS very probably lies entirely at the excess-sulfur side. The hole mobility in a plane perpendicular to the c axis, ≈90 cm.2/v. sec. at room temp., was proportional to T-2.2 for higher temps. The mobility in the direction of the c axis was about 1/5 as great. Reversible annealing effects were found for temps, above 200°C. which could be explained by assuming assocn. of neutral Sn vacancies. Absorption measurements showed that the edge absorption is due to indirect transitions. The bandgap was 1.08 e.v. at 300°K. and 1.115 e.v. at 77°K. Interband transitions in the valence band were also found. The effective charge of the atoms (e* = 0.7 c0) and the effective masses of the holes in the 3 principal crystal directions (ma* = mb* = 0.20 m0; mc* ≈ m0) were detd. from reflection measurements in the infrared. From these values and the value for the d. of states mass obtained by means of the Seebeck effect (md* ≥0.95 m0), the no. of equiv. max. of the valence band was at least 4.
16
Fthenakis, V. Renew. Sust. Energy Rev. 2009, 13, 2746– 2750
Google Scholar
16
Sustainability of photovoltaics: The case for thin-film solar cells
Fthenakis, Vasilis
Renewable & Sustainable Energy Reviews (2009), 13 (9), 2746-2750CODEN: RSERFH; ISSN:1364-0321. (Elsevier Ltd.)
To ensure photovoltaics become a major sustainable player in a competitive power-generation market, they must provide abundant, affordable electricity, with environmental impacts drastically lower than those from conventional power generation. The recent redn. in the cost of 2nd generation thin-film PV is remarkable, meeting the prodn. milestone of $1 per W in the fourth quarter of 2008. This achievement holds great promise for the future. However, the questions remaining are whether the expense of PV modules can be lowered further, and if there are resource- and environmental-impact constraints to growth. I examine the potential of thin-films in a prospective life-cycle anal., focusing on direct costs, resource availability, and environmental impacts. These three aspects are closely related; developing thinner solar cells and recycling spent modules will become increasingly important in resolving cost, resource, and environmental constraints to large scales of sustainable growth.
17
Sinsermsuksakul, P.; Hartman, K.; Kim, S. B.; Heo, J.; Sun, L.; Park, H. H.; Chakraborty, R.; Buonassisi, T.; Gordon, R. G. Appl. Phys. Lett. 2013, 102, 053901
Google Scholar
There is no corresponding record for this reference.
18
Reddy, N.; Reddy, K. T. R.Conference Record of the Twenty Sixth IEEE Photovoltaic Specialists Conference;
Anaheim, CA, Sept 29–Oct 3, 2007
IEEE: Piscataway, NJ, 1997.
Google Scholar
There is no corresponding record for this reference.
19
Burton, L. A.; Walsh, A. Appl. Phys. Lett. 2013, 102, 132111
Google Scholar
There is no corresponding record for this reference.
20
Scragg, J. J.; Watjen, J. T.; Edoff, M.; Ericson, T.; Kubart, T.; Platzer-Bjorkman, C. J. Am. Chem. Soc. 2012, 134, 19330– 19333
Google Scholar
There is no corresponding record for this reference.
21
Richard, A. P. Single Crystal Growth, Powder Synthesis and Characterization of Layered Chalcogenide Semiconductors. Ph.D. thesis, Oregon State University, Corvallis, OR, 2011.
Google Scholar
There is no corresponding record for this reference.
22
Reddy, K. R.; Reddy, P. P.; Miles, R.; Datta, P. Opt. Mater. 2001, 17, 295– 298
Google Scholar
There is no corresponding record for this reference.
23
Vidal, J.; Lany, S.; d’Avezac, M.; Zunger, A.; Zakutayev, A.; Francis, J.; Tate, J. Appl. Phys. Lett. 2012, 100, 032104
Google Scholar
23
Band-structure, optical properties, and defect physics of the photovoltaic semiconductor SnS
Vidal, Julien; Lany, Stephan; d'Avezac, Mayeul; Zunger, Alex; Zakutayev, Andriy; Francis, Jason; Tate, Janet
Applied Physics Letters (2012), 100 (3), 032104/1-032104/4CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)
SnS is a potential earth-abundant photovoltaic (PV) material. Employing both theory and expt. to assess the PV relevant properties of SnS, we clarify on whether SnS has an indirect or direct band gap and what is the minority carrier effective mass as a function of the film orientation. SnS has a 1.07 eV indirect band gap with an effective absorption onset located 0.4 eV higher. The effective mass of minority carrier ranges from 0.5 m0 perpendicular to the van der Waals layers to 0.2 m0 into the van der Waals layers. The pos. characteristics of SnS feature a desirable p-type carrier concn. due to the easy formation of acceptor-like intrinsic Sn vacancy defects. Potentially detrimental deep levels due to SnS antisite or S vacancy defects can be suppressed by suitable adjustment of the growth condition towards S-rich. (c) 2012 American Institute of Physics.
24
Sinsermsuksakul, P.; Heo, J.; Noh, W.; Hock, A. S.; Gordon, R. G. Adv. Energy Mater. 2011, 1116– 1125
Google Scholar
24
Atomic layer deposition of tin monosulfide thin films
Sinsermsuksakul, Prasert; Heo, Jaeyeong; Noh, Wontae; Hock, Adam S.; Gordon, Roy G.
Advanced Energy Materials (2011), 1 (6), 1116-1125CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
Thin film solar cells made from earth-abundant, non-toxic materials are needed to replace the current technol. that uses Cu(In,Ga)(S,Se)2 and CdTe, which contain scarce and toxic elements. One promising candidate absorber material is tin monosulfide (SnS). In this report, pure, stoichiometric, single-phase SnS films were obtained by at. layer deposition (ALD) using the reaction of bis(N,N'-diisopropylacetamidinato)tin(II) [Sn(MeC(N-iPr)2)2] and hydrogen sulfide (H2S) at low temps. (100 to 200 °C). The direct optical band gap of SnS is around 1.3 eV and strong optical absorption (α > 104 cm-1) is obsd. throughout the visible and near-IR spectral regions. The films are p-type semiconductors with carrier concn. on the order of 1016 cm-3 and hole mobility 0.82-15.3 cm2V-1s-1 in the plane of the films. The elec. properties are anisotropic, with three times higher mobility in the direction through the film, compared to the in-plane direction.
25
Sinsermsuksakul, P.; Chakraborty, R.; Kim, S. B.; Heald, S. M.; Buonassisi, T.; Gordon, R. G. Chem. Mater. 2012, 24, 4556
Google Scholar
There is no corresponding record for this reference.
26
Walsh, A.; Woodley, S. M.Phys. Chem. Chem. Phys. 2010, 12.
Google Scholar
There is no corresponding record for this reference.
27
Burton, L. A.; Walsh, A. J. Phys. Chem. C 2012, 116, 24262– 24267
Google Scholar
There is no corresponding record for this reference.
28
P. Boudjouk, S. R. B.; Seidler, D. J.; McCarthey, G. J. Chem. Mater. 1994, 6, 2108
Google Scholar
There is no corresponding record for this reference.
29
Sanchez-Juarez, A.; Ortiz, A. Semicond. Sci. Technol. 2002, 17, 931
Google Scholar
29
Effects of precursor concentration on the optical and electrical properties of SnxSy thin films prepared by plasma-enhanced chemical vapor deposition
Sanchez-Juarez, A.; Ortiz, A.
Semiconductor Science and Technology (2002), 17 (9), 931-937CODEN: SSTEET; ISSN:0268-1242. (Institute of Physics Publishing)
The authors have carried out the elec. and optical characterization of thin films of compds. based on Sn-S bonds (SnS2, Sn2S3), prepd. by plasma-enhanced CVD (PECVD), as a function of the relative concn. of the precursor vapors, SnCl4 and H2S, keeping all other deposition parameters const. In all studied cases, the deposited films were formed by polycryst. materials. The optical bandgap values of deposited materials were calcd. from optical transmittance and reflectance measurements. The SnS2 compd. produced under certain deposition conditions has a forbidden bandgap around 2.2 eV. This compd. shows n-type elec. cond., whose dark value at room temp. is 2 × 10-2 (Ω cm)-1. Also, it shows the typical semiconductor dependence of its elec. cond. on the temp. with an activation energy of ∼0.15 eV. However, thin films of a mixt. of SnS2 and Sn2S3 compds. were deposited with higher values of the relative concn. of source vapors than those used to obtain the SnS2 compd. The optical bandgap shows a decreasing trend as the relative concn. increases. A similar trend is obsd. for dark elec. cond. These results create the opportunity to use SnxSy compds. in thin films for building heterojunction solar cells prepd. completely by PECVD.
30
Khadraoui, M.; Benramdane, N.; Mathieu, C.; Bouzidi, A.; Miloua, R.; Kebbab, Z.; Sahraoui, K.; Desfeux, R. Solid State Commun. 2010, 150, 297– 300
Google Scholar
There is no corresponding record for this reference.
31
Nassary, M. J. Alloys Compd. 2005, 398, 21– 25
Google Scholar
31
Temperature dependence of the electrical conductivity, Hall effect and thermoelectric power of SnS single crystals
Nassary, M. M.
Journal of Alloys and Compounds (2005), 398 (1-2), 21-25CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)
The elec. cond. and the Hall effect were measured on a SnS single crystal, grown by the Bridgman method over the temp. range 141-523 K, in two crystallog. directions. The investigated sample was found to be of p-type cond. The cond. at room temp. was σ// = 0.193 Ω-1 cm-1, σ.perp. = 0.063 Ω-1 cm-1 parallel and perpendicular to layers plane, resp. The energy gap was calcd. to be Eg// = 1.106 eV and Eg.perp. = 0.56 eV parallel and perpendicular to layers plane, resp. The thermoelec. power measurements of SnS were made in temp. range from 172 to 410 K. The combination of the elec. and thermal measurements makes it possible to deduce a lot of phys. parameters, such as mobilities ratio, effective masses, relaxation times, diffusion lengths and diffusion coeffs. for majority and minority carriers at room temp.
32
Huang, C.-C.; Lin, Y.-J.; Chuang, C.-Y.; Liu, C.-J.; Yang, Y.-W. J. Alloys Compd. 2013, 553, 208– 211
Google Scholar
32
Conduction-type control of SnSx films prepared by the sol-gel method for different sulfur contents
Huang, Chung-Cheng; Lin, Yow-Jon; Chuang, Cheng-Yu; Liu, Chia-Jyi; Yang, Yao-Wei
Journal of Alloys and Compounds (2013), 553 (), 208-211CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)
The effect of S content on the elec. property of the sol-gel SnSx films was examd. The obsd. conduction-type changes are related to the different ratios between the concns. of Sn4+ and Sn2+. The exptl. identification confirms that n-type conversion is due to an increase in the at. concn. ratio of Sn4+/(Sn4+ + Sn2+) in the S-rich film. The probability of having formed Sn vacancies (VSn) should be high under S-rich growth conditions. Transformation from VSn to V2-Sn is accompanied by lattice relaxation. Therefore, transformation from Sn2+ to Sn4+ is an offset to lattice relaxation under S-rich growth conditions, increasing the electron d. and producing n-type conversion. A suitable sulfur concn. is an important issue for tuning conduction type of SnSx.
33
Sanchez-Juarez, A.; Tiburcio-Silver, A.; Ortiz, A. Thin Solid Films 2005, 480?481, 452– 456
Google Scholar
There is no corresponding record for this reference.
34
Ogah, O. E.; Zoppi, G.; Forbes, I.; Miles, R. Thin Solid Films 2009, 517, 2485– 2488
Google Scholar
There is no corresponding record for this reference.
35
Cruz, M.; Morales, J.; Espinos, J. P.; Sanz, J. J. Solid State Chem. 2003, 175, 359– 365
Google Scholar
35
XRD, XPS and 119Sn NMR study of tin sulfides obtained by using chemical vapor transport methods
Cruz, M.; Morales, J.; Espinos, J. P.; Sanz, J.
Journal of Solid State Chemistry (2003), 175 (2), 359-365CODEN: JSSCBI; ISSN:0022-4596. (Elsevier Science)
Application of the chem. vapor transport method to the Sn-S system allowed three different phases (viz. SnS, SnS2 and Sn2S3) to be synthesized. No evidence of the formation of other, previously reported mixed valence compds. such as Sn3S4 or Sn4S5 was found, whichever the Sn:S at. ratio and temp. gradient used. Except for SnS2, which was always obtained as a pure phase as a result of starting from the required stoichiometry, a mixed phase was invariably obtained. The XPS spectrum for Sn2S3 was only slightly different from those for SnS and SnS2 in spite of the presence of Sn(II) and Sn(IV) in the former compd., which hindered the identification of mixed valence compds. in the Sn-S system using this spectroscopic technique. By contrast, the chem. shifts, anisotropy and skew parameters for Sn2S3 as obtained by 119Sn NMR were markedly different from those for SnS and SnS2, and reflected the severe distortion of Sn(IV) and, esp., Sn(II) in the former compd. relative to the latter two. The time scale for this resonance technique is shorter than the lifetime of the valence states, which allows one to unambiguously distinguish the two oxidn. states of Sn.
36
Kana, A. T.; Hibbert, T. G.; Mahon, M. F.; Molloy, K. C.; Parkin, I. P.; Price, L. S. Polyhedron 2001, 20, 2989– 2995
Google Scholar
There is no corresponding record for this reference.
37
Nair, P. K.; Nair, M. T. S.; Garcia, V. M.; Arenas, O. L.; Pena, Y.; Castillo, A.; Ayala, I. T.; Gomezdaza, O.; Sanchez, A.; Campos, J.; Hu, H.; Suarez, R.; Rincon, M. E. Sol. Energy Mater. Sol. Cells 1998, 52, 313– 344
Google Scholar
37
Semiconductor thin films by chemical bath deposition for solar energy related applications
Nair, P. K.; Nair, M. T. S.; Garcia, V. M.; Arenas, O. L.; Pena, Y.; Castillo, A.; Ayala, I. T.; Gomezdaza, O.; Sanchez, A.; Campos, J.; Hu, H.; Suarez, R.; Rincon, M. E.
Solar Energy Materials and Solar Cells (1998), 52 (3-4), 313-344CODEN: SEMCEQ; ISSN:0927-0248. (Elsevier Science B.V.)
A review with 84 refs. In this paper we present the basic concepts underlying the chem. bath deposition technique and the recipes developed in our lab. during the past ten years for the deposition of good-quality thin films of CdS, CdSe, ZnS, ZnSe, PbS, SnS, Bi2S3, Bi2Se3, Sb2S3, CuS, CuSe, etc. Typical growth curves, and optical and elec. properties of these films are presented. The effect of annealing the films in air on their structure and compn. and on the elec. properties is notable: CdS and ZnS films become conductive through a partial conversion to oxide phase; CdSe becomes photosensitive, SnS converts to SnO2, etc. The use of ppts. formed during deposition for screen printing and sintering, in polymer composites and as a source for vapor-phase deposition is presented. Some examples of the application of the films in solar energy related work are presented.
38
Ghazali, A.; Zainal, Z.; Hussein, M. Z.; Kassim, A. Sol. Energy Mater. Sol. Cells 1998, 55, 237– 249
Google Scholar
38
Cathodic electrodeposition of SnS in the presence of EDTA in aqueous media
Ghazali, Arniza; Zainal, Zulkarnain; Zobir Hussein, Mohd; Kassim, Anuar
Solar Energy Materials and Solar Cells (1998), 55 (3), 237-249CODEN: SEMCEQ; ISSN:0927-0248. (Elsevier Science B.V.)
Cathodic electrodeposition in the presence of EDTA in aq. soln. was found to offer some noteworthy improvements in our attempt to synthesize an SnS thin film. EDTA has shown its capacity for improving the longevity of the deposition bath as well as the adhesion of the deposited film on a titanium substrate. Photoelectrochem. anal. reveals outstanding photoactivity of the electrodeposited thin film, while an optical study shows an energy gap of approx. 1.1 eV. The effects of chelating agent were extd. from the results of cyclic voltammetry, photoelectrochem. test, SEM and X-ray diffraction spectroscopy. The latter which displays better defined signals reaffirms the appreciable improvement in the polycrystallinity of the thin film. Anal. of peak locations, coincidentally, confirms that SnS of Herzenbergite form has been obtained.
39
Sugiyama, M.; Miyauchi, K.; Minemura, T.; Ohtsuka, K.; Noguchi, K.; Nakanishi, H. Jpn. J. Appl. Phys. 2008, 47, 4494– 4495
Google Scholar
39
Preparation of SnS films by sulfurization of Sn sheet
Sugiyama, Mutsumi; Miyauchi, Keisuke; Minemura, Takehiro; Ohtsuka, Kenichi; Noguchi, Koji; Nakanishi, Hisayuki
Japanese Journal of Applied Physics (2008), 47 (6, Pt. 1), 4494-4495CODEN: JJAPB6 ISSN:. (Japan Society of Applied Physics)
SnS films were grown by sulfurization using an inexpensive Sn sheet and S powder. The Sn sheet was sulfurized in a closed ampoule at a low temp. between 150 and 300°. The resulting sulfurized films had a flat surface and large grains, and exhibited adhered very well to the substrate. These samples exhibited X-ray diffraction peaks corresponding to SnS and contained no extra phases. These results represent the first step toward realizing an optical device such as a solar cell using a SnS film grown by a sulfurization method.
40
Xu, Z.; Chen, Y. Semicond. Sci. Technol. 2012, 27, 035007
Google Scholar
There is no corresponding record for this reference.
41
Ghosh, B.; Das, M.; Banerjee, P.; Das, S. Appl. Surf. Sci. 2008, 254, 6436– 6440
Google Scholar
There is no corresponding record for this reference.
42
Hartman, K.; Johnson, J.; Bertoni, M. I.; Recht, D.; Aziz, M. J.; Scarpulla, M. A.; Buonassisi, T. Thin Solid Films 2011, 519, 7421– 7424
Google Scholar
There is no corresponding record for this reference.
43
Schafer, H. Z. Anorg. Chem 1956, 286, 42
Google Scholar
There is no corresponding record for this reference.
44
Nitsche, R.; Bolsterli, H. U.; Lichtensteiger, M. J. Phys. Chem. Solids 1961, 21, 199– 205
Google Scholar
44
Crystal growth by chemical transport reactions. I. Binary, ternary, and mixed-crystal chalcogenides
Nitsche, R.; Bolsterli, H. U.; Lichtensteiger, M.
Physics and Chemistry of Solids (1961), 21 (), 199-205CODEN: PCSOA7; ISSN:0369-8726.
The concept of chem. transport reactions (volatilization of a material via a low-volatile chem. intermediate at a temp. T1 and back-reaction of the mixt. at a temp. T2, using the temp. dependence of the chem. equil. involved) is a valuable tool for growing single crystals of many materials which cannot be easily obtained from the melt. The main advantage is the use of growth temps. well below the melting or sublimation point. The method was used to grow crystals of the binary chalcogenides: ZnS, ZnSe, CdS, CdSe, MnS, SnS, SnS2, In2S3, Ga2S3, GaS, and GaSe. Ternary chalcogenides of the type AB2X4 (A = Zn, Cd, Hg; B = Ga, In; X = S, Se) were obtained for the first time as single crystals. Mixed crystals of ZnS.MnS were prepd. over a wide range of compn.
45
Colombara, D.; Delsante, S.; Borzone, G.; Mitchels, J.; Molloy, K.; Thomas, L.; Mendis, B.; Cummings, C.; Marken, F.; Peter, L. J. Cryst. Growth 2013, 364, 101– 110
Google Scholar
45
Crystal growth of Cu2ZnSnS4 solar cell absorber by chemical vapor transport with I2
Colombara, D.; Delsante, S.; Borzone, G.; Mitchels, J. M.; Molloy, K. C.; Thomas, L. H.; Mendis, B. G.; Cummings, C. Y.; Marken, F.; Peter, L. M.
Journal of Crystal Growth (2013), 364 (), 101-110CODEN: JCRGAE; ISSN:0022-0248. (Elsevier B.V.)
Single crystals of Cu2ZnSnS4 have been produced within sealed quartz ampuls via the chem. vapor transport technique using I2 as the transporting agent. The effects of temp. gradient and I2 load on the crystal habit and compn. are considered. Crystals have been analyzed with XRD, SEM, and TEM for compositional and structural uniformities at both microscopic and nanoscopic levels. The synthesized crystals have suitable (I2-load dependent) properties and are useful for further solar absorber structural and phys. characterizations. A new chem. vapor transport method based on longitudinally isothermal treatments is attempted. Based on a proposed simplistic mechanism of crystal growth, conditions for crystal enlargement with the new method are envisaged.
46
Schouten, P. G.; Warman, J. M.; de Haas, M. P. J. Phys. Chem. 1993, 97, 9863– 9870
Google Scholar
There is no corresponding record for this reference.
47
Warman, J. M.; de Haas, M. P.; Dicker, G.; Grozema, F. C.; Piris, J.; Debije, M. G. Chem. Mater. 2004, 16, 4600– 4609
Google Scholar
There is no corresponding record for this reference.
48
Hohenberg, P.; Kohn, W. Phys. Rev. 1964, 136, B864– B871
Google Scholar
There is no corresponding record for this reference.
49
Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1133– A1138
Google Scholar
There is no corresponding record for this reference.
50
Kresse, G.; Furthmüller, J. Phys. Rev. B 1996, 54, 11169
Google Scholar
50
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
Kresse, G.; Furthmueller, J.
Physical Review B: Condensed Matter (1996), 54 (16), 11169-11186CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
The authors present an efficient scheme for calcg. the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrixes will be discussed. This approach is stable, reliable, and minimizes the no. of order Natoms3 operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special "metric" and a special "preconditioning" optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calcns. It will be shown that the no. of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order Natoms2 scaling is found for systems contg. up to 1000 electrons. If we take into account that the no. of k points can be decreased linearly with the system size, the overall scaling can approach Natoms. They have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large no. of different systems (liq. and amorphous semiconductors, liq. simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable.
51
Kresse, G.; Joubert, D. Phys. Rev. B 1999, 59, 1758
Google Scholar
51
From ultrasoft pseudopotentials to the projector augmented-wave method
Kresse, G.; Joubert, D.
Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
52
Perdew, J. P.; Ruzsinszky, A.; Csonka, G. I.; Vydrov, O. A.; Scuseria, G. E.; Constantin, L. A.; Zhou, X.; Burke, K. Phys. Rev. Lett. 2008, 100, 136406
Google Scholar
52
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gabor I.; Vydrov, Oleg A.; Scuseria, Gustavo E.; Constantin, Lucian A.; Zhou, Xiaolan; Burke, Kieron
Physical Review Letters (2008), 100 (13), 136406/1-136406/4CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
Popular modern generalized gradient approxns. are biased toward the description of free-atom energies. Restoration of the first-principles gradient expansion for exchange over a wide range of d. gradients eliminates this bias. We introduce a revised Perdew-Burke-Ernzerhof generalized gradient approxn. that improves equil. properties of densely packed solids and their surfaces.
53
Heyd, J.; Scuseria, G. E.; Ernzerhof, M. J. Chem. Phys. 2006, 124, 219906
Google Scholar
53
Hybrid functionals based on a screened Coulomb potential. [Erratum to document cited in CA139:042043]
Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
Journal of Chemical Physics (2006), 124 (21), 219906/1CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
The screening parameter quoted in this paper (ω=0.15) is not the one that was actually used in the code. In order to reproduce our results, two ω values are needed: ω =0.15 2≈0.106 for Hartree-Fock and ω=0.15x21/3 ≈0.189 for the PBE part. This erratum applies to all of our ωPBEh and HSE calcns. published to date. The authors emphasize that all the results obtained with this functional are reproducible using the two ω values quoted. The validity of all the published HSE values is not affected. Optimization of a single value of ω for a functional of the type reported in this paper will be presented elsewhere.
54
Head, J. D.; Zerner, M. C. Chem. Phys. Lett. 1985, 122, 264– 270
Google Scholar
There is no corresponding record for this reference.
55
Blum, V.; Gehrke, R.; Hanke, F.; Havu, P.; Havu, V.; Ren, X.; Reuter, K.; Scheffler, M. Comput. Phys. Commun. 2009, 180, 2175– 2196
Google Scholar
55
Ab initio molecular simulations with numeric atom-centered orbitals
Blum, Volker; Gehrke, Ralf; Hanke, Felix; Havu, Paula; Havu, Ville; Ren, Xinguo; Reuter, Karsten; Scheffler, Matthias
Computer Physics Communications (2009), 180 (11), 2175-2196CODEN: CPHCBZ; ISSN:0010-4655. (Elsevier B.V.)
We describe a complete set of algorithms for ab initio mol. simulations based on numerically tabulated atom-centered orbitals (NAOs) to capture a wide range of mol. and materials properties from quantum-mech. first principles. The full algorithmic framework described here is embodied in the Fritz Haber Institute "ab initio mol. simulations" (FHI-aims) computer program package. Its comprehensive description should be relevant to any other first-principles implementation based on NAOs. The focus here is on d.-functional theory (DFT) in the local and semilocal (generalized gradient) approxns., but an extension to hybrid functionals, Hartree-Fock theory, and MP2/GW electron self-energies for total energies and excited states is possible within the same underlying algorithms. An all-electron/full-potential treatment that is both computationally efficient and accurate is achieved for periodic and cluster geometries on equal footing, including relaxation and ab initio mol. dynamics. We demonstrate the construction of transferable, hierarchical basis sets, allowing the calcn. to range from qual. tight-binding like accuracy to meV-level total energy convergence with the basis set. Since all basis functions are strictly localized, the otherwise computationally dominant grid-based operations scale as O(N) with system size N. Together with a scalar-relativistic treatment, the basis sets provide access to all elements from light to heavy. Both low-communication parallelization of all real-space grid based algorithms and a ScaLapack-based, customized handling of the linear algebra for all matrix operations are possible, guaranteeing efficient scaling (CPU time and memory) up to massively parallel computer systems with thousands of CPUs.
56
Knacke, O.; Kubaschewski, O. Thermochemical Properties of Inorganic Substances, 2nd ed.; Springer-Verlag: Dusseldorf, Germany, 1991.
Google Scholar
There is no corresponding record for this reference.
57
Colombara, D. Investigation of Chalcogenide Absorber Materials for Photovoltaic Applications. Ph.D. thesis,University of Bath, Bath, U.K., 2012.
Google Scholar
There is no corresponding record for this reference.
58
Lambros, A.; Geraleas, D.; Economou, N. J. Phys. Chem. Solids 1974, 35, 537– 541
Google Scholar
58
Optical absorption edge in tin sulfide
Lambros, A. P.; Geraleas, D.; Economou, N. A.
Journal of Physics and Chemistry of Solids (1974), 35 (4), 537-41CODEN: JPCSAW; ISSN:0022-3697.
Optical absorption in single crystals of SnS was studied at many temps. at 100-300°K, at 2.2-0.8 μ. From the interference fringe patterns the absorption coeff., reflection coeff. and n as a function of wavelength were detd. for 2 light polarizations (ε‖a and ε‖b). From an anal. of the data, indirect band gaps of 1.142 and 1.095 eV were found for the 2 directions of polarization. Also it was found that the phonon assisted transitions required the participation of 2 phonons at different energy thresholds with energies 0.033 or 0.038 eV and 0.082 or 0.113 eV, with ref. to the 2 axes. The temp. dependence of the indirect band gap for each direction of light polarization is linear with a slope -4.05 × 10-3 and -4.37 × 10-3 eV, resp.
59
Kniep, R.; Mootz, D.; Severin, U.; Wunderlich, H. Acta Crystallogr., Sect. B 1982, 38, 2022– 2023
Google Scholar
There is no corresponding record for this reference.
60
Hazen, M. R.; Finger, L. W. Am. Mineral. 1978, 63, 289– 292
Google Scholar
There is no corresponding record for this reference.
61
Chattopadhyay, T.; Pannetier, J.; Von Schnering, H. G. J. Phys. Chem. Solids 1986, 47, 879– 885
Google Scholar
61
Neutron diffraction study on the structural phase transition in tin sulfide (SnS) and tin selenide (SnSe)
Chattopadhyay, T.; Pannetier, J.; Von Schnering, H. G.
Journal of Physics and Chemistry of Solids (1986), 47 (9), 879-85CODEN: JPCSAW; ISSN:0022-3697.
The structural phase transitions in SnS and SnSe were investigated by neutron diffraction at 295-1000 K using a high temp. furnace. Accurate positional and thermal parameters were obtained as a function of temp. both in the α- (GeS-type, B16) and β-phase (TII-type, B33). These investigations indicate that the α →β phase transitions in SnS and SnSe are of 2nd-order displacive type, and consist mainly of the continuous movement of Sn and S/Se atoms almost entirely along the [100] direction, and suggest the soft-mode behavior of a zone-boundary phonon of the β-phase.
62
Price, L. S.; Parkin, I. P.; Hardy, A. M. E.; Clark, R. J. H.; Hibbert, T. G.; Molloy, K. C. Chem. Mater. 1999, 11, 1792– 1799
Google Scholar
There is no corresponding record for this reference.
63
Guang-Pu, W.; Zhi-Lin, Z.; Wei-Ming, Z.; Xiang-Hong, G.; Wei-Qun, C.; Tanamura, H.; Yamaguchi, M.; Noguchi, H.; Nagatomo, T.; Omoto, O.Photovoltaic Energy Conversion, 1994, Conference Record of the Twenty Fourth IEEE Photovoltaic Specialists Conference;
Waikoloa, HI, Dec 5–9, 1994
; IEEE: Piscataway, NJ, 1994.
Google Scholar
There is no corresponding record for this reference.
64
Ristova, M.; Ristov, M. Sol. Energ. Mat. Sol. C. 1998, 53, 95– 102
Google Scholar
There is no corresponding record for this reference.
65
Yanuar; Guastavino, F.; Llinares, C.; Djessas, K.; Masse, G. J. Mater. Sci. Lett. 2000, 19, 2135– 2137
Google Scholar
There is no corresponding record for this reference.
66
Calixto-Rodriguez, M.; Martinez, H.; Sanchez-Juarez, A.; Campos-Alvarez, J.; Tiburcio-Silver, A.; Calixto, M. Thin Solid Films 2009, 517, 2497– 2499
Google Scholar
There is no corresponding record for this reference.
67
Madelung, O. Semiconductors: Data Handbook, 3rd ed.; Springer: New York, 2004.
Google Scholar
There is no corresponding record for this reference.
68
Reddy, N. K.; Reddy, K. R. Solid-State Electron. 2005, 49, 902– 906
Google Scholar
68
Electrical properties of spray pyrolytic tin sulfide films
Reddy, N. Koteeswara; Reddy, K. T. Ramakrishna
Solid-State Electronics (2005), 49 (6), 902-906CODEN: SSELA5; ISSN:0038-1101. (Elsevier Ltd.)
Tin sulfide (SnxSy) films were prepd. using spray pyrolysis technique at different substrate temps. (Ts), (100-450°C) on Corning 7059 glass substrates. The phys. parameters such as elec. resistivity, Hall mobility and net carrier d. of the films were detd. at room temp. The films grown in the substrate temp. range, 300-375°C, were found to be p-type conducting. These SnS films showed av. elec. resistivity of ∼30 Ω cm, Hall mobility of ∼130 cm2/V s and carrier d., >1015 cm-3. The temp. dependence of elec. cond. of the films was also studied and the activation energies evaluated. The results obtained were discussed and reported.
69
Reddy, N. K.; Reddy, K. T. R. Mater. Chem. Phys. 2007, 102, 13– 18
Google Scholar
69
Preparation and characterisation of sprayed tin sulphide films grown at different precursor concentrations
Reddy, N. Koteeswara; Reddy, K. T. Ramakrishna
Materials Chemistry and Physics (2007), 102 (1), 13-18CODEN: MCHPDR; ISSN:0254-0584. (Elsevier B.V.)
Tin sulfide films were grown by spray pyrolysis technique at different precursor concns. varied in the range, 0.01-0.2 M keeping other deposition parameters const. The phys. properties of the deposited films were systematically studied in relation to the precursor concn. The studies indicated that the films grown in the precursor concn. range, 0.09-0.13 M were nearly stoichiometric with the Sn, S ratio of 1.06 and exhibited only SnS phase with a strong (1 1 1) preferred orientation that belongs to the orthorhombic crystal structure. These single-phase films showed an av. elec. resistivity of 32.9 Ω cm, Hall mobility of 139 cm2 V-1/s and carrier d. of ∼1015 cm-3. These films had an av. optical band gap of 1.32 eV with an absorption coeff. greater than 104 cm-1. These properties demonstrated that single-phase SnS films could be used as an absorber layer in the fabrication of heterojunction solar cells.
70
Amalraj, L.; Sanjeeviraja, C.; Jayachandran, M. J. Cryst. Growth 2002, 234, 683– 689
Google Scholar
70
Spray pyrolysed tin disulphide thin film and characterisation
Amalraj, L.; Sanjeeviraja, C.; Jayachandran, M.
Journal of Crystal Growth (2002), 234 (4), 683-689CODEN: JCRGAE; ISSN:0022-0248. (Elsevier Science B.V.)
Thin film of tin disulfide on glass substrate is prepd. by spray pyrolysis technique at a substrate temp. of 458 K. Using the hot probe technique the type of semiconductor is found to be n-type. X-ray diffraction anal. revealed the polycryst. nature of the film with hexagonal structure and a preferential orientation along the (0 0 1) plane. Fiber-like surface morphol. has been obsd. on the film. The surface compn. of the elements is analyzed with EDAX spectrum. A value of 3.85×10-7 Ω-1 cm-1 for the room temp. (302 K) cond. is detd. using the four-probe method. Activation energy of about 0.25 eV is detd. by plotting a graph between log (cond.) vs. reciprocal temp. The optical absorption and transmittance spectra have been recorded for this film in the wavelength range 380-900 nm. Thickness of the film and variation of absorption coeff. with wavelength are detd. using these spectral data. Band gap values of 2.16 eV with indirect allowed and 1.82 eV with indirect forbidden nature are obsd. for this pyrolyzed SnS2 thin film.
71
Julien, C.; Eddrief, M.; Samaras, I.; Balkanski, M. Mater. Sci. Eng., B 1992, 15, 70– 72
Google Scholar
There is no corresponding record for this reference.
72
Noguchi, H.; Setiyadi, A.; Tanamura, H.; Nagatomo, T.; Omoto, O. Sol. Energy Mater. Sol. Cells 1994, 35, 325– 331
Google Scholar
72
Characterization of vacuum-evaporated tin sulfide film for solar cell materials
Noguchi, Hidenori; Setiyadi, Agus; Tanamura, Hiromasa; Nagatomo, Takao; Omoto, Osamu
Solar Energy Materials and Solar Cells (1994), 35 (1-4), 325-31CODEN: SEMCEQ; ISSN:0927-0248. (Elsevier)
SnS films were prepd. by vacuum evapn. As-grown SnS films showed p-type conduction with a resistivity of 13-20 Ω cm, a carrier d. of 6.3×1014-1.2×1015 cm-3, and a Hall mobility of 400-500 cm2/V-s. The absorption coeffs. of the films were an order of 104 cm-1 at the fundamental absorption edge. The n-CdS/p-SnS heterojunctions were made by depositing n-CdS, p-SnS and Ag ohmic electrode on the transparent electrode (ITO) in the order ITO/n-CdS/p-SnS/Ag structure. The photovoltaic properties of a short-circuit current of 7 mA/cm2, an open-circuit voltage of 0.12 V, a fill factor of 0.35, and a conversion efficiency of 0.29% were obtained under the illumination of 100 mW/cm2.
73
Nair, M. T. S.; Nair, P. K. Semicond. Sci. Technol. 1991, 6, 132
Google Scholar
73
Simplified chemical deposition technique for good quality tin monosulfide thin films
Nair, M. T. S.; Nair, P. K.
Semiconductor Science and Technology (1991), 6 (2), 132-4CODEN: SSTEET; ISSN:0268-1242.
A chem. deposition technique, much simpler and more versatile than previously reported and capable of yielding good quality SnS films of thickness up to ≃1.2 μm under a choice of deposition conditions, is presented. The as-prepd. films are polycryst. with p-type dark cond. in the range 10-5-10-4 Ω-1cm-1 for the thicker (∼1 μm) films and showing a photocurrent to dark current ratio of 5-10 under 500 W m-2 tungsten halogen illumination. The optical transmittance and reflectance spectra and the photocurrent response curves of a series of SnS samples are explicitly presented to provide insight into possible applications of these films.
74
Wangperawong, A.; Herron, S. M.; Runser, R. R.; Hägglund, C.; Tanskanen, J. T.; Lee, H.-B.-R.; Clemens, B. M.; Bent, S. F. Appl. Phys. Lett. 2013, 103052105
Google Scholar
There is no corresponding record for this reference.
75
Sellin, P.; Davies, A. W.; Lohstroh, A.; Ozsan, M.; Parkin, J. IEEE Trans. Nucl. Sci. 2005, 52, 3074– 3078
Google Scholar
75
Drift mobility and mobility-lifetime products in CdTe:Cl grown by the traveling heater method
Sellin, P. J.; Davies, A. W.; Lohstroh, A.; Ozsan, M. E.; Parkin, J.
IEEE Transactions on Nuclear Science (2005), 52 (6, Pt. 2), 3074-3078CODEN: IETNAE; ISSN:0018-9499. (Institute of Electrical and Electronics Engineers)
Electron and hole charge transport properties of semi insulating CdTe:Cl grown by the traveling heater method (THM) were measured. An alpha-particle time of flight method was used to measure electron and hole drift mobility, with room temp. values of 880 cm2/Vs for electrons and 90 cm2/Vs for holes. The variation in mobility was also investigated as a function of temp., with electron and hole mobilities at 190 K of 1150 cm2/Vs and 20 cm2/Vs, resp. Using a Hecht anal., the electron and hole mobility-lifetime products were also measured over the same temp. range, with values at room temp. of 8 × 10-4 cm2/V and 7 × 10-5 cm2/V, resp. Time-resolved ion beam induced charge (IBIC) imaging was used to produce micrometer resoln. maps of electron drift mobility and signal amplitude, which showed excellent spatial uniformity.
76
Patil, R. H.; Tredgold, S G J. Phys. D: Appl. Phys. 1971, 4, 718– 722
Google Scholar
76
Electrical and photoconductive properties of tin(II) sulfide crystals
Patil, S. G.; Tredgold, R. H.
Journal of Physics D: Applied Physics (1971), 4 (5), 718-22CODEN: JPAPBE; ISSN:0022-3727.
Single crystals of SnS2 were prepd. by vapor transport. The elec. cond. of these crystals was measured along and perpendicular to their c direction by a probe method. The thermal activation energy assocd. with elec. conduction in the c direction exceeds that in the direction perpendicular to it by ∼0.18 eV. The spectral response of photocond. showed a band gap of 2.34 eV (at 300°K) with a temp. coeff. of -1.02 × 10-3 eV K-1.
77
Markvart, T. Prog. Quant. Electron. 2000, 24, 107– 186
Google Scholar
77
Light harvesting for quantum solar energy conversion
Markvart, Tomas
Progress in Quantum Electronics (2000), 24 (3-4), 107-186CODEN: PQUEAH; ISSN:0079-6727. (Elsevier Science Ltd.)
A review with 134 refs. of charge sepn. in photosynthesis, energy collection and minority carrier transport in solar cells, excitations and the resonant energy transfer, and exciton transport in the photosynthetic unit. This paper considers two examples of light harvesting (semiconductor solar cells and the photosynthetic app.) to illustrate the basic operation and principles that apply. In both cases it is shown that the rate of energy conversion is described by a law which parallels the Shockley's solar cell equation, and the light harvesting energy collection is subject to reciprocity relations which resemble Onsager's reciprocity relations between coeffs. which couple appropriate forces and flows in non-equil. thermodn. Differences in the basic at. make-up in the two systems lead to different energy transport equations. In both cases, however, similar math. techniques based on Green's functions can be used to advantage. The Green's function provides a convenient vehicle for the detn. of the probability of energy collection - known as the trapping probability in the photosynthetic unit. Using the reciprocity relation, both quantities are shown to be closely related to the distribution of the energy carriers in the dark. The collection probability can then be discussed in detail, by solving the semiconductor device equations in the case of solar cell, and by linking the Green's function formalism to the random walk model in the case of the photosynthetic unit. The concept of resonant energy transfer is beginning to enter the arena of solid-state optoelectronics. It is an aim of this paper to show that similar phenomena (which exist in the domain of bioenergetics) can throw new light on a range of energy transfer and collection processes that are of considerable importance in many modern optoelectronic devices.
78
de Walle, C. G. V.; Neugebauer, J. J. Appl. Phys. 2004, 95, 3851– 3879
Google Scholar
There is no corresponding record for this reference.
79
Engelken, R. D.; McCloud, H. E.; Lee, C.; Slayton, M.; Ghoreishi, H. J. Electrochem. Soc. 1987, 134, 2696– 2707
Google Scholar
There is no corresponding record for this reference.
80
Cheng, S.; Zhang, H. Micro Nano Lett. 2011, 6, 473– 475
Google Scholar
80
Influence of thickness on structural and optical properties of evaporated tin sulphide films
Cheng, Shuying; Zhang, Hong
Micro & Nano Letters (2011), 6 (7), 473-475CODEN: MNLIBX; ISSN:1750-0443. (Institution of Engineering and Technology)
Tin sulfide (SnS) films with thicknesses of 65-580 nm have been deposited on glass substrates by thermal evapn. The phys. properties of the films were investigated using X-ray diffraction, SEM, at. force microscopy, Raman spectroscopy and UV-visible-near-IR spectroscopy measurements at room temp. It is indicated that the deposited films mainly exhibit SnS phase, but they contain tiny SnO2. The deposited SnS films are pinhole free, smooth and strongly adherent to the surface of the substrate. With the increase of the film thickness from 65 to 580 nm, the color of the SnS films changes from brown to dark brown to gray, and the grains and roughness of the films become larger and larger, but the direct bandgap decreases. All the films have larger direct bandgap of 1.55-2.28 eV, which is much larger than the 1.3 eV of bulk SnS.
81
Yu, L.; Lany, S.; Kykyneshi, R.; Jieratum, V.; Ravichandran, R.; Pelatt, B.; Altschul, E.; Platt, H. A. S.; Wager, J. F.; Keszler, D. A.; Zunger, A. Adv. Energy Mater. 2011, 1, 748– 753
Google Scholar
81
Iron chalcogenide photovoltaic absorbers
Yu, Liping; Lany, Stephan; Kykyneshi, Robert; Jieratum, Vorranutch; Ravichandran, Ram; Pelatt, Brian; Altschul, Emmeline; Platt, Heather A. S.; Wager, John F.; Keszler, Douglas A.; Zunger, Alex
Advanced Energy Materials (2011), 1 (5), 748-753CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
The properties were studied of Fe2SiS4, Fe2GeS4, FeS2, FeS2-x, and related compds. The suitability of these materials as solar cells is discussed.
82
Atkins, P.; Overton, T.; Rourke, J.; Weller, M.; Armstrong, F. Inorganic Chemistry; Oxford University Press: Oxford, U.K., 2006.
Google Scholar
There is no corresponding record for this reference.
83
Malone, B. D.; Kaxiras, E. Phys. Rev. B 2013, 87, 245312
Google Scholar
There is no corresponding record for this reference.
84
Zainal, Z.; Hussein, M. Z.; Ghazali, A. Sol. Energy Mater. Sol. Cells 1996, 40, 347– 357
Google Scholar
84
Cathodic electrodeposition of SnS thin films from aqueous solution
Zainal, Zulkarnain; Hussein, Mohd. Zobir; Ghazali, Arniza
Solar Energy Materials and Solar Cells (1996), 40 (4), 347-357CODEN: SEMCEQ; ISSN:0927-0248. (Elsevier)
SnS thin films were prepd. by cathodic electrodeposition on ITO/glass and Ti substrates from a soln. contg. SnCl2 and thiosulfate ions. Cyclic voltammetry expts. were performed to elucidate the electrodic processes occurred when potentials were applied and to det. the optimum potential for electrodeposition. The photoactivity of the deposited films and their conduction types were evaluated using the photoelectrochem. technique. The bandgap energy and type of optical transitions were detd. from optical absorbance data. Structural and compositional anal. were accomplished using x-ray diffractometry, electron dispersive anal. of x-ray, and XPS. The morphol. of the films were examd. using SEM.
85
Lopez, S.; Ortiz, A. Semicond. Sci. Technol. 1994, 9, 2130– 2133
Google Scholar
85
Spray pyrolysis deposition of tin sulfide (SnxSy) thin films
Lopez, S.; Ortiz, A.
Semiconductor Science and Technology (1994), 9 (11), 2130-3CODEN: SSTEET; ISSN:0268-1242. (Institute of Physics Publishing)
Tin sulfide (SnxSy) thin films have been prepd. on Pyrex glass substrates by the spray pyrolysis technique using tin chloride (SnCl2) and N,N-dimethylthiourea (CH3NHCSNHCH3) as starting materials. The depositions were carried out in the range of substrate temps. from 320 to 450°. From x-ray diffraction measurements and SEM micrographs, it is found that the values of x and y, which det. the type of deposited compd., depend on the substrate temp. At lower substrate temps. (320-360°), mixed phases such as Sn2S3 and γ-Sn2S3 are present. At intermediate substrate temps. (370-390°), the SnS phase is predominant. For substrate temps. higher than 390°, the deposited material is mainly SnO2. The optical reflectance and transmittance of SnS were used in an iterative method to obtain the refractive index (n) and the excitation coeff. (k). The values of n and k were used to calc. the absorption coeff. (k). These values of n and k were used to calc. the absorption coeff. (α) and the bandgap (EG), giving the result EG = 1.27 eV. Measurements of the dark conductance (σ) as a function of T were made and an activation energy of 0.54 eV was detd. from the slope of a plot of ln σ vs. 1/T.
86
Ragina, A. J.; Murali, K. V.; Preetha, K. C.; Deepa, K.; Remadevi, T. L. A Study of Optical Parameters of Tin Sulphide Thin Films Using the Swanepoel Method. Optics: Phenomena, Materials, Devices, and Characterization 2011: International Conference on Light ;
Calicut, India, May 23–25, 2011
; American Institute of Physics: College Park, MD, 2011
Google Scholar
There is no corresponding record for this reference.
87
Domingo, G.; Itoga, R. S.; Kannewurf, C. R. Phys. Rev. 1966, 143, 536– 541
Google Scholar
87
Fundamental optical absorption in SnS2 and SnSe2
Domingo, G.; Itoga, R. S.; Kannewurf, C. R.
Physical Review (1966), 143 (2), 536-41CODEN: PHRVAO; ISSN:0031-899X.
Optical absorption in single-crystal n-type SnS2 and SnSe2 has been studied at 300°K., 0.26-6.5 μ. Samples suitable for optical measurements were prepd. by various vapor-deposition techniques. The elec. characteristics of the samples used in the absorption measurements were: for SnSe2, cond. 3.6 (Ω cm.)-1, electron concn. 1018/cc., mobility 27 cm.2/v.-sec.; and for SnS2, cond. 10-7 (Ω cm.)-1. From transmittance and reflectance measurements, the absorption coeff. and n were detd. for light polarized perpendicular to the crystallographic symmetry axis. From an analysis of the data in the high-absorption region, directtransition band gaps of 1.62 and 2.88 ev. were found for SnSe2 and SnS2, resp. A threshold for possible indirect phonon-assisted transitions occurs at 0.97 ev. for SnSe2 and at 2.07 ev. for SnS2. Photocond. data for SnS2 are also presented.
88
Shi, C.; Chen, Z.; Shi, G.; Sun, R.; Zhan, X.; Shen, X. Thin Solid Films 2012, 520, 4898– 4901
Google Scholar
There is no corresponding record for this reference.
89
Alpen, U.; Fenner, J.; Gmelin, E. Mater. Res. Bull. 1975, 10, 175– 180
Google Scholar
There is no corresponding record for this reference.
90
Lopez, S.; Granados, S.; Ortiz, A. Semicond. Sci. Technol. 1996, 11, 433
Google Scholar
90
Spray pyrolysis deposition of Sn2S3 thin films
Lopez, S.; Granados, S.; Ortiz, A.
Semiconductor Science and Technology (1996), 11 (3), 433-6CODEN: SSTEET; ISSN:0268-1242. (Institute of Physics Publishing)
Ternary compd. SnIISnIVS3 thin films were prepd. on Pyrex glass substrates by the spray pyrolysis process using Sn chloride (SnCl2) and n,n-dimethylthiourea as starting materials. The depositions were carried out at a substrate temp. of 320°. The identification of the Sn2S3 phase was achieved by x-ray diffraction measurements. The optical reflectance and transmittance of the prepd. films were used to obtain the variation of the refractive index and the extinction coeff. as a function of the wavelength. These calcd. values were used to find the absorption coeff. and the optical bandgap and gave Eg = 1.16 eV. From measurements of the conductance as a function of T-1, a dark activation energy was detd. with a value of 1.02 eV.
91
Salah, H. B. H.; Bouzouita, H.; Rezig, B. Thin Solid Films 2005, 480?481, 439– 442
Google Scholar
There is no corresponding record for this reference.
92
Walsh, A.; Chen, S.; Wei, S.-H.; Gong, X.-G. Adv. Energy Mater. 2012, 2, 400– 409
Google Scholar
92
Kesterite thin-film solar cells: advances in materials modelling of Cu2ZnSnS4
Walsh, Aron; Chen, Shiyou; Wei, Su-Huai; Gong, Xin-Gao
Advanced Energy Materials (2012), 2 (4), 400-409CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
A review. Quaternary semiconducting materials based on the kesterite (A2BCX4) mineral structure are the most promising candidates to overtake the current generation of light-absorbing materials for thin-film solar cells. Cu2ZnSnS4 (CZTS), Cu2ZnSnSe4 (CZTSe) and their alloy Cu2ZnSn(Se,S)4 consist of abundant, low-cost and non-toxic elements, unlike current CdTe and Cu(In,Ga)Se2 based technologies. Zinc-blende related structures are formed by quaternary compds., but the complexity assocd. with the multi-component system introduces difficulties in material growth, characterization, and application. First-principles electronic structure simulations, performed over the past five years, that address the structural, electronic, and defect properties of this family of compds. are reviewed. Initial predictions of the bandgaps and crystal structures have recently been verified exptl. The calcns. highlight the role of at. disorder on the cation sub-lattice, as well as phase sepn. of Cu2ZnSnS4 into ZnS and CuSnS3, on the material performance for light-to-electricity conversion in photovoltaic devices. Finally, the current grand challenges for materials modeling of thin-film solar cells are highlighted.
93
Yu, P. Y.; Cardona, M. Fundamentals of Semiconductors, 3rd ed.; Springer-Verlag: New York, 2003.
Google Scholar
There is no corresponding record for this reference.
94
Mathews, N. R.; Anaya, H. B. M.; Cortes-Jacome, M. A.; Angeles-Chavez, C.; Toledo-Antonio, J. A. J. Electrochem. Soc. 2010, 157, H337– H341
Google Scholar
There is no corresponding record for this reference.
95
Miles, R. W.; Ogah, O. E.; Zoppi, G.; Forbes, I. Thin Solid Films 2009, 517, 4702– 4705
Google Scholar
There is no corresponding record for this reference.
96
Barone, G.; Hibbert, T. G.; Mahon, M. F.; Molloy, K. C.; Price, L. S.; Parkin, I. P.; Hardy, A. M. E.; Field, M. N. J. Mater. Chem. 2001, 11, 464– 468
Google Scholar
There is no corresponding record for this reference.
97
Scragg, J. J.; Kubart, T.; Watjen, J. T.; Ericson, T.; Linnarsson, M. K.; Platzer-Bjorkman, C. Chem. Mater. 2013, 25, 3162– 3171
Google Scholar
There is no corresponding record for this reference.
98
Moore, A. R. Appl. Phys. Lett. 1977, 31, 762– 764
Google Scholar
There is no corresponding record for this reference.
99
Handbook of Optical Constants of Solids, 3rd ed.; Academic Press: London, 1998.
Google Scholar
There is no corresponding record for this reference.
100
Momma, K.; Izumi, F. J. Appl. Crystallogr. 2011, 44, 1272– 1276
Google Scholar
100
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
Momma, Koichi; Izumi, Fujio
Journal of Applied Crystallography (2011), 44 (6), 1272-1276CODEN: JACGAR; ISSN:0021-8898. (International Union of Crystallography)
VESTA is a 3D visualization system for crystallog. studies and electronic state calcns. It was upgraded to the latest version, VESTA 3, implementing new features including drawing the external morphpol. of crysals; superimposing multiple structural models, volumetric data and crystal faces; calcn. of electron and nuclear densities from structure parameters; calcn. of Patterson functions from the structure parameters or volumetric data; integration of electron and nuclear densities by Voronoi tessellation; visualization of isosurfaces with multiple levels, detn. of the best plane for selected atoms; an extended bond-search algorithm to enable more sophisticated searches in complex mols. and cage-like structures; undo and redo is graphical user interface operations; and significant performance improvements in rendering isosurfaces and calcg. slices.

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Prashant Bhaskar, Alexander W. Achtstein, Martien J. W. Vermeulen, Laurens D. A. Siebbeles. Unconventional Thermally Activated Indirect to Direct Radiative Recombination of Electrons and Holes in Tin Disulfide Two-Dimensional van der Waals Material. The Journal of Physical Chemistry C 2019, 123 (18) , 11968-11973. https://doi.org/10.1021/acs.jpcc.9b01842
Eli Sutter, Jia Wang, Peter Sutter. Nanoparticle-Templated Thickness Controlled Growth, Thermal Stability, and Decomposition of Ultrathin Tin Sulfide Plates. Chemistry of Materials 2019, 31 (7) , 2563-2570. https://doi.org/10.1021/acs.chemmater.9b00177
Raja Sen, Priya Johari. One-Dimensional-Sn2X3 (X = S, Se) as Promising Optoelectronic and Thermoelectronic Materials: A Comparison with Three-Dimensional-Sn2X3. ACS Applied Materials & Interfaces 2019, 11 (13) , 12733-12744. https://doi.org/10.1021/acsami.8b18430
Meng Cao, Kefeng Yao, Chuangsheng Wu, Jian Huang, Weiguang Yang, Lei Zhang, Fang Lei, Yan Sun, Linjun Wang, Yue Shen. Facile Synthesis of SnS and SnS2 Nanosheets for FTO/SnS/SnS2/Pt Photocathode. ACS Applied Energy Materials 2018, 1 (11) , 6497-6504. https://doi.org/10.1021/acsaem.8b01414
Adam J. Biacchi, Son T. Le, Brian G. Alberding, Joseph A. Hagmann, Sujitra J. Pookpanratana, Edwin J. Heilweil, Curt A. Richter, Angela R. Hight Walker. Contact and Noncontact Measurement of Electronic Transport in Individual 2D SnS Colloidal Semiconductor Nanocrystals. ACS Nano 2018, 12 (10) , 10045-10060. https://doi.org/10.1021/acsnano.8b04620
Peter Sutter, Eli Sutter. Growth Mechanisms of Anisotropic Layered Group IV Chalcogenides on van der Waals Substrates for Energy Conversion Applications. ACS Applied Nano Materials 2018, 1 (6) , 3026-3034. https://doi.org/10.1021/acsanm.8b00660
Yuki Iguchi, Kazutoshi Inoue, Taiki Sugiyama, Hiroshi Yanagi. Single-Crystal Growth of Cl-Doped n-Type SnS Using SnCl2 Self-Flux. Inorganic Chemistry 2018, 57 (12) , 6769-6772. https://doi.org/10.1021/acs.inorgchem.8b00646
Bo-In Park, Yoon Hee Jang, Seung Yong Lee, Doh-Kwon Lee. Mechanochemically Synthesized SnS Nanocrystals: Impact of Nonstoichiometry on Phase Purity and Solar Cell Performance. ACS Sustainable Chemistry & Engineering 2018, 6 (3) , 3002-3009. https://doi.org/10.1021/acssuschemeng.7b02711
Juran Kim, Jayeong Kim, Seokhyun Yoon, Jeong-yoon Kang, Chan-Wook Jeon, and William Jo . Single Phase Formation of SnS Competing with SnS2 and Sn2S3 for Photovoltaic Applications: Optoelectronic Characteristics of Thin-Film Surfaces and Interfaces. The Journal of Physical Chemistry C 2018, 122 (6) , 3523-3532. https://doi.org/10.1021/acs.jpcc.8b00179
Jonathan M. Skelton, Lee A. Burton, Fumiyasu Oba, and Aron Walsh . Chemical and Lattice Stability of the Tin Sulfides. The Journal of Physical Chemistry C 2017, 121 (12) , 6446-6454. https://doi.org/10.1021/acs.jpcc.6b12581
Xinyi Chia, Petr Lazar, Zdeněk Sofer, Jan Luxa, and Martin Pumera . Layered SnS versus SnS2: Valence and Structural Implications on Electrochemistry and Clean Energy Electrocatalysis. The Journal of Physical Chemistry C 2016, 120 (42) , 24098-24111. https://doi.org/10.1021/acs.jpcc.6b06977
Leith Samad, Sage M. Bladow, Qi Ding, Junqiao Zhuo, Robert M. Jacobberger, Michael S. Arnold, and Song Jin . Layer-Controlled Chemical Vapor Deposition Growth of MoS2 Vertical Heterostructures via van der Waals Epitaxy. ACS Nano 2016, 10 (7) , 7039-7046. https://doi.org/10.1021/acsnano.6b03112
Brian G. Alberding, Adam J. Biacchi, Angela R. Hight Walker, and Edwin J. Heilweil . Charge Carrier Dynamics and Mobility Determined by Time-Resolved Terahertz Spectroscopy on Films of Nano-to-Micrometer-Sized Colloidal Tin(II) Monosulfide. The Journal of Physical Chemistry C 2016, 120 (28) , 15395-15406. https://doi.org/10.1021/acs.jpcc.6b01684
E. Sutter, Y. Huang, H.-P. Komsa, M. Ghorbani-Asl, A.V. Krasheninnikov, and P. Sutter . Electron-Beam Induced Transformations of Layered Tin Dichalcogenides. Nano Letters 2016, 16 (7) , 4410-4416. https://doi.org/10.1021/acs.nanolett.6b01541
Y.-B. Yang, J. K. Dash, Y. Xiang, Y. Wang, J. Shi, P. H. Dinolfo, T.-M. Lu, and G.-C. Wang . Tuning the Phase and Optical Properties of Ultrathin SnSx Films. The Journal of Physical Chemistry C 2016, 120 (24) , 13199-13214. https://doi.org/10.1021/acs.jpcc.6b03529
Guangmao Li, Kui Wu, Qiong Liu, Zhihua Yang, and Shilie Pan . Na2ZnGe2S6: A New Infrared Nonlinear Optical Material with Good Balance between Large Second-Harmonic Generation Response and High Laser Damage Threshold. Journal of the American Chemical Society 2016, 138 (23) , 7422-7428. https://doi.org/10.1021/jacs.6b03734
Giovanni Altamura and Julien Vidal . Impact of Minor Phases on the Performances of CZTSSe Thin-Film Solar Cells. Chemistry of Materials 2016, 28 (11) , 3540-3563. https://doi.org/10.1021/acs.chemmater.6b00069
Thomas J. Whittles, Lee A. Burton, Jonathan M. Skelton, Aron Walsh, Tim D. Veal, and Vin R. Dhanak . Band Alignments, Valence Bands, and Core Levels in the Tin Sulfides SnS, SnS2, and Sn2S3: Experiment and Theory. Chemistry of Materials 2016, 28 (11) , 3718-3726. https://doi.org/10.1021/acs.chemmater.6b00397
Y.-B. Yang, J. K. Dash, A. J. Littlejohn, Y. Xiang, Y. Wang, J. Shi, L. H. Zhang, K. Kisslinger, T.-M. Lu, and G.-C. Wang . Large Single Crystal SnS2 Flakes Synthesized from Coevaporation of Sn and S. Crystal Growth & Design 2016, 16 (2) , 961-973. https://doi.org/10.1021/acs.cgd.5b01512
Ibbi Y. Ahmet, Michael S. Hill, Andrew L. Johnson, and Laurence M. Peter . Polymorph-Selective Deposition of High Purity SnS Thin Films from a Single Source Precursor. Chemistry of Materials 2015, 27 (22) , 7680-7688. https://doi.org/10.1021/acs.chemmater.5b03220
Antoine de Kergommeaux, Miguel Lopez-Haro, Stéphanie Pouget, Jian-Min Zuo, Colette Lebrun, Frédéric Chandezon, Dmitry Aldakov, and Peter Reiss . Synthesis, Internal Structure, and Formation Mechanism of Monodisperse Tin Sulfide Nanoplatelets. Journal of the American Chemical Society 2015, 137 (31) , 9943-9952. https://doi.org/10.1021/jacs.5b05576
Jie Ge, Junhao Chu, Yanfa Yan, Jinchun Jiang, and Pingxiong Yang . Co-electroplated Kesterite Bifacial Thin-Film Solar Cells: A Study of Sulfurization Temperature. ACS Applied Materials & Interfaces 2015, 7 (19) , 10414-10428. https://doi.org/10.1021/acsami.5b01641
Guoxiong Su, Viktor G. Hadjiev, Phillip E. Loya, Jing Zhang, Sidong Lei, Surendra Maharjan, Pei Dong, Pulickel M. Ajayan, Jun Lou, and Haibing Peng . Chemical Vapor Deposition of Thin Crystals of Layered Semiconductor SnS2 for Fast Photodetection Application. Nano Letters 2015, 15 (1) , 506-513. https://doi.org/10.1021/nl503857r
Yaqi Liu, Yichen Liu, Guicheng Luo, Wentao Zhu, Ning Li, Yi Song, Huaju Song, Yun Shan, Qifan Wu, Yanan Ding, Aiping Liang, Lizhe Liu. Photothermally inducing SnS2 phase transition in Cu2O@CuS@SnS2 core–shell heterostructure to trigger efficient photocatalytic CO2 reduction. Chemical Engineering Journal 2025, 510 , 161537. https://doi.org/10.1016/j.cej.2025.161537
Saurabh Mishra, Himanshu Meena, Horesh Kumar. Effect of sulphur (S) incorporation on structural and electrical properties of selenium-rich ternary chalcogenide Se97-xSn3Sx (x = 0, 4, 8, and 12) alloys. Journal of Alloys and Compounds 2025, 1020 , 179454. https://doi.org/10.1016/j.jallcom.2025.179454
Taichi Nogami, Issei Suzuki, Daiki Motai, Hiroshi Tanimura, Tetsu Ichitsubo, Takahisa Omata. Non-stoichiometry in SnS: How it affects thin-film morphology and electrical properties. APL Materials 2025, 13 (3) https://doi.org/10.1063/5.0248310
Liuping Liu, Sheng Ni, Fengyi Zhu, Yuling Zhu, Changlong Liu, Xutao Zhang, He Zhu, Jiazhen Zhang, Donghai Zhang, Changyi Pan, Li Han, Weiwei Tang, Guanhai Li, Haibo Shu, Xiaoshuang Chen. Highly sensitive multicolor uncooled photoresponse and imaging based on symmetry breaking heterojunction. InfoMat 2025, 7 (3) https://doi.org/10.1002/inf2.12641
Mohd Arif Dar, M. Satgunam, Khalid Mujasam Batoo, S. Kalpnan, P. Arularasan, Umar Ali Dar, Selvakumar Suthakaran, L. Guganathan, Aafaq A. Rather, Madhulika Mishra, S. R. Majid. Future Photovoltaic Applications of Nanostructured Metal Chalcogenides. Comments on Inorganic Chemistry 2025, 1 , 1-54. https://doi.org/10.1080/02603594.2025.2464732
Dwaipayan Chakraborty, Zubair Nabi Ganaie, Priya Johari. High-performance Sn 2 S 3 as a conversion-alloying anode material for lithium-ion batteries: insights from first-principles calculations. Journal of Materials Chemistry A 2025, 13 (6) , 4650-4661. https://doi.org/10.1039/D4TA05403B
Premkumar Jayaraman, Hamed Pourzolfaghar, Yuan-Yao Li, Helen Annal Therese. Boosted ion switching at the electrode-electrolyte interfaces of architecture interdigitated flexible supercapacitors. Materials Today Physics 2025, 51 , 101668. https://doi.org/10.1016/j.mtphys.2025.101668
Yumo Zhu, Cheng Chang, Yanling Pei. SnxSey: New promising thermoelectric materials. Chinese Science Bulletin 2025, 70 (6) , 697-704. https://doi.org/10.1360/TB-2024-0810
A. M. S. Arulanantham, K. V. Gunavathy, P. Mohanraj, S. Rex Rosario, S. Kumaresan, A. Mani. Influence of sulfur concentration on phase formation in SxnSy thin films deposited through nebulizer spray pyrolysis technique. Applied Physics A 2025, 131 (1) https://doi.org/10.1007/s00339-024-08147-6
Priyanka V. P., R. Venkatesh, S. S. Hegde, S. Valanarasu, K. S. Nivedhitha, N. R. Banapurmath. Remarkable fast-response visible light photodetectors based on SnS thin films on silicon substrates. Applied Physics A 2025, 131 (1) https://doi.org/10.1007/s00339-024-08189-w
R. Grijalva-Saavedra, G. Suárez-Campos, J. Fuentes-Ríos, M. Ruiz-Molina, J. Solís-Mosquera, M. A. Quevedo-Lopez, D. Cabrera-German, M. Sotelo-Lerma. Enhanced optical and electrical properties of Co-doped SnS thin films synthesized via chemical bath deposition. Journal of Materials Science: Materials in Electronics 2025, 36 (1) https://doi.org/10.1007/s10854-024-14126-7
Yanping Lv, Zhuanzhuan Song, Ziyi Qin, Jun Zhang, Ming Yang, Hao Wu. Probing into the low efficiency of CdS/SnS-based solar cells and remediation through surface treatments. Vacuum 2025, 231 , 113776. https://doi.org/10.1016/j.vacuum.2024.113776
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Yujuan Pei, Miaoran Kang, Weilong Deng, Qiang Fu, Xiangyu Fan, Yu Sui, Jubei Hu, Mengting Liu, Xianjie Wang, Bo Song. A self-powered photodetector of SnSeS/p-Si heterojunction with high-performance. Journal of Materials Chemistry C 2025, 19 https://doi.org/10.1039/D5TC00243E
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Yu P Gnatenko, A P Bukivskii, V Yu Yevdokymenko, A S Opanasyuk, P M Bukivskij, S A Iliash, I G Vertegel, O I Ovcharenko, R V Gamernyk. Optical and photoelectric properties of nanostructured SnS films obtained by spraying ink using a nanoparticle suspension. Materials Research Express 2024, 11 (12) , 125002. https://doi.org/10.1088/2053-1591/ad9b73
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M. Arabieh, M.R. Basaadat. Adsorbtive removal of HF toxic gas via tinsulfide monolayer modification: A molecular perspective. Chemosphere 2024, 364 , 143231. https://doi.org/10.1016/j.chemosphere.2024.143231
Dingding Jiang, Ya‐Nan Tang, Di Wang, Xiangpeng Xu, Jiang Sun, Rong Ma, Wenhao Li, Zhiya Han, Yunqi Liu, Dacheng Wei. Self‐Anchored Van‐Der‐Waals Stacking Growth of Transition‐Metal Dichalcogenide Nanoplates. Advanced Materials 2024, 160 https://doi.org/10.1002/adma.202407586
Benjamin Hudson Baby, Nirmal T Shajan, D. Paul Joseph, Fathima C A, Gincy K. Varghese, D. Bharathi Mohan. Phase stabilization of Fe doped SnS by solvothermal method and its structural, morphological and optoelectronic properties for photovoltaic applications. Solid State Communications 2024, 386 , 115525. https://doi.org/10.1016/j.ssc.2024.115525
M. S. Nithyapriya, S. Athithya, Sivalingam Muthu Mariappan, S. Harish, M. Navaneethan, J. Archana. Tailoring the work function of SnS2/SnO2 composites for improved counter electrode performance in dye-sensitized solar cells. Emergent Materials 2024, 7 (3) , 867-878. https://doi.org/10.1007/s42247-023-00618-5
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Rajneesh Kumar Mishra, Gyu Jin Choi, Ranjana Verma, Sun Hun Jin, Rajesh Bhardwaj, Sandeep Arya, Jay Singh, Jin Seog Gwag. Revolutionizing energy evolution: SnS-Sn2S3 layered structures as exceptional electrocatalytic materials for H2 and O2 generation. Materials Science and Engineering: B 2024, 303 , 117292. https://doi.org/10.1016/j.mseb.2024.117292
M.I. Khan, Shahar bano, Saddam Hussain, Norah Alwadai, Mahvish Fatima, Urram Shahzad, El Sayed Yousef, Munawar Iqbal. Heterostructure of TiO2 and SnS for enhancing the structural, optical and photovoltaic properties of solar cells. Optik 2024, 300 , 171625. https://doi.org/10.1016/j.ijleo.2024.171625
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Cite this: Chem. Mater. 2013, 25, 24, 4908–4916

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https://doi.org/10.1021/cm403046m

Published November 27, 2013

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Abstract
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Figure 1
Figure 1. Ground-state crystal structures of the three phases of tin (gray) sulfide (yellow): (a) SnS, (b) SnS₂, and (c) Sn₂S₃.
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Figure 2
Figure 2. Schematic of the CVT process, with red showing higher and blue showing cooler temperatures. The crystals are in yellow and the solid components black. Tin migrates as tin iodide toward the cooler end of the ampule, where Sn–S stoichiometries form and release the iodine. I₂ diffuses back toward the tin to create a cycle.
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Figure 3
Figure 3. Standard Gibbs free energies of the reactions involved in the tin iodide formation for the vapor transport of SnS, Sn₂S₃, and SnS₂ as a function of the temperature.
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Figure 4
Figure 4. Normalized pulse radiolysis TRMC traces recorded for SnS₂ and Sn₂S₃ using a pulsed 3 MeV electron beam.
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Figure 5
Figure 5. Dose-normalized change in conductivity for SnS₂ and Sn₂S₃. The x-axis shows time in nanoseconds and the y-axis shows the fractional change in microwave power reflected by the cell divided by the integrated beam charge per pulse (Q) in nano-Coulombs.
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Figure 6
Figure 6. Calculated band offset diagram, using the HSE06 functional, for each of the three tin sulfide phases using a vacuum alignment procedure and that of CZTS for reference. (92)
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References
This article references 100 other publications.
1. 1
  Wadia, C.; Alivisatos, A. P.; Kammen, D. M. Energy Environ. Sci. 2009, 43, 2072– 2077
  There is no corresponding record for this reference.
2. 2
  Peter, L. M. Philos. Trans. R. Soc. London, Ser. A 2011, 369, 1840– 1856
  2
  Towards sustainable photovoltaics: the search for new materials
  Peter, L. M.
  Philosophical Transactions of the Royal Society, A: Mathematical, Physical & Engineering Sciences (2011), 369 (1942), 1840-1856CODEN: PTRMAD; ISSN:1364-503X. (Royal Society)
  A review. The opportunities for photovoltaic (PV) solar energy conversion are reviewed in the context of projected world energy demands for the twenty-first century. Conventional single-crystal silicon solar cells are facing increasingly strong competition from thin-film solar cells based primarily on polycryst. absorber materials, such as cadmium telluride (CdTe) and copper indium gallium diselenide (CIGS). However, if PVs are to make a significant contribution to satisfy global energy requirements, issues of sustainability and cost will need to be addressed with increased urgency. There is a clear need to expand the range of materials and processes that is available for thin-film solar cell manuf., placing particular emphasis on low-energy processing and sustainable non-toxic raw materials. The potential of new materials is exemplified by copper zinc tin sulfide, which is emerging as a viable alternative to the more toxic CdTe and the more expensive CIGS absorber materials.
3. 3
  Scragg, J. J.; Dale, P. J.; Peter, L. M.; Zoppi, G.; Forbes, I. Physica Status Solidi (b) 2008, 245, 1772– 1778
  There is no corresponding record for this reference.
4. 4
  Chen, S.; Gong, X. G.; Walsh, A.; Wei, S. H. Appl. Phys. Lett. 2010, 96, 021902– 3
  4
  Defect physics of the kesterite thin-film solar cell absorber Cu2ZnSnS4
  Chen, Shiyou; Gong, X. G.; Walsh, Aron; Wei, Su-Huai
  Applied Physics Letters (2010), 96 (2), 021902/1-021902/3CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)
  Cu2ZnSnS4 is one of the most promising quaternary absorber materials for thin-film solar cells. Examn. of the thermodn. stability of this quaternary compd. reveals that the stable chem. potential region for the formation of stoichiometric compd. is small. Under these conditions, the dominant defect will be p-type CuZn antisite, which has an acceptor level deeper than the Cu vacancy. The dominant self-compensated defect pair in this quaternary compd. is [Cu-Zn+Zn+Cu]0, which gives various polytype structures of Cu2ZnSnS4. Probably to maximize the solar cell performance, growth of Cu2ZnSnS4 under Cu-poor/Zn-rich conditions will be optimal, if the pptn. of ZnS can be avoided by kinetic barriers. (c) 2010 American Institute of Physics.
5. 5
  Reddy, K. R.; Reddy, N. K.; Miles, R. Sol. Energy Mater. Sol. Cells 2006, 90, 3041– 3046
  There is no corresponding record for this reference.
6. 6
  Ferekides, C. S.; Balasubramanian, U.; Mamazza, R.; Viswanathan, V.; Zhao, H.; Morel, D. L. Sol. Energy 2004, 77, 823– 830
  6
  CdTe thin film solar cells: device and technology issues
  Ferekides, C. S.; Balasubramanian, U.; Mamazza, R.; Viswanathan, V.; Zhao, H.; Morel, D. L.
  Solar Energy (2004), 77 (6), 823-830CODEN: SRENA4; ISSN:0038-092X. (Elsevier Ltd.)
  A review of work on CdTe thin-film solar cells sponsored by the National Renewable Energy Lab. Thin film CdTe solar cells and modules are typically heterojunctions with CdS being the n-type partner, or window layer. The preferred configuration for CdTe solar cells is the superstrate structure. The cadmium chloride heat treatment, the back contact formation process, and the utilization of resistive buffer layers in tandem with a thin cadmium sulfide window layer, are important areas of research in thin film CdTe solar cells. Results for a vapor chloride heat treatment with high throughput characteristics, a dry back contact process, and a comparative study of resistive buffer layers and their effect on the performance of CdTe solar cells are presented.
7. 7
  Abou-Helal, M.; Boshta, M. J. Am. Sci. 2012, 8, 61– 63
  There is no corresponding record for this reference.
8. 8
  Reddy, K. R.; Reddy, P. P.; Datta, P.; Miles, R. Thin Solid Films 2002, 403–404, 116– 119
  There is no corresponding record for this reference.
9. 9
  Parenteau, M.; Carlone, C. Phys. Rev. B 1990, 41, 5227– 5234
  There is no corresponding record for this reference.
10. 10
  Anderson, J. S.; Morton, C. M. Proc. Russ. Soc. A 1945, 184, 873
  There is no corresponding record for this reference.
11. 11
  Shockley, W.; Queisser, H. J. J. Appl. Phys. 1961, 32, 510– 520
  11
  Detailed balance limit of efficiency of p-n junction solar cells
  Shockley, William; Queisser, Hans J.
  Journal of Applied Physics (1961), 32 (), 510-19CODEN: JAPIAU; ISSN:0021-8979.
  In order to find an upper theoretical limit for the efficiency of p-n junction solar energy converters, a limiting efficiency, called the detailed balance limit of efficiency, has been calcd. for an ideal case in which the only recombination mechanism of hole-electron pairs is radiative, as required by the principle of detailed balance. The efficiency is also calcd. for the case in which radiative recombination is only a fixed fraction fc of the total recombination, the rest being nonradiative. Efficiencies at the matched loads were calcd. with band gap and fc as parameters, the sun and cell being assumed to be black bodies with temps. of 6000°K. and 300°K., resp. The max. efficiency is 30% for an energy gap of 1.1 e.v. and fc = 1. Actual junctions do not obey the predicted current-voltage relation, and reasons for the difference and its relevance to efficiency are discussed.
12. 12
  Nair, M. T. S.; Nair, P. K. Semicond. Sci. Technol. 1991, 6, 132
  12
  Simplified chemical deposition technique for good quality tin monosulfide thin films
  Nair, M. T. S.; Nair, P. K.
  Semiconductor Science and Technology (1991), 6 (2), 132-4CODEN: SSTEET; ISSN:0268-1242.
  A chem. deposition technique, much simpler and more versatile than previously reported and capable of yielding good quality SnS films of thickness up to ≃1.2 μm under a choice of deposition conditions, is presented. The as-prepd. films are polycryst. with p-type dark cond. in the range 10-5-10-4 Ω-1cm-1 for the thicker (∼1 μm) films and showing a photocurrent to dark current ratio of 5-10 under 500 W m-2 tungsten halogen illumination. The optical transmittance and reflectance spectra and the photocurrent response curves of a series of SnS samples are explicitly presented to provide insight into possible applications of these films.
13. 13
  Prince, M. B. J. Appl. Phys. 1955, 26, 534– 540
  There is no corresponding record for this reference.
14. 14
  Loferski, J. J. J. Appl. Phys. 1956, 27, 777– 784
  14
  Theoretical considerations governing the choice of the optimum semiconductor for photovoltaic solar energy conversion
  Loferski, Joseph J.
  Journal of Applied Physics (1956), 27 (), 777-84CODEN: JAPIAU; ISSN:0021-8979.
  Diode reverse satn. current is computed from the published values of the semiconductor parameters of 3 intermetallic compounds, i.e., InP, GaAs, and CdTe, and it is shown that the efficiencies predicted for these materials are greater than those predicted for other materials which have been proposed, i.e., Si, CdS, Se, and AlSb.
15. 15
  Albers, W.; Haas, C.; J. Vink, H.; Wasscher, J. D. J. Appl. Phys. 1961, 32, 2220
  15
  Investigations on SnS
  Albers, W.; Haas, C.; Vink, H. J.; Wasscher, J. D.
  Journal of Applied Physics (1961), 32 (), 2220-5CODEN: JAPIAU; ISSN:0021-8979.
  The p, T, x diagram of the Sn-S system was detd., especially in the region of the compd. SnS. The pressure of S2 in equil. with SnS and a liquid phase was found to extend over several decades up to 25 mm. Hg at the "Sn-rich" side, whereas at the "S-rich" side the S2 pressures in equil. with solid SnS and a liquid phase lie between 25 mm. Hg and 100 mm. Hg. The existence region of solid SnS very probably lies entirely at the excess-sulfur side. The hole mobility in a plane perpendicular to the c axis, ≈90 cm.2/v. sec. at room temp., was proportional to T-2.2 for higher temps. The mobility in the direction of the c axis was about 1/5 as great. Reversible annealing effects were found for temps, above 200°C. which could be explained by assuming assocn. of neutral Sn vacancies. Absorption measurements showed that the edge absorption is due to indirect transitions. The bandgap was 1.08 e.v. at 300°K. and 1.115 e.v. at 77°K. Interband transitions in the valence band were also found. The effective charge of the atoms (e* = 0.7 c0) and the effective masses of the holes in the 3 principal crystal directions (ma* = mb* = 0.20 m0; mc* ≈ m0) were detd. from reflection measurements in the infrared. From these values and the value for the d. of states mass obtained by means of the Seebeck effect (md* ≥0.95 m0), the no. of equiv. max. of the valence band was at least 4.
16. 16
  Fthenakis, V. Renew. Sust. Energy Rev. 2009, 13, 2746– 2750
  16
  Sustainability of photovoltaics: The case for thin-film solar cells
  Fthenakis, Vasilis
  Renewable & Sustainable Energy Reviews (2009), 13 (9), 2746-2750CODEN: RSERFH; ISSN:1364-0321. (Elsevier Ltd.)
  To ensure photovoltaics become a major sustainable player in a competitive power-generation market, they must provide abundant, affordable electricity, with environmental impacts drastically lower than those from conventional power generation. The recent redn. in the cost of 2nd generation thin-film PV is remarkable, meeting the prodn. milestone of $1 per W in the fourth quarter of 2008. This achievement holds great promise for the future. However, the questions remaining are whether the expense of PV modules can be lowered further, and if there are resource- and environmental-impact constraints to growth. I examine the potential of thin-films in a prospective life-cycle anal., focusing on direct costs, resource availability, and environmental impacts. These three aspects are closely related; developing thinner solar cells and recycling spent modules will become increasingly important in resolving cost, resource, and environmental constraints to large scales of sustainable growth.
17. 17
  Sinsermsuksakul, P.; Hartman, K.; Kim, S. B.; Heo, J.; Sun, L.; Park, H. H.; Chakraborty, R.; Buonassisi, T.; Gordon, R. G. Appl. Phys. Lett. 2013, 102, 053901
  There is no corresponding record for this reference.
18. 18
  Reddy, N.; Reddy, K. T. R.Conference Record of the Twenty Sixth IEEE Photovoltaic Specialists Conference;
  Anaheim, CA, Sept 29–Oct 3, 2007
  IEEE: Piscataway, NJ, 1997.
  There is no corresponding record for this reference.
19. 19
  Burton, L. A.; Walsh, A. Appl. Phys. Lett. 2013, 102, 132111
  There is no corresponding record for this reference.
20. 20
  Scragg, J. J.; Watjen, J. T.; Edoff, M.; Ericson, T.; Kubart, T.; Platzer-Bjorkman, C. J. Am. Chem. Soc. 2012, 134, 19330– 19333
  There is no corresponding record for this reference.
21. 21
  Richard, A. P. Single Crystal Growth, Powder Synthesis and Characterization of Layered Chalcogenide Semiconductors. Ph.D. thesis, Oregon State University, Corvallis, OR, 2011.
  There is no corresponding record for this reference.
22. 22
  Reddy, K. R.; Reddy, P. P.; Miles, R.; Datta, P. Opt. Mater. 2001, 17, 295– 298
  There is no corresponding record for this reference.
23. 23
  Vidal, J.; Lany, S.; d’Avezac, M.; Zunger, A.; Zakutayev, A.; Francis, J.; Tate, J. Appl. Phys. Lett. 2012, 100, 032104
  23
  Band-structure, optical properties, and defect physics of the photovoltaic semiconductor SnS
  Vidal, Julien; Lany, Stephan; d'Avezac, Mayeul; Zunger, Alex; Zakutayev, Andriy; Francis, Jason; Tate, Janet
  Applied Physics Letters (2012), 100 (3), 032104/1-032104/4CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)
  SnS is a potential earth-abundant photovoltaic (PV) material. Employing both theory and expt. to assess the PV relevant properties of SnS, we clarify on whether SnS has an indirect or direct band gap and what is the minority carrier effective mass as a function of the film orientation. SnS has a 1.07 eV indirect band gap with an effective absorption onset located 0.4 eV higher. The effective mass of minority carrier ranges from 0.5 m0 perpendicular to the van der Waals layers to 0.2 m0 into the van der Waals layers. The pos. characteristics of SnS feature a desirable p-type carrier concn. due to the easy formation of acceptor-like intrinsic Sn vacancy defects. Potentially detrimental deep levels due to SnS antisite or S vacancy defects can be suppressed by suitable adjustment of the growth condition towards S-rich. (c) 2012 American Institute of Physics.
24. 24
  Sinsermsuksakul, P.; Heo, J.; Noh, W.; Hock, A. S.; Gordon, R. G. Adv. Energy Mater. 2011, 1116– 1125
  24
  Atomic layer deposition of tin monosulfide thin films
  Sinsermsuksakul, Prasert; Heo, Jaeyeong; Noh, Wontae; Hock, Adam S.; Gordon, Roy G.
  Advanced Energy Materials (2011), 1 (6), 1116-1125CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
  Thin film solar cells made from earth-abundant, non-toxic materials are needed to replace the current technol. that uses Cu(In,Ga)(S,Se)2 and CdTe, which contain scarce and toxic elements. One promising candidate absorber material is tin monosulfide (SnS). In this report, pure, stoichiometric, single-phase SnS films were obtained by at. layer deposition (ALD) using the reaction of bis(N,N'-diisopropylacetamidinato)tin(II) [Sn(MeC(N-iPr)2)2] and hydrogen sulfide (H2S) at low temps. (100 to 200 °C). The direct optical band gap of SnS is around 1.3 eV and strong optical absorption (α > 104 cm-1) is obsd. throughout the visible and near-IR spectral regions. The films are p-type semiconductors with carrier concn. on the order of 1016 cm-3 and hole mobility 0.82-15.3 cm2V-1s-1 in the plane of the films. The elec. properties are anisotropic, with three times higher mobility in the direction through the film, compared to the in-plane direction.
25. 25
  Sinsermsuksakul, P.; Chakraborty, R.; Kim, S. B.; Heald, S. M.; Buonassisi, T.; Gordon, R. G. Chem. Mater. 2012, 24, 4556
  There is no corresponding record for this reference.
26. 26
  Walsh, A.; Woodley, S. M.Phys. Chem. Chem. Phys. 2010, 12.
  There is no corresponding record for this reference.
27. 27
  Burton, L. A.; Walsh, A. J. Phys. Chem. C 2012, 116, 24262– 24267
  There is no corresponding record for this reference.
28. 28
  P. Boudjouk, S. R. B.; Seidler, D. J.; McCarthey, G. J. Chem. Mater. 1994, 6, 2108
  There is no corresponding record for this reference.
29. 29
  Sanchez-Juarez, A.; Ortiz, A. Semicond. Sci. Technol. 2002, 17, 931
  29
  Effects of precursor concentration on the optical and electrical properties of SnxSy thin films prepared by plasma-enhanced chemical vapor deposition
  Sanchez-Juarez, A.; Ortiz, A.
  Semiconductor Science and Technology (2002), 17 (9), 931-937CODEN: SSTEET; ISSN:0268-1242. (Institute of Physics Publishing)
  The authors have carried out the elec. and optical characterization of thin films of compds. based on Sn-S bonds (SnS2, Sn2S3), prepd. by plasma-enhanced CVD (PECVD), as a function of the relative concn. of the precursor vapors, SnCl4 and H2S, keeping all other deposition parameters const. In all studied cases, the deposited films were formed by polycryst. materials. The optical bandgap values of deposited materials were calcd. from optical transmittance and reflectance measurements. The SnS2 compd. produced under certain deposition conditions has a forbidden bandgap around 2.2 eV. This compd. shows n-type elec. cond., whose dark value at room temp. is 2 × 10-2 (Ω cm)-1. Also, it shows the typical semiconductor dependence of its elec. cond. on the temp. with an activation energy of ∼0.15 eV. However, thin films of a mixt. of SnS2 and Sn2S3 compds. were deposited with higher values of the relative concn. of source vapors than those used to obtain the SnS2 compd. The optical bandgap shows a decreasing trend as the relative concn. increases. A similar trend is obsd. for dark elec. cond. These results create the opportunity to use SnxSy compds. in thin films for building heterojunction solar cells prepd. completely by PECVD.
30. 30
  Khadraoui, M.; Benramdane, N.; Mathieu, C.; Bouzidi, A.; Miloua, R.; Kebbab, Z.; Sahraoui, K.; Desfeux, R. Solid State Commun. 2010, 150, 297– 300
  There is no corresponding record for this reference.
31. 31
  Nassary, M. J. Alloys Compd. 2005, 398, 21– 25
  31
  Temperature dependence of the electrical conductivity, Hall effect and thermoelectric power of SnS single crystals
  Nassary, M. M.
  Journal of Alloys and Compounds (2005), 398 (1-2), 21-25CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)
  The elec. cond. and the Hall effect were measured on a SnS single crystal, grown by the Bridgman method over the temp. range 141-523 K, in two crystallog. directions. The investigated sample was found to be of p-type cond. The cond. at room temp. was σ// = 0.193 Ω-1 cm-1, σ.perp. = 0.063 Ω-1 cm-1 parallel and perpendicular to layers plane, resp. The energy gap was calcd. to be Eg// = 1.106 eV and Eg.perp. = 0.56 eV parallel and perpendicular to layers plane, resp. The thermoelec. power measurements of SnS were made in temp. range from 172 to 410 K. The combination of the elec. and thermal measurements makes it possible to deduce a lot of phys. parameters, such as mobilities ratio, effective masses, relaxation times, diffusion lengths and diffusion coeffs. for majority and minority carriers at room temp.
32. 32
  Huang, C.-C.; Lin, Y.-J.; Chuang, C.-Y.; Liu, C.-J.; Yang, Y.-W. J. Alloys Compd. 2013, 553, 208– 211
  32
  Conduction-type control of SnSx films prepared by the sol-gel method for different sulfur contents
  Huang, Chung-Cheng; Lin, Yow-Jon; Chuang, Cheng-Yu; Liu, Chia-Jyi; Yang, Yao-Wei
  Journal of Alloys and Compounds (2013), 553 (), 208-211CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)
  The effect of S content on the elec. property of the sol-gel SnSx films was examd. The obsd. conduction-type changes are related to the different ratios between the concns. of Sn4+ and Sn2+. The exptl. identification confirms that n-type conversion is due to an increase in the at. concn. ratio of Sn4+/(Sn4+ + Sn2+) in the S-rich film. The probability of having formed Sn vacancies (VSn) should be high under S-rich growth conditions. Transformation from VSn to V2-Sn is accompanied by lattice relaxation. Therefore, transformation from Sn2+ to Sn4+ is an offset to lattice relaxation under S-rich growth conditions, increasing the electron d. and producing n-type conversion. A suitable sulfur concn. is an important issue for tuning conduction type of SnSx.
33. 33
  Sanchez-Juarez, A.; Tiburcio-Silver, A.; Ortiz, A. Thin Solid Films 2005, 480?481, 452– 456
  There is no corresponding record for this reference.
34. 34
  Ogah, O. E.; Zoppi, G.; Forbes, I.; Miles, R. Thin Solid Films 2009, 517, 2485– 2488
  There is no corresponding record for this reference.
35. 35
  Cruz, M.; Morales, J.; Espinos, J. P.; Sanz, J. J. Solid State Chem. 2003, 175, 359– 365
  35
  XRD, XPS and 119Sn NMR study of tin sulfides obtained by using chemical vapor transport methods
  Cruz, M.; Morales, J.; Espinos, J. P.; Sanz, J.
  Journal of Solid State Chemistry (2003), 175 (2), 359-365CODEN: JSSCBI; ISSN:0022-4596. (Elsevier Science)
  Application of the chem. vapor transport method to the Sn-S system allowed three different phases (viz. SnS, SnS2 and Sn2S3) to be synthesized. No evidence of the formation of other, previously reported mixed valence compds. such as Sn3S4 or Sn4S5 was found, whichever the Sn:S at. ratio and temp. gradient used. Except for SnS2, which was always obtained as a pure phase as a result of starting from the required stoichiometry, a mixed phase was invariably obtained. The XPS spectrum for Sn2S3 was only slightly different from those for SnS and SnS2 in spite of the presence of Sn(II) and Sn(IV) in the former compd., which hindered the identification of mixed valence compds. in the Sn-S system using this spectroscopic technique. By contrast, the chem. shifts, anisotropy and skew parameters for Sn2S3 as obtained by 119Sn NMR were markedly different from those for SnS and SnS2, and reflected the severe distortion of Sn(IV) and, esp., Sn(II) in the former compd. relative to the latter two. The time scale for this resonance technique is shorter than the lifetime of the valence states, which allows one to unambiguously distinguish the two oxidn. states of Sn.
36. 36
  Kana, A. T.; Hibbert, T. G.; Mahon, M. F.; Molloy, K. C.; Parkin, I. P.; Price, L. S. Polyhedron 2001, 20, 2989– 2995
  There is no corresponding record for this reference.
37. 37
  Nair, P. K.; Nair, M. T. S.; Garcia, V. M.; Arenas, O. L.; Pena, Y.; Castillo, A.; Ayala, I. T.; Gomezdaza, O.; Sanchez, A.; Campos, J.; Hu, H.; Suarez, R.; Rincon, M. E. Sol. Energy Mater. Sol. Cells 1998, 52, 313– 344
  37
  Semiconductor thin films by chemical bath deposition for solar energy related applications
  Nair, P. K.; Nair, M. T. S.; Garcia, V. M.; Arenas, O. L.; Pena, Y.; Castillo, A.; Ayala, I. T.; Gomezdaza, O.; Sanchez, A.; Campos, J.; Hu, H.; Suarez, R.; Rincon, M. E.
  Solar Energy Materials and Solar Cells (1998), 52 (3-4), 313-344CODEN: SEMCEQ; ISSN:0927-0248. (Elsevier Science B.V.)
  A review with 84 refs. In this paper we present the basic concepts underlying the chem. bath deposition technique and the recipes developed in our lab. during the past ten years for the deposition of good-quality thin films of CdS, CdSe, ZnS, ZnSe, PbS, SnS, Bi2S3, Bi2Se3, Sb2S3, CuS, CuSe, etc. Typical growth curves, and optical and elec. properties of these films are presented. The effect of annealing the films in air on their structure and compn. and on the elec. properties is notable: CdS and ZnS films become conductive through a partial conversion to oxide phase; CdSe becomes photosensitive, SnS converts to SnO2, etc. The use of ppts. formed during deposition for screen printing and sintering, in polymer composites and as a source for vapor-phase deposition is presented. Some examples of the application of the films in solar energy related work are presented.
38. 38
  Ghazali, A.; Zainal, Z.; Hussein, M. Z.; Kassim, A. Sol. Energy Mater. Sol. Cells 1998, 55, 237– 249
  38
  Cathodic electrodeposition of SnS in the presence of EDTA in aqueous media
  Ghazali, Arniza; Zainal, Zulkarnain; Zobir Hussein, Mohd; Kassim, Anuar
  Solar Energy Materials and Solar Cells (1998), 55 (3), 237-249CODEN: SEMCEQ; ISSN:0927-0248. (Elsevier Science B.V.)
  Cathodic electrodeposition in the presence of EDTA in aq. soln. was found to offer some noteworthy improvements in our attempt to synthesize an SnS thin film. EDTA has shown its capacity for improving the longevity of the deposition bath as well as the adhesion of the deposited film on a titanium substrate. Photoelectrochem. anal. reveals outstanding photoactivity of the electrodeposited thin film, while an optical study shows an energy gap of approx. 1.1 eV. The effects of chelating agent were extd. from the results of cyclic voltammetry, photoelectrochem. test, SEM and X-ray diffraction spectroscopy. The latter which displays better defined signals reaffirms the appreciable improvement in the polycrystallinity of the thin film. Anal. of peak locations, coincidentally, confirms that SnS of Herzenbergite form has been obtained.
39. 39
  Sugiyama, M.; Miyauchi, K.; Minemura, T.; Ohtsuka, K.; Noguchi, K.; Nakanishi, H. Jpn. J. Appl. Phys. 2008, 47, 4494– 4495
  39
  Preparation of SnS films by sulfurization of Sn sheet
  Sugiyama, Mutsumi; Miyauchi, Keisuke; Minemura, Takehiro; Ohtsuka, Kenichi; Noguchi, Koji; Nakanishi, Hisayuki
  Japanese Journal of Applied Physics (2008), 47 (6, Pt. 1), 4494-4495CODEN: JJAPB6 ISSN:. (Japan Society of Applied Physics)
  SnS films were grown by sulfurization using an inexpensive Sn sheet and S powder. The Sn sheet was sulfurized in a closed ampoule at a low temp. between 150 and 300°. The resulting sulfurized films had a flat surface and large grains, and exhibited adhered very well to the substrate. These samples exhibited X-ray diffraction peaks corresponding to SnS and contained no extra phases. These results represent the first step toward realizing an optical device such as a solar cell using a SnS film grown by a sulfurization method.
40. 40
  Xu, Z.; Chen, Y. Semicond. Sci. Technol. 2012, 27, 035007
  There is no corresponding record for this reference.
41. 41
  Ghosh, B.; Das, M.; Banerjee, P.; Das, S. Appl. Surf. Sci. 2008, 254, 6436– 6440
  There is no corresponding record for this reference.
42. 42
  Hartman, K.; Johnson, J.; Bertoni, M. I.; Recht, D.; Aziz, M. J.; Scarpulla, M. A.; Buonassisi, T. Thin Solid Films 2011, 519, 7421– 7424
  There is no corresponding record for this reference.
43. 43
  Schafer, H. Z. Anorg. Chem 1956, 286, 42
  There is no corresponding record for this reference.
44. 44
  Nitsche, R.; Bolsterli, H. U.; Lichtensteiger, M. J. Phys. Chem. Solids 1961, 21, 199– 205
  44
  Crystal growth by chemical transport reactions. I. Binary, ternary, and mixed-crystal chalcogenides
  Nitsche, R.; Bolsterli, H. U.; Lichtensteiger, M.
  Physics and Chemistry of Solids (1961), 21 (), 199-205CODEN: PCSOA7; ISSN:0369-8726.
  The concept of chem. transport reactions (volatilization of a material via a low-volatile chem. intermediate at a temp. T1 and back-reaction of the mixt. at a temp. T2, using the temp. dependence of the chem. equil. involved) is a valuable tool for growing single crystals of many materials which cannot be easily obtained from the melt. The main advantage is the use of growth temps. well below the melting or sublimation point. The method was used to grow crystals of the binary chalcogenides: ZnS, ZnSe, CdS, CdSe, MnS, SnS, SnS2, In2S3, Ga2S3, GaS, and GaSe. Ternary chalcogenides of the type AB2X4 (A = Zn, Cd, Hg; B = Ga, In; X = S, Se) were obtained for the first time as single crystals. Mixed crystals of ZnS.MnS were prepd. over a wide range of compn.
45. 45
  Colombara, D.; Delsante, S.; Borzone, G.; Mitchels, J.; Molloy, K.; Thomas, L.; Mendis, B.; Cummings, C.; Marken, F.; Peter, L. J. Cryst. Growth 2013, 364, 101– 110
  45
  Crystal growth of Cu2ZnSnS4 solar cell absorber by chemical vapor transport with I2
  Colombara, D.; Delsante, S.; Borzone, G.; Mitchels, J. M.; Molloy, K. C.; Thomas, L. H.; Mendis, B. G.; Cummings, C. Y.; Marken, F.; Peter, L. M.
  Journal of Crystal Growth (2013), 364 (), 101-110CODEN: JCRGAE; ISSN:0022-0248. (Elsevier B.V.)
  Single crystals of Cu2ZnSnS4 have been produced within sealed quartz ampuls via the chem. vapor transport technique using I2 as the transporting agent. The effects of temp. gradient and I2 load on the crystal habit and compn. are considered. Crystals have been analyzed with XRD, SEM, and TEM for compositional and structural uniformities at both microscopic and nanoscopic levels. The synthesized crystals have suitable (I2-load dependent) properties and are useful for further solar absorber structural and phys. characterizations. A new chem. vapor transport method based on longitudinally isothermal treatments is attempted. Based on a proposed simplistic mechanism of crystal growth, conditions for crystal enlargement with the new method are envisaged.
46. 46
  Schouten, P. G.; Warman, J. M.; de Haas, M. P. J. Phys. Chem. 1993, 97, 9863– 9870
  There is no corresponding record for this reference.
47. 47
  Warman, J. M.; de Haas, M. P.; Dicker, G.; Grozema, F. C.; Piris, J.; Debije, M. G. Chem. Mater. 2004, 16, 4600– 4609
  There is no corresponding record for this reference.
48. 48
  Hohenberg, P.; Kohn, W. Phys. Rev. 1964, 136, B864– B871
  There is no corresponding record for this reference.
49. 49
  Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1133– A1138
  There is no corresponding record for this reference.
50. 50
  Kresse, G.; Furthmüller, J. Phys. Rev. B 1996, 54, 11169
  50
  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
  Kresse, G.; Furthmueller, J.
  Physical Review B: Condensed Matter (1996), 54 (16), 11169-11186CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
  The authors present an efficient scheme for calcg. the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrixes will be discussed. This approach is stable, reliable, and minimizes the no. of order Natoms3 operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special "metric" and a special "preconditioning" optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calcns. It will be shown that the no. of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order Natoms2 scaling is found for systems contg. up to 1000 electrons. If we take into account that the no. of k points can be decreased linearly with the system size, the overall scaling can approach Natoms. They have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large no. of different systems (liq. and amorphous semiconductors, liq. simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable.
51. 51
  Kresse, G.; Joubert, D. Phys. Rev. B 1999, 59, 1758
  51
  From ultrasoft pseudopotentials to the projector augmented-wave method
  Kresse, G.; Joubert, D.
  Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
  The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
52. 52
  Perdew, J. P.; Ruzsinszky, A.; Csonka, G. I.; Vydrov, O. A.; Scuseria, G. E.; Constantin, L. A.; Zhou, X.; Burke, K. Phys. Rev. Lett. 2008, 100, 136406
  52
  Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
  Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gabor I.; Vydrov, Oleg A.; Scuseria, Gustavo E.; Constantin, Lucian A.; Zhou, Xiaolan; Burke, Kieron
  Physical Review Letters (2008), 100 (13), 136406/1-136406/4CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
  Popular modern generalized gradient approxns. are biased toward the description of free-atom energies. Restoration of the first-principles gradient expansion for exchange over a wide range of d. gradients eliminates this bias. We introduce a revised Perdew-Burke-Ernzerhof generalized gradient approxn. that improves equil. properties of densely packed solids and their surfaces.
53. 53
  Heyd, J.; Scuseria, G. E.; Ernzerhof, M. J. Chem. Phys. 2006, 124, 219906
  53
  Hybrid functionals based on a screened Coulomb potential. [Erratum to document cited in CA139:042043]
  Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  Journal of Chemical Physics (2006), 124 (21), 219906/1CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
  The screening parameter quoted in this paper (ω=0.15) is not the one that was actually used in the code. In order to reproduce our results, two ω values are needed: ω =0.15 2≈0.106 for Hartree-Fock and ω=0.15x21/3 ≈0.189 for the PBE part. This erratum applies to all of our ωPBEh and HSE calcns. published to date. The authors emphasize that all the results obtained with this functional are reproducible using the two ω values quoted. The validity of all the published HSE values is not affected. Optimization of a single value of ω for a functional of the type reported in this paper will be presented elsewhere.
54. 54
  Head, J. D.; Zerner, M. C. Chem. Phys. Lett. 1985, 122, 264– 270
  There is no corresponding record for this reference.
55. 55
  Blum, V.; Gehrke, R.; Hanke, F.; Havu, P.; Havu, V.; Ren, X.; Reuter, K.; Scheffler, M. Comput. Phys. Commun. 2009, 180, 2175– 2196
  55
  Ab initio molecular simulations with numeric atom-centered orbitals
  Blum, Volker; Gehrke, Ralf; Hanke, Felix; Havu, Paula; Havu, Ville; Ren, Xinguo; Reuter, Karsten; Scheffler, Matthias
  Computer Physics Communications (2009), 180 (11), 2175-2196CODEN: CPHCBZ; ISSN:0010-4655. (Elsevier B.V.)
  We describe a complete set of algorithms for ab initio mol. simulations based on numerically tabulated atom-centered orbitals (NAOs) to capture a wide range of mol. and materials properties from quantum-mech. first principles. The full algorithmic framework described here is embodied in the Fritz Haber Institute "ab initio mol. simulations" (FHI-aims) computer program package. Its comprehensive description should be relevant to any other first-principles implementation based on NAOs. The focus here is on d.-functional theory (DFT) in the local and semilocal (generalized gradient) approxns., but an extension to hybrid functionals, Hartree-Fock theory, and MP2/GW electron self-energies for total energies and excited states is possible within the same underlying algorithms. An all-electron/full-potential treatment that is both computationally efficient and accurate is achieved for periodic and cluster geometries on equal footing, including relaxation and ab initio mol. dynamics. We demonstrate the construction of transferable, hierarchical basis sets, allowing the calcn. to range from qual. tight-binding like accuracy to meV-level total energy convergence with the basis set. Since all basis functions are strictly localized, the otherwise computationally dominant grid-based operations scale as O(N) with system size N. Together with a scalar-relativistic treatment, the basis sets provide access to all elements from light to heavy. Both low-communication parallelization of all real-space grid based algorithms and a ScaLapack-based, customized handling of the linear algebra for all matrix operations are possible, guaranteeing efficient scaling (CPU time and memory) up to massively parallel computer systems with thousands of CPUs.
56. 56
  Knacke, O.; Kubaschewski, O. Thermochemical Properties of Inorganic Substances, 2nd ed.; Springer-Verlag: Dusseldorf, Germany, 1991.
  There is no corresponding record for this reference.
57. 57
  Colombara, D. Investigation of Chalcogenide Absorber Materials for Photovoltaic Applications. Ph.D. thesis,University of Bath, Bath, U.K., 2012.
  There is no corresponding record for this reference.
58. 58
  Lambros, A.; Geraleas, D.; Economou, N. J. Phys. Chem. Solids 1974, 35, 537– 541
  58
  Optical absorption edge in tin sulfide
  Lambros, A. P.; Geraleas, D.; Economou, N. A.
  Journal of Physics and Chemistry of Solids (1974), 35 (4), 537-41CODEN: JPCSAW; ISSN:0022-3697.
  Optical absorption in single crystals of SnS was studied at many temps. at 100-300°K, at 2.2-0.8 μ. From the interference fringe patterns the absorption coeff., reflection coeff. and n as a function of wavelength were detd. for 2 light polarizations (ε‖a and ε‖b). From an anal. of the data, indirect band gaps of 1.142 and 1.095 eV were found for the 2 directions of polarization. Also it was found that the phonon assisted transitions required the participation of 2 phonons at different energy thresholds with energies 0.033 or 0.038 eV and 0.082 or 0.113 eV, with ref. to the 2 axes. The temp. dependence of the indirect band gap for each direction of light polarization is linear with a slope -4.05 × 10-3 and -4.37 × 10-3 eV, resp.
59. 59
  Kniep, R.; Mootz, D.; Severin, U.; Wunderlich, H. Acta Crystallogr., Sect. B 1982, 38, 2022– 2023
  There is no corresponding record for this reference.
60. 60
  Hazen, M. R.; Finger, L. W. Am. Mineral. 1978, 63, 289– 292
  There is no corresponding record for this reference.
61. 61
  Chattopadhyay, T.; Pannetier, J.; Von Schnering, H. G. J. Phys. Chem. Solids 1986, 47, 879– 885
  61
  Neutron diffraction study on the structural phase transition in tin sulfide (SnS) and tin selenide (SnSe)
  Chattopadhyay, T.; Pannetier, J.; Von Schnering, H. G.
  Journal of Physics and Chemistry of Solids (1986), 47 (9), 879-85CODEN: JPCSAW; ISSN:0022-3697.
  The structural phase transitions in SnS and SnSe were investigated by neutron diffraction at 295-1000 K using a high temp. furnace. Accurate positional and thermal parameters were obtained as a function of temp. both in the α- (GeS-type, B16) and β-phase (TII-type, B33). These investigations indicate that the α →β phase transitions in SnS and SnSe are of 2nd-order displacive type, and consist mainly of the continuous movement of Sn and S/Se atoms almost entirely along the [100] direction, and suggest the soft-mode behavior of a zone-boundary phonon of the β-phase.
62. 62
  Price, L. S.; Parkin, I. P.; Hardy, A. M. E.; Clark, R. J. H.; Hibbert, T. G.; Molloy, K. C. Chem. Mater. 1999, 11, 1792– 1799
  There is no corresponding record for this reference.
63. 63
  Guang-Pu, W.; Zhi-Lin, Z.; Wei-Ming, Z.; Xiang-Hong, G.; Wei-Qun, C.; Tanamura, H.; Yamaguchi, M.; Noguchi, H.; Nagatomo, T.; Omoto, O.Photovoltaic Energy Conversion, 1994, Conference Record of the Twenty Fourth IEEE Photovoltaic Specialists Conference;
  Waikoloa, HI, Dec 5–9, 1994
  ; IEEE: Piscataway, NJ, 1994.
  There is no corresponding record for this reference.
64. 64
  Ristova, M.; Ristov, M. Sol. Energ. Mat. Sol. C. 1998, 53, 95– 102
  There is no corresponding record for this reference.
65. 65
  Yanuar; Guastavino, F.; Llinares, C.; Djessas, K.; Masse, G. J. Mater. Sci. Lett. 2000, 19, 2135– 2137
  There is no corresponding record for this reference.
66. 66
  Calixto-Rodriguez, M.; Martinez, H.; Sanchez-Juarez, A.; Campos-Alvarez, J.; Tiburcio-Silver, A.; Calixto, M. Thin Solid Films 2009, 517, 2497– 2499
  There is no corresponding record for this reference.
67. 67
  Madelung, O. Semiconductors: Data Handbook, 3rd ed.; Springer: New York, 2004.
  There is no corresponding record for this reference.
68. 68
  Reddy, N. K.; Reddy, K. R. Solid-State Electron. 2005, 49, 902– 906
  68
  Electrical properties of spray pyrolytic tin sulfide films
  Reddy, N. Koteeswara; Reddy, K. T. Ramakrishna
  Solid-State Electronics (2005), 49 (6), 902-906CODEN: SSELA5; ISSN:0038-1101. (Elsevier Ltd.)
  Tin sulfide (SnxSy) films were prepd. using spray pyrolysis technique at different substrate temps. (Ts), (100-450°C) on Corning 7059 glass substrates. The phys. parameters such as elec. resistivity, Hall mobility and net carrier d. of the films were detd. at room temp. The films grown in the substrate temp. range, 300-375°C, were found to be p-type conducting. These SnS films showed av. elec. resistivity of ∼30 Ω cm, Hall mobility of ∼130 cm2/V s and carrier d., >1015 cm-3. The temp. dependence of elec. cond. of the films was also studied and the activation energies evaluated. The results obtained were discussed and reported.
69. 69
  Reddy, N. K.; Reddy, K. T. R. Mater. Chem. Phys. 2007, 102, 13– 18
  69
  Preparation and characterisation of sprayed tin sulphide films grown at different precursor concentrations
  Reddy, N. Koteeswara; Reddy, K. T. Ramakrishna
  Materials Chemistry and Physics (2007), 102 (1), 13-18CODEN: MCHPDR; ISSN:0254-0584. (Elsevier B.V.)
  Tin sulfide films were grown by spray pyrolysis technique at different precursor concns. varied in the range, 0.01-0.2 M keeping other deposition parameters const. The phys. properties of the deposited films were systematically studied in relation to the precursor concn. The studies indicated that the films grown in the precursor concn. range, 0.09-0.13 M were nearly stoichiometric with the Sn, S ratio of 1.06 and exhibited only SnS phase with a strong (1 1 1) preferred orientation that belongs to the orthorhombic crystal structure. These single-phase films showed an av. elec. resistivity of 32.9 Ω cm, Hall mobility of 139 cm2 V-1/s and carrier d. of ∼1015 cm-3. These films had an av. optical band gap of 1.32 eV with an absorption coeff. greater than 104 cm-1. These properties demonstrated that single-phase SnS films could be used as an absorber layer in the fabrication of heterojunction solar cells.
70. 70
  Amalraj, L.; Sanjeeviraja, C.; Jayachandran, M. J. Cryst. Growth 2002, 234, 683– 689
  70
  Spray pyrolysed tin disulphide thin film and characterisation
  Amalraj, L.; Sanjeeviraja, C.; Jayachandran, M.
  Journal of Crystal Growth (2002), 234 (4), 683-689CODEN: JCRGAE; ISSN:0022-0248. (Elsevier Science B.V.)
  Thin film of tin disulfide on glass substrate is prepd. by spray pyrolysis technique at a substrate temp. of 458 K. Using the hot probe technique the type of semiconductor is found to be n-type. X-ray diffraction anal. revealed the polycryst. nature of the film with hexagonal structure and a preferential orientation along the (0 0 1) plane. Fiber-like surface morphol. has been obsd. on the film. The surface compn. of the elements is analyzed with EDAX spectrum. A value of 3.85×10-7 Ω-1 cm-1 for the room temp. (302 K) cond. is detd. using the four-probe method. Activation energy of about 0.25 eV is detd. by plotting a graph between log (cond.) vs. reciprocal temp. The optical absorption and transmittance spectra have been recorded for this film in the wavelength range 380-900 nm. Thickness of the film and variation of absorption coeff. with wavelength are detd. using these spectral data. Band gap values of 2.16 eV with indirect allowed and 1.82 eV with indirect forbidden nature are obsd. for this pyrolyzed SnS2 thin film.
71. 71
  Julien, C.; Eddrief, M.; Samaras, I.; Balkanski, M. Mater. Sci. Eng., B 1992, 15, 70– 72
  There is no corresponding record for this reference.
72. 72
  Noguchi, H.; Setiyadi, A.; Tanamura, H.; Nagatomo, T.; Omoto, O. Sol. Energy Mater. Sol. Cells 1994, 35, 325– 331
  72
  Characterization of vacuum-evaporated tin sulfide film for solar cell materials
  Noguchi, Hidenori; Setiyadi, Agus; Tanamura, Hiromasa; Nagatomo, Takao; Omoto, Osamu
  Solar Energy Materials and Solar Cells (1994), 35 (1-4), 325-31CODEN: SEMCEQ; ISSN:0927-0248. (Elsevier)
  SnS films were prepd. by vacuum evapn. As-grown SnS films showed p-type conduction with a resistivity of 13-20 Ω cm, a carrier d. of 6.3×1014-1.2×1015 cm-3, and a Hall mobility of 400-500 cm2/V-s. The absorption coeffs. of the films were an order of 104 cm-1 at the fundamental absorption edge. The n-CdS/p-SnS heterojunctions were made by depositing n-CdS, p-SnS and Ag ohmic electrode on the transparent electrode (ITO) in the order ITO/n-CdS/p-SnS/Ag structure. The photovoltaic properties of a short-circuit current of 7 mA/cm2, an open-circuit voltage of 0.12 V, a fill factor of 0.35, and a conversion efficiency of 0.29% were obtained under the illumination of 100 mW/cm2.
73. 73
  Nair, M. T. S.; Nair, P. K. Semicond. Sci. Technol. 1991, 6, 132
  73
  Simplified chemical deposition technique for good quality tin monosulfide thin films
  Nair, M. T. S.; Nair, P. K.
  Semiconductor Science and Technology (1991), 6 (2), 132-4CODEN: SSTEET; ISSN:0268-1242.
  A chem. deposition technique, much simpler and more versatile than previously reported and capable of yielding good quality SnS films of thickness up to ≃1.2 μm under a choice of deposition conditions, is presented. The as-prepd. films are polycryst. with p-type dark cond. in the range 10-5-10-4 Ω-1cm-1 for the thicker (∼1 μm) films and showing a photocurrent to dark current ratio of 5-10 under 500 W m-2 tungsten halogen illumination. The optical transmittance and reflectance spectra and the photocurrent response curves of a series of SnS samples are explicitly presented to provide insight into possible applications of these films.
74. 74
  Wangperawong, A.; Herron, S. M.; Runser, R. R.; Hägglund, C.; Tanskanen, J. T.; Lee, H.-B.-R.; Clemens, B. M.; Bent, S. F. Appl. Phys. Lett. 2013, 103052105
  There is no corresponding record for this reference.
75. 75
  Sellin, P.; Davies, A. W.; Lohstroh, A.; Ozsan, M.; Parkin, J. IEEE Trans. Nucl. Sci. 2005, 52, 3074– 3078
  75
  Drift mobility and mobility-lifetime products in CdTe:Cl grown by the traveling heater method
  Sellin, P. J.; Davies, A. W.; Lohstroh, A.; Ozsan, M. E.; Parkin, J.
  IEEE Transactions on Nuclear Science (2005), 52 (6, Pt. 2), 3074-3078CODEN: IETNAE; ISSN:0018-9499. (Institute of Electrical and Electronics Engineers)
  Electron and hole charge transport properties of semi insulating CdTe:Cl grown by the traveling heater method (THM) were measured. An alpha-particle time of flight method was used to measure electron and hole drift mobility, with room temp. values of 880 cm2/Vs for electrons and 90 cm2/Vs for holes. The variation in mobility was also investigated as a function of temp., with electron and hole mobilities at 190 K of 1150 cm2/Vs and 20 cm2/Vs, resp. Using a Hecht anal., the electron and hole mobility-lifetime products were also measured over the same temp. range, with values at room temp. of 8 × 10-4 cm2/V and 7 × 10-5 cm2/V, resp. Time-resolved ion beam induced charge (IBIC) imaging was used to produce micrometer resoln. maps of electron drift mobility and signal amplitude, which showed excellent spatial uniformity.
76. 76
  Patil, R. H.; Tredgold, S G J. Phys. D: Appl. Phys. 1971, 4, 718– 722
  76
  Electrical and photoconductive properties of tin(II) sulfide crystals
  Patil, S. G.; Tredgold, R. H.
  Journal of Physics D: Applied Physics (1971), 4 (5), 718-22CODEN: JPAPBE; ISSN:0022-3727.
  Single crystals of SnS2 were prepd. by vapor transport. The elec. cond. of these crystals was measured along and perpendicular to their c direction by a probe method. The thermal activation energy assocd. with elec. conduction in the c direction exceeds that in the direction perpendicular to it by ∼0.18 eV. The spectral response of photocond. showed a band gap of 2.34 eV (at 300°K) with a temp. coeff. of -1.02 × 10-3 eV K-1.
77. 77
  Markvart, T. Prog. Quant. Electron. 2000, 24, 107– 186
  77
  Light harvesting for quantum solar energy conversion
  Markvart, Tomas
  Progress in Quantum Electronics (2000), 24 (3-4), 107-186CODEN: PQUEAH; ISSN:0079-6727. (Elsevier Science Ltd.)
  A review with 134 refs. of charge sepn. in photosynthesis, energy collection and minority carrier transport in solar cells, excitations and the resonant energy transfer, and exciton transport in the photosynthetic unit. This paper considers two examples of light harvesting (semiconductor solar cells and the photosynthetic app.) to illustrate the basic operation and principles that apply. In both cases it is shown that the rate of energy conversion is described by a law which parallels the Shockley's solar cell equation, and the light harvesting energy collection is subject to reciprocity relations which resemble Onsager's reciprocity relations between coeffs. which couple appropriate forces and flows in non-equil. thermodn. Differences in the basic at. make-up in the two systems lead to different energy transport equations. In both cases, however, similar math. techniques based on Green's functions can be used to advantage. The Green's function provides a convenient vehicle for the detn. of the probability of energy collection - known as the trapping probability in the photosynthetic unit. Using the reciprocity relation, both quantities are shown to be closely related to the distribution of the energy carriers in the dark. The collection probability can then be discussed in detail, by solving the semiconductor device equations in the case of solar cell, and by linking the Green's function formalism to the random walk model in the case of the photosynthetic unit. The concept of resonant energy transfer is beginning to enter the arena of solid-state optoelectronics. It is an aim of this paper to show that similar phenomena (which exist in the domain of bioenergetics) can throw new light on a range of energy transfer and collection processes that are of considerable importance in many modern optoelectronic devices.
78. 78
  de Walle, C. G. V.; Neugebauer, J. J. Appl. Phys. 2004, 95, 3851– 3879
  There is no corresponding record for this reference.
79. 79
  Engelken, R. D.; McCloud, H. E.; Lee, C.; Slayton, M.; Ghoreishi, H. J. Electrochem. Soc. 1987, 134, 2696– 2707
  There is no corresponding record for this reference.
80. 80
  Cheng, S.; Zhang, H. Micro Nano Lett. 2011, 6, 473– 475
  80
  Influence of thickness on structural and optical properties of evaporated tin sulphide films
  Cheng, Shuying; Zhang, Hong
  Micro & Nano Letters (2011), 6 (7), 473-475CODEN: MNLIBX; ISSN:1750-0443. (Institution of Engineering and Technology)
  Tin sulfide (SnS) films with thicknesses of 65-580 nm have been deposited on glass substrates by thermal evapn. The phys. properties of the films were investigated using X-ray diffraction, SEM, at. force microscopy, Raman spectroscopy and UV-visible-near-IR spectroscopy measurements at room temp. It is indicated that the deposited films mainly exhibit SnS phase, but they contain tiny SnO2. The deposited SnS films are pinhole free, smooth and strongly adherent to the surface of the substrate. With the increase of the film thickness from 65 to 580 nm, the color of the SnS films changes from brown to dark brown to gray, and the grains and roughness of the films become larger and larger, but the direct bandgap decreases. All the films have larger direct bandgap of 1.55-2.28 eV, which is much larger than the 1.3 eV of bulk SnS.
81. 81
  Yu, L.; Lany, S.; Kykyneshi, R.; Jieratum, V.; Ravichandran, R.; Pelatt, B.; Altschul, E.; Platt, H. A. S.; Wager, J. F.; Keszler, D. A.; Zunger, A. Adv. Energy Mater. 2011, 1, 748– 753
  81
  Iron chalcogenide photovoltaic absorbers
  Yu, Liping; Lany, Stephan; Kykyneshi, Robert; Jieratum, Vorranutch; Ravichandran, Ram; Pelatt, Brian; Altschul, Emmeline; Platt, Heather A. S.; Wager, John F.; Keszler, Douglas A.; Zunger, Alex
  Advanced Energy Materials (2011), 1 (5), 748-753CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
  The properties were studied of Fe2SiS4, Fe2GeS4, FeS2, FeS2-x, and related compds. The suitability of these materials as solar cells is discussed.
82. 82
  Atkins, P.; Overton, T.; Rourke, J.; Weller, M.; Armstrong, F. Inorganic Chemistry; Oxford University Press: Oxford, U.K., 2006.
  There is no corresponding record for this reference.
83. 83
  Malone, B. D.; Kaxiras, E. Phys. Rev. B 2013, 87, 245312
  There is no corresponding record for this reference.
84. 84
  Zainal, Z.; Hussein, M. Z.; Ghazali, A. Sol. Energy Mater. Sol. Cells 1996, 40, 347– 357
  84
  Cathodic electrodeposition of SnS thin films from aqueous solution
  Zainal, Zulkarnain; Hussein, Mohd. Zobir; Ghazali, Arniza
  Solar Energy Materials and Solar Cells (1996), 40 (4), 347-357CODEN: SEMCEQ; ISSN:0927-0248. (Elsevier)
  SnS thin films were prepd. by cathodic electrodeposition on ITO/glass and Ti substrates from a soln. contg. SnCl2 and thiosulfate ions. Cyclic voltammetry expts. were performed to elucidate the electrodic processes occurred when potentials were applied and to det. the optimum potential for electrodeposition. The photoactivity of the deposited films and their conduction types were evaluated using the photoelectrochem. technique. The bandgap energy and type of optical transitions were detd. from optical absorbance data. Structural and compositional anal. were accomplished using x-ray diffractometry, electron dispersive anal. of x-ray, and XPS. The morphol. of the films were examd. using SEM.
85. 85
  Lopez, S.; Ortiz, A. Semicond. Sci. Technol. 1994, 9, 2130– 2133
  85
  Spray pyrolysis deposition of tin sulfide (SnxSy) thin films
  Lopez, S.; Ortiz, A.
  Semiconductor Science and Technology (1994), 9 (11), 2130-3CODEN: SSTEET; ISSN:0268-1242. (Institute of Physics Publishing)
  Tin sulfide (SnxSy) thin films have been prepd. on Pyrex glass substrates by the spray pyrolysis technique using tin chloride (SnCl2) and N,N-dimethylthiourea (CH3NHCSNHCH3) as starting materials. The depositions were carried out in the range of substrate temps. from 320 to 450°. From x-ray diffraction measurements and SEM micrographs, it is found that the values of x and y, which det. the type of deposited compd., depend on the substrate temp. At lower substrate temps. (320-360°), mixed phases such as Sn2S3 and γ-Sn2S3 are present. At intermediate substrate temps. (370-390°), the SnS phase is predominant. For substrate temps. higher than 390°, the deposited material is mainly SnO2. The optical reflectance and transmittance of SnS were used in an iterative method to obtain the refractive index (n) and the excitation coeff. (k). The values of n and k were used to calc. the absorption coeff. (k). These values of n and k were used to calc. the absorption coeff. (α) and the bandgap (EG), giving the result EG = 1.27 eV. Measurements of the dark conductance (σ) as a function of T were made and an activation energy of 0.54 eV was detd. from the slope of a plot of ln σ vs. 1/T.
86. 86
  Ragina, A. J.; Murali, K. V.; Preetha, K. C.; Deepa, K.; Remadevi, T. L. A Study of Optical Parameters of Tin Sulphide Thin Films Using the Swanepoel Method. Optics: Phenomena, Materials, Devices, and Characterization 2011: International Conference on Light ;
  Calicut, India, May 23–25, 2011
  ; American Institute of Physics: College Park, MD, 2011
  There is no corresponding record for this reference.
87. 87
  Domingo, G.; Itoga, R. S.; Kannewurf, C. R. Phys. Rev. 1966, 143, 536– 541
  87
  Fundamental optical absorption in SnS2 and SnSe2
  Domingo, G.; Itoga, R. S.; Kannewurf, C. R.
  Physical Review (1966), 143 (2), 536-41CODEN: PHRVAO; ISSN:0031-899X.
  Optical absorption in single-crystal n-type SnS2 and SnSe2 has been studied at 300°K., 0.26-6.5 μ. Samples suitable for optical measurements were prepd. by various vapor-deposition techniques. The elec. characteristics of the samples used in the absorption measurements were: for SnSe2, cond. 3.6 (Ω cm.)-1, electron concn. 1018/cc., mobility 27 cm.2/v.-sec.; and for SnS2, cond. 10-7 (Ω cm.)-1. From transmittance and reflectance measurements, the absorption coeff. and n were detd. for light polarized perpendicular to the crystallographic symmetry axis. From an analysis of the data in the high-absorption region, directtransition band gaps of 1.62 and 2.88 ev. were found for SnSe2 and SnS2, resp. A threshold for possible indirect phonon-assisted transitions occurs at 0.97 ev. for SnSe2 and at 2.07 ev. for SnS2. Photocond. data for SnS2 are also presented.
88. 88
  Shi, C.; Chen, Z.; Shi, G.; Sun, R.; Zhan, X.; Shen, X. Thin Solid Films 2012, 520, 4898– 4901
  There is no corresponding record for this reference.
89. 89
  Alpen, U.; Fenner, J.; Gmelin, E. Mater. Res. Bull. 1975, 10, 175– 180
  There is no corresponding record for this reference.
90. 90
  Lopez, S.; Granados, S.; Ortiz, A. Semicond. Sci. Technol. 1996, 11, 433
  90
  Spray pyrolysis deposition of Sn2S3 thin films
  Lopez, S.; Granados, S.; Ortiz, A.
  Semiconductor Science and Technology (1996), 11 (3), 433-6CODEN: SSTEET; ISSN:0268-1242. (Institute of Physics Publishing)
  Ternary compd. SnIISnIVS3 thin films were prepd. on Pyrex glass substrates by the spray pyrolysis process using Sn chloride (SnCl2) and n,n-dimethylthiourea as starting materials. The depositions were carried out at a substrate temp. of 320°. The identification of the Sn2S3 phase was achieved by x-ray diffraction measurements. The optical reflectance and transmittance of the prepd. films were used to obtain the variation of the refractive index and the extinction coeff. as a function of the wavelength. These calcd. values were used to find the absorption coeff. and the optical bandgap and gave Eg = 1.16 eV. From measurements of the conductance as a function of T-1, a dark activation energy was detd. with a value of 1.02 eV.
91. 91
  Salah, H. B. H.; Bouzouita, H.; Rezig, B. Thin Solid Films 2005, 480?481, 439– 442
  There is no corresponding record for this reference.
92. 92
  Walsh, A.; Chen, S.; Wei, S.-H.; Gong, X.-G. Adv. Energy Mater. 2012, 2, 400– 409
  92
  Kesterite thin-film solar cells: advances in materials modelling of Cu2ZnSnS4
  Walsh, Aron; Chen, Shiyou; Wei, Su-Huai; Gong, Xin-Gao
  Advanced Energy Materials (2012), 2 (4), 400-409CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
  A review. Quaternary semiconducting materials based on the kesterite (A2BCX4) mineral structure are the most promising candidates to overtake the current generation of light-absorbing materials for thin-film solar cells. Cu2ZnSnS4 (CZTS), Cu2ZnSnSe4 (CZTSe) and their alloy Cu2ZnSn(Se,S)4 consist of abundant, low-cost and non-toxic elements, unlike current CdTe and Cu(In,Ga)Se2 based technologies. Zinc-blende related structures are formed by quaternary compds., but the complexity assocd. with the multi-component system introduces difficulties in material growth, characterization, and application. First-principles electronic structure simulations, performed over the past five years, that address the structural, electronic, and defect properties of this family of compds. are reviewed. Initial predictions of the bandgaps and crystal structures have recently been verified exptl. The calcns. highlight the role of at. disorder on the cation sub-lattice, as well as phase sepn. of Cu2ZnSnS4 into ZnS and CuSnS3, on the material performance for light-to-electricity conversion in photovoltaic devices. Finally, the current grand challenges for materials modeling of thin-film solar cells are highlighted.
93. 93
  Yu, P. Y.; Cardona, M. Fundamentals of Semiconductors, 3rd ed.; Springer-Verlag: New York, 2003.
  There is no corresponding record for this reference.
94. 94
  Mathews, N. R.; Anaya, H. B. M.; Cortes-Jacome, M. A.; Angeles-Chavez, C.; Toledo-Antonio, J. A. J. Electrochem. Soc. 2010, 157, H337– H341
  There is no corresponding record for this reference.
95. 95
  Miles, R. W.; Ogah, O. E.; Zoppi, G.; Forbes, I. Thin Solid Films 2009, 517, 4702– 4705
  There is no corresponding record for this reference.
96. 96
  Barone, G.; Hibbert, T. G.; Mahon, M. F.; Molloy, K. C.; Price, L. S.; Parkin, I. P.; Hardy, A. M. E.; Field, M. N. J. Mater. Chem. 2001, 11, 464– 468
  There is no corresponding record for this reference.
97. 97
  Scragg, J. J.; Kubart, T.; Watjen, J. T.; Ericson, T.; Linnarsson, M. K.; Platzer-Bjorkman, C. Chem. Mater. 2013, 25, 3162– 3171
  There is no corresponding record for this reference.
98. 98
  Moore, A. R. Appl. Phys. Lett. 1977, 31, 762– 764
  There is no corresponding record for this reference.
99. 99
  Handbook of Optical Constants of Solids, 3rd ed.; Academic Press: London, 1998.
  There is no corresponding record for this reference.
100. 100
  Momma, K.; Izumi, F. J. Appl. Crystallogr. 2011, 44, 1272– 1276
  100
  VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
  Momma, Koichi; Izumi, Fujio
  Journal of Applied Crystallography (2011), 44 (6), 1272-1276CODEN: JACGAR; ISSN:0021-8898. (International Union of Crystallography)
  VESTA is a 3D visualization system for crystallog. studies and electronic state calcns. It was upgraded to the latest version, VESTA 3, implementing new features including drawing the external morphpol. of crysals; superimposing multiple structural models, volumetric data and crystal faces; calcn. of electron and nuclear densities from structure parameters; calcn. of Patterson functions from the structure parameters or volumetric data; integration of electron and nuclear densities by Voronoi tessellation; visualization of isosurfaces with multiple levels, detn. of the best plane for selected atoms; an extended bond-search algorithm to enable more sophisticated searches in complex mols. and cage-like structures; undo and redo is graphical user interface operations; and significant performance improvements in rendering isosurfaces and calcg. slices.
Supporting Information
Supporting Information
Full X-ray crystallographic data for the three phases discussed in this paper and additional TRMC results for SnS₂. This material is available free of charge via the Internet at http://pubs.acs.org/.
- cm403046m_si_001.pdf (316.44 kb)
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Synthesis, Characterization, and Electronic Structure of Single-Crystal SnS, Sn2S3, and SnS2Click to copy article linkArticle link copied!

Chemistry of Materials

Abstract

Introduction

Figure 1

Methods

Chemical Vapor Transport

Composition and Structural Characterization

Figure 2

Time-Resolved Microwave Conductivity

Computational Methods

Results

Thermodynamics of Sn–I Transport

Figure 3

Single-Crystal Growth

Stoichiometry and Structure Identification

Transport Properties

Microwave Conductivity

Figure 4

Figure 5

Defect Theory

Electronic Structure

Figure 6

Discussion and Conclusions

Supporting Information

Terms & Conditions

Author Information

Acknowledgment

References

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Chemistry of Materials

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Abstract

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

References

Supporting Information

Supporting Information

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Synthesis, Characterization, and Electronic Structure of Single-Crystal SnS, Sn₂S₃, and SnS₂
Click to copy article linkArticle link copied!