Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect
ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Recombination in Perovskite Solar Cells: Significance of Grain Boundaries, Interface Traps, and Defect Ions

View Author Information
Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747AG Groningen, The Netherlands
Instituto de Ciencia Molecular, Universidad de Valencia, C/Catedrático J. Beltrán 2, 46980 Paterna Valencia, Spain
Cite this: ACS Energy Lett. 2017, 2, 5, 1214–1222
Publication Date (Web):May 2, 2017
https://doi.org/10.1021/acsenergylett.7b00236

Copyright © 2017 American Chemical Society. This publication is licensed under CC-BY-NC-ND.

  • Open Access

Article Views

26338

Altmetric

-

Citations

LEARN ABOUT THESE METRICS
PDF (1 MB)
Supporting Info (1)»

Abstract

Trap-assisted recombination, despite being lower as compared with traditional inorganic solar cells, is still the dominant recombination mechanism in perovskite solar cells (PSCs) and limits their efficiency. We investigate the attributes of the primary trap-assisted recombination channels (grain boundaries and interfaces) and their correlation to defect ions in PSCs. We achieve this by using a validated device model to fit the simulations to the experimental data of efficient vacuum-deposited p–i–n and n–i–p CH3NH3PbI3 solar cells, including the light intensity dependence of the open-circuit voltage and fill factor. We find that, despite the presence of traps at interfaces and grain boundaries (GBs), their neutral (when filled with photogenerated charges) disposition along with the long-lived nature of holes leads to the high performance of PSCs. The sign of the traps (when filled) is of little importance in efficient solar cells with compact morphologies (fused GBs, low trap density). On the other hand, solar cells with noncompact morphologies (open GBs, high trap density) are sensitive to the sign of the traps and hence to the cell preparation methods. Even in the presence of traps at GBs, trap-assisted recombination at interfaces (between the transport layers and the perovskite) is the dominant loss mechanism. We find a direct correlation between the density of traps, the density of mobile ionic defects, and the degree of hysteresis observed in the current–voltage (JV) characteristics. The presence of defect states or mobile ions not only limits the device performance but also plays a role in the JV hysteresis.

Thin-film solar cells making use of hybrid halide perovskites, CH3NH3PbX3 (X = Cl, Br, I), as a photoactive material show device power conversion efficiencies upward of 22%. (1) High device efficiency arises from the many desirable properties of perovskites, including a high absorption coefficient, high carrier mobilities, and long charge carrier diffusion lengths. (2-4) Efficient perovskite solar cells (PSCs) can be prepared by vacuum deposition (5, 6) and solution processing (7, 8) and in p–i–n as well as n–i–p configurations. (9) While the efficiency of PSCs is high, it is still far from the theoretical maximum (31%). (10) One of the reasons (others being optical losses, nonideal transport layers, and contact energy offsets) is the recombination of charge carriers in the device, which reduces the fill factor (FF) and the open-circuit voltage (VOC) of the solar cell. At solar fluences, radiative recombination (between free electrons and free holes) is weak in PSCs. (11) On the other hand, nonradiative recombination has been shown to be the dominant recombination mechanism in PSCs, (12, 13) which limits the efficiency of existing PSCs. (14, 15)

Nonradiative recombination takes place when a electron (or hole) trapped in a defect/impurity (energy level in the band gap of the perovskite) recombines with a hole (or electron) in the valence (or conduction) band of the perovskite. In polycrystalline perovskite thin films, defects or impurities are likely to be concentrated at grain boundaries (GBs) and at film surfaces. (16-18) The surface of the photoactive perovskite in PSCs is covered with ETL and HTL, which forms an interface. While nonradiative recombination at interfaces has been shown to severely influence the PSC performance, (15) the role of the GBs on the overall device performance is still under debate. (19-22) A few studies suggest that traps at GBs lead to increased trap-assisted recombination, (23, 24) insulating products (e.g., PbI2) formed at GBs passivate the traps and hence minimize trap-assisted recombination, (19, 20) and GBs act as hole transport highways, which leads to improved hole collection. (21) With the nature of GBs possibly changing with processing conditions and stoichiometry, (22, 25) it is important to investigate their role on the charge carrier dynamics in PSCs and quantify their influence (detrimental or otherwise) on the device performance. This would help to identify appropriate approaches for further increasing the efficiency of PSCs.

GBs are ubiquitous in polycrystalline films and are formed due to a break in the crystal structure of the material. The different orientations of neighboring crystal grains give rise to dislocations, misplaced atoms (interstitials), vacancies, distorted bond angles, and bond distances at the GBs. (26) These GBs are known to play a critical role in the charge carrier dynamics and photophysics of CdTe, poly-Si, and copper indium gallium selenide (CIGS) thin films used in solar cells. (27-30) Several GB models exist in the literature to explain their influence on the charge carrier dynamics in inorganic polycrystalline solar cells. (31-33) However, hybrid perovskites are different from the above-mentioned inorganic photovoltaic materials in terms of doping levels and the nature of GB defect traps. Perovskites are lightly doped materials, and due to the presence of charged ionic defects, it is likely that the traps are electrically charged when empty (34-36) and neutral when filled with photogenerated charges. A different perspective to GB physics is thus essential in the case of PSCs. It could help answer the question, is there a need to move toward single-crystalline materials or are polycrystalline films prepared using existing methods sufficient to achieve high-performing PSCs?

In this Letter, we investigate the attributes of the primary trap-assisted recombination channels, namely, GBs and interfaces, and their correlation to ionic defects in existing PSCs. We accomplish this by using our device model (15) to fit the simulation to the experimental data of vacuum-deposited p–i–n and n–i–p CH3NH3PbI3 solar cells. (9) The model takes as input the full experimental data sets, and the only free parameters (to fit) are the carrier mobility in the perovskite and the trap density plus the charge capture coefficients. The model achieves excellent agreement with the experimental measurements (for both p–i–n and n–i–p cells), including the light intensity dependence of the VOC and FF. We find that we can quantitatively describe all of the experimental data set only when we consider trap-assisted recombination at GBs and predominantly at interfaces (HTL/perovskite and perovskite/ETL) and weak bimolecular recombination in the perovskite absorber, ruling out the scenario of strong bulk trap-assisted recombination in the perovskite. Despite the presence of traps, their neutral (when filled) disposition along with the long-lived nature of holes leads to the high performance of PSCs. The sign (if charged or neutral when filled) of traps is of little importance in efficient solar cells with compact morphologies (fused GBs, low trap density). On the other hand, solar cells that have noncompact morphologies (open GBs, high trap density) are sensitive to the sign of the traps and hence to the preparation methods (e.g., under/overstoichiometric routes, environmental conditions). Even in the presence of traps at GBs, trap-assisted recombination at interfaces is the dominant recombination channel. Finally, we simulate fast forward/reverse current–voltage (JV) scans, which reveal little JV hysteresis, consistent with that observed experimentally for the p–i–n cell. (9) We observe direct correlation between the density of traps, the density of mobile ionic defects, and the degree of hysteresis in PSCs. Defect states (or mobile ions) not only retard the device performance but also play a role in the JV hysteresis. Finally, we give an estimate of the mobile ion density in this specific set of solar cells studied here.

The experimental data considered in this Letter were obtained from full vacuum-deposited CH3NH3PbI3 devices prepared by some of the authors and published recently. (9) Both p–i–n and n–i–p device configurations are studied (Figure 1), where i is the perovskite absorber layer, p is the hole transport layer (HTL), and n is the electron transport layer (ETL). For the p–i–n cell, indium tin oxide (ITO) and silver (Ag) are used as the anode and cathode, respectively, and for the n–i–p cell, the anode is gold (Au) and the cathode is ITO. The HTL is composed of a 10 nm thick film of N4,N4,N4″,N4″-tetra([1,1′-biphenyl]-4-yl)-[1,1′:4′,1″-terphenyl]-4,4″-diamine (TaTm) in contact with the perovskite, followed by a 40 nm thick TaTm film doped with 2,2′-(perfluoronaphthalene-2,6-diylidene) dimalononitrile (F6-TCNNQ) in contact with the anode. Analogously, the ETL comprises an undoped C60 fullerene film (10 nm) and a C60 layer (40 nm) doped with N1,N4-bis(tri-p-tolylphosphoranylidene)-benzene-1,4-diamine (PhIm) in contact with the cathode. The perovskite (CH3NH3PbI3) thin films are prepared by co-evaporation of CH3NH3I and PbI2 in a vacuum chamber, to a final thickness of 500 nm. The perovskite shows a band-to-band transition at 780 nm, which translates into a band gap (Egap) of 1.59 eV. (9) The p–i–n and n–i–p solar cells show efficiencies of around 16 and 18%, respectively, with a record efficiency of 20.3% using the n–i–p configuration. (9) Doping of HTL and ETL increases their conductivity and also increases the electric field strength in the perovskite layer, resulting in efficient charge extraction from the perovskite to the external contacts. (9, 15) This is reflected in a high FF and VOC for both p–i–n and n–i–p cells. (9)

Figure 1

Figure 1. (a) Schematics of the vacuum-deposited perovskite cells used and (b) scanning electron microscope (SEM) image of the CH3NH3PbI3 surface.

We recently developed a device model (15) that describes the operation of PSCs and quantitatively explains the role of contacts, the ETL and HTL, charge generation, transport of charge carriers, and recombination. Our 1D device model is based on the drift–diffusion equations for electrons and holes throughout the device and on solving the Poisson equation in one dimension. In the perovskite layer, the absorption of light generates free electrons and holes. The transport of these free charges is governed by drift–diffusion and electrically induced drift; for electrons (37)(1)and for holes(2)where Jn and Jp are electron and hole current densities, respectively, q is the electronic charge (1.602 × 10–19 C), V is the electrostatic potential, n and p are electron and hole concentrations, μn and μp are electron and hole mobilities, and Dn and Dp are electron and hole diffusion constants, respectively. The diffusion constants are assumed to obey the Einstein relation. (37)

The defect ion current density (Ja, anion; Jc, cation) is also given by the equations above. However, because the electrodes are ion-blocking, Ja = Jc = 0.

The electric potential throughout the device is solved from the Poisson equation(3)where ϵ is the permittivity, NA and ND+ are the ionized p-type and n-type doping, respectively, and Xc and Xa are the cationic and anionic defect densities, (36, 38-40) respectively, in the perovskite absorber. The trap density is ΣT, the sign of the trap when filled is QT ∈ {−1, 0, 1}, and the occupation probability of the trap is fT,ν=n,p, which is given by(4)where g0,1 are the degeneracy factors of empty and filled trap levels, respectively, Ncv is the effective density of states of both the conduction and valence band, Etrap (=Egap/2) is the midgap trap energy level, α is the sign of the trapped charge carrier (1 for holes, −1 for electrons), and Vt = kT/q is the thermal voltage, with k being the Boltzmann constant and T the temperature. We neglect the degeneracy of traps and set g0/g1 = 1.

The boundary condition on the electrostatic potential is(5)with Vapp being the externally applied voltage and Wa and Wc the anode and cathode work functions, respectively. The built-in potential is then given by Vbi = (WcWa)/q.

The boundary conditions for charge carrier densities at electrode contacts are given by (15)(6)where ϕn,p is the offset (in eV) between the cathode (anode) work function and the conduction (valence) band of the perovskite.

The generated charge carriers in CH3NH3PbI3 can recombine via both bimolecular and trap-assisted mechanisms. The bimolecular recombination rate (RBR) is given by(7)where kBR is the bimolecular recombination constant and ni is the intrinsic carrier concentration. The trap-assisted recombination rate (RSRH) is given by the Shockley–Read–Hall (SRH) equation (37)(8)where Cn and Cp are the capture coefficients for electrons and holes, respectively. Cn denotes the probability per unit time that the electron in the conduction band will be captured for the case that the trap is filled with a hole and able to capture the electron. Correspondingly, Cp denotes the probability per unit time that the hole in the valence band will be captured when the trap is filled with a electron and able to capture the hole. The constants n1 and p1 are defined as(9)The interface traps are located in a 2 nm thick region at HTL/perovskite (ΣT,p) and perovskite/ETL (ΣT,n) material interfaces and operate as recombination centers. (15) Recombination is most effective when traps are located midgap, and it is shown that recombination dynamics for an arbitrary distribution of traps near the middle of the band gap is identical. (41)

The details of the slow (“stabilized”) JV scans used to fit to the experimental data, fast forward/reverse JV scans, and hysteresis simulations, which include preconditioning, are presented in the Supporting Information (SI).

The numerical approaches and procedures to solve the above-mentioned equations can be found in refs 15 and 42.

Defects and impurities located at GBs and surfaces can act as traps for photogenerated charge carriers. In hybrid PSCs, electrons are the trapped carriers. (12, 43, 44) A negative GB is formed when electrons fill the empty uncharged GB traps, and a neutral GB is formed when electrons fill the empty charged traps. Figure 2 shows the case of a filled negative and a filled neutral GB. It is clear that GBs can act as (1) potential barriers (EB = qϕB) for electrons, which impedes their transport from one crystallite to another and thus affects their long-range mobility, and (2) recombination centers where the trapped electrons recombine nonradiatively with free holes in the valence band. Because hybrid perovskites are ionic conductors, the associated traps are expected to be electrically charged. (34-36)

Figure 2

Figure 2. (a) In typical inorganic solar cells (poly-Si, CdTe), the empty neutral traps at GBs and interfaces when filled with electrons result in a weakened transport due to the potential barrier (qϕB) and the nonradiative recombination between holes and trapped electrons is strong. (b) In PSCs, it is likely that the empty traps are positively charged due to accumulated iodide vacancies (VI+) at GBs and interfaces. Therefore, when filled with electrons, the traps are neutral, electron transport is relatively unaffected, and nonradiative recombination is weak.

Positively charged iodide vacancies (VI+) are the dominant defect ions, as indicated by recent theoretical studies. (35, 38) Migration of these defect ions has been shown to occur via the GBs rather than the crystal bulk. (16) GBs typically show weak emission in photoluminescence (PL) measurements, (23, 45) suggesting trapping and nonradiative recombination of carriers. It is therefore likely that accumulation of VI+ at GBs and surfaces (or interfaces) induces trap states that act as recombination centers for photogenerated carriers. Few theoretical studies predict the iodide vacancies to have energy states outside of the band gap; (46) however, these calculations are performed considering iodide vacancies as bulk point defects. The more relevant and performance-limiting features are the GBs and interfaces (or surfaces) where iodide vacancies and ions are most likely to reside at in thin films. (16, 20) Many recent experimental results point to the trapping nature of the accumulated iodide vacancies at GBs and interfaces. (43, 45, 47) A recently published theoretical study looked at carrier trapping at surface defects and reported that iodide vacancies do exhibit energy states inside of the band gap. (48) Therefore, we assume that the GB traps (accumulated VI+) when filled with charge carriers (electrons) are likely to be electrically neutral. Filled neutral traps are less likely to lead to rapid recombination as compared to filled charged traps, confirming the light-soaking experiments in PSCs where trap filling by photogenerated charges reduces the trap-assisted recombination in the device. (47)

A refinement of our full 3D drift–diffusion simulation (49) is currently a work in progress to take into account the accumulation of ionic defects at 3D GBs to explain the recently reported anomalous photovoltaic effect. (50)

In our devices, the experimentally observed crystal size is ∼100 nm on average. (9) Therefore, we incorporate GBs in our device model and place them LGB = 100 nm apart along the thickness of the perovskite absorber. The traps at GBs (ΣT,GB) and at interfaces (ΣT,p, ΣT,n) are charged when empty and neutral when filled. Because the device is electrically neutral in the dark, we assume in the model that the charged empty traps (accumulated VI+) are compensated by an equal density (volume) of mobile iodide ions given by(10)where nGB is the number of GBs along the absorber thickness (Labs). This makes the perovskite slightly p-type, in agreement with the literature. (43, 44, 51) The distribution of these mobile iodide ions in the perovskite layer is solved from the coupled continuity and Poisson equation discussed before and according to the device operating conditions (i.e., external bias, illumination, preconditioning), as detailed in SI.

Now, we fit the simulations to the experimental data of both p–i–n and n–i–p solar cells prepared by vacuum deposition. (9) The p–i–n device skeleton is shown in Figure 3. In the n–i–p device, the p and n layers are interchanged by reversing the order of vacuum deposition of the same materials. (9) The only difference is the top metal contact, silver (Ag) for the p–i–n cell and gold (Au) for the n–i–p cell. The model takes as input an extensive experimental data set (Table 1), and the only free parameters (to fit) are the carrier mobility in the perovskite and the trap density plus the charge capture coefficients.

Figure 3

Figure 3. The p–i–n device skeleton showing the energy levels, interface traps (red), and GBs (dashed lines). Upon illumination, free electrons and holes are transported through the respective materials and are extracted at the electrodes.

Table 1. Parameters Used in the Device Simulation of Both p–i–n and n–i–p Solar Cells to Simultaneously Fit to the JV Curves and Light Intensity Dependence of VOC and FF
parametersymbolvalue 
perovskite band gapEgap1.59 eVref  9
density of states (DOS)Ncv3.1 × 1018 cm–3 
perovskite conduction band minimumEc–5.43 eVref  9
perovskite valence band maximumEv–3.84 eVref  9
TaTm HOMO levelEHOMO–5.4 eVref  9
C60 LUMO levelELUMO–4.0 eVref  53
built-in voltageVbi1.4 Vref  9
hole mobility in TaTm (HTL)μ̅p4 × 10–3 cm2/(V s) 
electron mobility in C60 (ETL)μ̅n3 × 10–2 cm2/(V s)ref  53
perovskite relative permittivityϵ24.1ref  54
TaTm relative permittivityϵp3 
C60 relative permittivityϵn3.9ref  55
ionized doping in C60/PhImND+5 × 1018 cm–3ref  9
ionized doping in TaTm/F6TCNNQNA1 × 1016 cm–3ref  9
bimolecular recombination constantkBR1 × 10–9 cm3 s–1ref  11
electron and hole mobility in perovskiteμnp5 cm2/(V s)fit
HTL/perovskite interface trap densityΣT,p1 × 1010 cm–2fit
perovskite/ETL interface trap densityΣT,n2 × 109 cm–2fit
GB trap densityΣT,GB1.8 × 109 cm–2fit
electron and hole capture coefficientsCn, Cp1 × 10–6, 1 × 10–8 cm3 s–1fit
number of grid points 1000 
grid spacingΔx0.6 nm 
maximum charge generation rateGmax5.4 × 1021 cm–3 s–1 

We find that the model achieves quantitative agreement with the experimental data sets (both p–i–n and n–i–p cell) only when we consider (i) trap-assisted recombination at interfaces (HTL/perovskite and perovskite/ETL), (ii) trap-assisted recombination at GBs, and (ii) weak bimolecular recombination in the perovskite layer. When we considered other scenarios, mainly of bulk trap-assisted recombination in the perovskite, the simulations did not fit the experimental data of the light intensity dependence of the VOC and FF. The FF is more sensitive to the location and strength of different recombination channels in the device. For example, if we consider bulk trap-assisted recombination in simulations, the FF shows a positive dependence on light intensity. However, in our devices, we see the FF initially increasing and then decreasing with lowering of light intensity. Therefore, we rule out bulk trap-assisted recombination in perovskite as a primary recombination channel and a (device) performance-limiting attribute.

The experimental data under “stabilized” conditions (slow scan) for both p–i–n and n–i–p cells are shown in Figure 4a. The devices are illuminated by a standard AM 1.5G light source. Figure 4a also shows the fit to the experimental JV characteristics of both cells. The simulated fit is also performed under “stabilized” conditions, that is, an infinitely slow JV scan, where all mobile ions (calculated from eq 10) are redistributed in the perovskite layer according to the steady-state operating condition (applied bias, illumination) during the scan. In order to fit the simulation to the experimental data, we find that we need weak bimolecular recombination in the perovskite bulk and trap-assisted recombination at interfaces (HTL/perovskite and perovskite/ETL) and at GBs. The simulation of p–i–n and n–i–p cells is performed using the same set of device parameters, including all of the fitting parameters. The only change is the removal of the hole energetic offset (0.1 eV) in n–i–p cells where gold is used as the anode as compared to ITO as the anode in the p–i–n cell, which has a lower work function than gold (Au). (9) The calculated charge generation profile in both cells is shown in Figure 4b. The material optical constants (η, κ) as input to the transfer matrix model (52) in order to calculate the generation profile in p–i–n and n–i–p cells are obtained from the literature and are provided in the SI. Table 1 lists all of the device parameters used in the simulation to fit to the experimental data. The only free parameters (to fit) are the carrier mobility in the perovskite and the trap density plus the charge capture coefficients. The maximum generation rate (Gmax) is calculated by the transfer matrix model (52) and corresponds to a maximum short-circuit current density of 19.9 mA/cm2. The charge carrier mobilities extracted from the fit are in agreement with reported values for CH3NH3PbI3 solar cells. (11, 23) Bimolecular recombination takes place in the perovskite bulk with the recombination coefficient 1 × 10–9 cm3 s–1. (11) Trap-assisted recombination takes place at material interfaces (HTL/perovskite and perovskite/ETL) and at GBs. Here, Cp < Cn states that the probability per unit time of hole capture by a filled electron trap is lower than that of the electron capture by a filled hole trap. This is in agreement with the realization of long-lived holes (44) in PSCs.

Figure 4

Figure 4. (a) JV characteristics of p–i–n and n–i–p PSCs. The open symbols are experimental data for vacuum-deposited CH3NH3PbI3 solar cells. (9) The solid lines represent the simulations. (b) Normalized generation profile for the p–i–n and n–i–p (inset) solar cell as calculated using the transfer matrix model. (52)

Even in the presence of traps at GBs in the perovskite layer, trap-assisted recombination at interfaces is the dominant loss mechanism, in agreement with our previous report. (15) At solar fluences, traps at GBs are filled with photogenerated charges and become neutral and hence do not act as space charge. In addition, due to the low trap density at GBs and the existence of an alternate pathway (bimolecular) for charge carriers to recombine, GBs are benign at solar fluences.

As seen in Figure 4a, the n–i–p cell shows improved performance with the VOC and FF reaching 1.12 V and 81%, respectively. From the fit parameters in Table 1, the trap density at the HTL/perovskite interface (which is the front interface for the p–i–n cell) is higher than that at the perovskite/ETL interface (which is the front interface for the n–i–p cell). Because the quality of the front interface has a greater impact on the device performance, (15) the n–i–p cell performs better. The enhanced performance of the n–i–p cell also derives from the higher conductivity of the doped ETL as compared to doped HTL, which boosts charge extraction at the front interface, and in part due to the use of gold (Au) as the anode, which eliminates the hole energetic offset that is otherwise present in the p–i–n cell where ITO is used as the anode. (9)

The light intensity dependence of the VOC and FF for both p–i–n and n–i–p cells is shown in Figure 5a,b. The light intensity dependence of VOC reveals the dominant mechanism in solar cells, with slopes of kT/q and 2kT/q indicating dominant bimolecular and trap-assisted recombination, respectively. (56, 57) Due to the superior quality of the front interface in the n–i–p cell, trap-assisted recombination is suppressed (slope = 1.55kT/q) as compared to the p–i–n cell (slope = 2.1kT/q). Under open-circuit conditions, no current (hence no power) is extracted from the solar cell. As a solar cell is operated close to maximum power, the FF is the more relevant characteristic. The light intensity dependence of the FF trend reveals that there is some competition between bimolecular and trap-assisted recombination in these cells. In a pure bimolecular recombination scenario, FF increases with decreasing light intensity as the recombination rate is proportional to the product of charge carrier densities (which decreases with decreasing light intensity). For a pure trap-assisted recombination scenario, FF decreases with decreasing light intensity as the proportion of free charges recombining with trapped charges (the number of traps remains the same) increases with decreasing light intensity. Now, as can be seen in Figure 5b, bimolecular recombination dominates for light intensities above 0.1 Sun, while trap-assisted recombination does so below 0.1 Sun. The FF is more sensitive (as compared to VOC) to leakage at lower light intensities (58) and hence the anomalous FF value of the p–i–n cell at 0.001 Sun.

Figure 5

Figure 5. Light intensity dependence of (a) VOC and (b) FF for both p–i–n and n–i–p cells. The filled symbols and lines in (a) represent experimental data and simulation, respectively. The open and filled symbols in (b) represent experimental data and simulation, respectively.

Although traps at GBs and interfaces are likely to be charged (due to accumulated ionic defects) when empty and hence neutral when filled, the sign of the filled trap has little to do with the overall device performance when the solar cell in question is efficient, with fused GBs (low trap densities). The PSCs used here show compact morphology and have high efficiencies reaching 20% with little or no hysteresis, (9) and hence, the sign of the filled traps shows only a marginal change in device performance (Figure S2 in the SI). On the other hand, solar cells with open GBs (high trap densities) show high sensitivity to the sign of filled traps at GBs, as shown in Figure S2. Charged filled traps lead to faster SRH recombination due to the Coulombic attraction between opposite charged species (a negative filled trap and a hole). However, even then, some PSCs with open GBs (high trap densities) show decent efficiencies (∼12%). (47) This can be attributed to the likely case of the existence of charged empty traps (accumulated VI+ at GBs and interfaces) and thus neutral filled traps, which lowers the SRH recombination rate in PSCs. Solar cell preparation methods are likely to influence the properties of traps, which is why there seems to be no agreement in the literature about the impact of GBs on the device performance. (19-21, 23, 24)

Until this point, we simulated the current–voltage (JV) scans under “stabilized” conditions (an infinitely slow JV scan), such that all mobile iodide ions (Xa) given by eq 10 (compensating the presence of accumulated iodide vacancies VI+ at GBs/interfaces acting as traps and recombination centers for photogenerated charge carriers) were allowed to redistribute at every step of the scan. This naturally resulted in hysteresis-free device characteristics as the forward and reverse scans yielded the same JV curve. While the role of preconditioning and scan rate is more or less clear in the context of JV hysteresis in CH3NH3PbI3 solar cells, (59-63) we would like to answer the following question: Is there a relation between the density of trap states, the density of defect mobile ions, and the degree of hysteresis seen in PSCs?

The trap density in the p–i–n and n–i–p cells studied here is known from Table 1. In the model, the mobile iodide ion (Xa) density is assumed to be related to the trap density (accumulated VI+) by eq 10 because their origin is the same (dislocation of iodide ions). We now simulate the extreme case (where cells would show maximum hysteresis) of a fast voltage scan rate (Vscan = ∞) after preconditioning (infinitely long) at −0.2 V (for forward scan) and l.2 V (for reverse scan) bias. The fast forward scan simulation is performed after preconditioning the device at −0.2 V under illumination such that negative iodide ions are pushed toward the ETL and stay put throughout the scan. For the fast reverse scan, the device is preconditioned at 1.2 V under illumination such that the iodide ions are pushed away from the ETL and their distribution remains fixed during the scan. This gives us an envelope (two JV curves enclosing a small area) that relates to the degree of hysteresis. The simulated hysteresis is shown in Figure 6 and is consistent with the experimentally observed little hysteresis in p–i–n cells and no hysteresis in n–i–p cells that we study here. (9) In these cells made by some of us, the degree of measured JV hysteresis is relatively unchanged when the scans are performed with or without preconditioning, irrespective of the scan rate. (9) The simulation details of the fast scans and “stabilized” scans are included in the SI. It is clear that high-performing PSCs are likely to show little or no hysteresis because they contain a low density of traps and hence mobile defect ions. This is in agreement with Calado et al., (64) who provide evidence that devices with minimal hysteresis still have moving ions but low trap densities that results in decreased recombination strength in the device and therefore little hysteresis. As shown in Figure S3, poor solar cells with high trap density (and thus defect ions) show more hysteresis in the JV characteristics. Therefore, defect states or mobile ions not only limit the device performance but also play a role in the hysteresis observed in their JV characteristics of PSCs.

Figure 6

Figure 6. Simulated forward/reverse scan of p–i–n and n–i–p cells showing hysteresis in the JV curves when negative iodide ions (Xa = 4 × 1014 cm–3) are mobile. The forward scan is performed after preconditioning at −0.2 V, and the reverse scan is carried out after preconditioning at 1.2 V.

An estimate of the density of the mobile ions in the specific set of PSCs studied in this paper would be Xa ≈ 1015 cm–3 at the most.

It is possible that ionic defects other than the iodide complexes act as trap-assisted recombination centers and contribute to JV hysteresis. However, the activation energies for migration of I complexes are much lower as compared to those of other ionic (CH3NH3, Pb, etc.) complexes, (38, 63) and hence, I complexes are more likely to influence the device optoelectronic performance. (45)

In conclusion, we investigated the attributes of the primary trap-assisted recombination channels (GBs and interfaces) and their correlation to defect ions in PSCs. We achieved this by using a device model (15) to fit the simulations to the experimental data of efficient p–i–n and n–i–p CH3NH3PbI3 solar cells. The model utilized an extensive experimental data set (Table 1) as input, and the only free parameters (to fit) were the carrier mobility in the perovskite and the trap density plus the charge capture coefficients. Excellent agreement was found between the simulated data and experimental data, including the light intensity dependence of VOC and FF. We found that despite the presence of traps at GBs, their neutral (when filled with photogenerated charges) disposition along with the long-lived nature of holes leads to the high performance of PSCs. The sign (if charged or neutral when filled) of traps is of little importance in efficient solar cells with compact morphologies (fused GBs, low trap density). On the other hand, solar cells with noncompact morphologies (open GBs, high trap density) are sensitive to the sign of the traps and hence cell preparation methods (e.g., under/overstoichiometric routes, environmental conditions). Even in the presence of traps at GBs in the perovskite layer, trap-assisted recombination at interfaces is the dominant loss mechanism, in agreement with our previous report. (15) We found a direct correlation between the density of trap states, the density of mobile ions, and the degree of hysteresis observed in the current–voltage (JV) characteristics. High-performing PSCs are likely to show little or no hysteresis because they contain low density of traps and hence ions, while poor solar cells with high trap density (and thus ions) show more hysteresis. Therefore, defects states or mobile ions not only limit the device performance but also play a role in the hysteresis observed in the JV characteristics of PSCs. We found that the specific set of devices studied in this Letter contain a defect mobile ion density on the order 1015 cm–3 at the most.

Focus should be directed toward passivation of traps at interfaces (HTL/perovskite and perovskite/ETL) where trap-assisted recombination dominates, while the use of polycrystalline perovskite films with fused GBs as absorber is good enough to achieve high-performance solar cells.

Supporting Information

ARTICLE SECTIONS
Jump To

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsenergylett.7b00236.

  • Simulation details, optical data, and additional results (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

ARTICLE SECTIONS
Jump To

  • Corresponding Author
  • Authors
    • Tejas S. Sherkar - Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747AG Groningen, The Netherlands
    • Cristina Momblona - Instituto de Ciencia Molecular, Universidad de Valencia, C/Catedrático J. Beltrán 2, 46980 Paterna Valencia, Spain
    • Lidón Gil-Escrig - Instituto de Ciencia Molecular, Universidad de Valencia, C/Catedrático J. Beltrán 2, 46980 Paterna Valencia, Spain
    • Jorge Ávila - Instituto de Ciencia Molecular, Universidad de Valencia, C/Catedrático J. Beltrán 2, 46980 Paterna Valencia, Spain
    • Michele Sessolo - Instituto de Ciencia Molecular, Universidad de Valencia, C/Catedrático J. Beltrán 2, 46980 Paterna Valencia, Spain
    • Henk J. Bolink - Instituto de Ciencia Molecular, Universidad de Valencia, C/Catedrático J. Beltrán 2, 46980 Paterna Valencia, SpainOrcidhttp://orcid.org/0000-0001-9784-6253
  • Notes
    The authors declare no competing financial interest.

Acknowledgment

ARTICLE SECTIONS
Jump To

The Valencian team acknowledges financial support from the Spanish Ministry of Economy and Competitiveness (MINECO) via the Unidad de Excelencia María de Maeztu MDM-2015-0538 and MAT2014-55200, PCIN-2015-255, and the Generalitat Valenciana (Prometeo/2016/135). C.M. and M.S. thank the MINECO for their pre- and postdoctoral (JdC) contracts. This work is part of the Industrial Partnership Programme (IPP) “Computational sciences for energy research” of the Foundation for Fundamental Research on Matter (FOM), which is part of The Netherlands Organisation for Scientific Research (NWO). This research programme is cofinanced by Shell Global Solutions International B.V. This is a publication by the FOM Focus Group “Next Generation Organic Photovoltaics”, participating in the Dutch Institute for Fundamental Energy Research (DIFFER).

References

ARTICLE SECTIONS
Jump To

This article references 64 other publications.

  1. 1
    Green, M. A.; Emery, K.; Hishikawa, Y.; Warta, W.; Dunlop, E. D.; Levi, D. H.; Ho-Baillie, A. W. Solar cell efficiency tables (version 49) Prog. Photovoltaics 2017, 25, 3 DOI: 10.1002/pip.2855
  2. 2
    Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells J. Am. Chem. Soc. 2009, 131, 6050 6051 DOI: 10.1021/ja809598r
  3. 3
    Stranks, S. D.; Eperon, G. E.; Grancini, G.; Menelaou, C.; Alcocer, M. J.; Leijtens, T.; Herz, L. M.; Petrozza, A.; Snaith, H. J. Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber Science 2013, 342, 341 344 DOI: 10.1126/science.1243982
  4. 4
    Edri, E.; Kirmayer, S.; Mukhopadhyay, S.; Gartsman, K.; Hodes, G.; Cahen, D. Elucidating the charge carrier separation and working mechanism of CH3NH3PbI3-xClx perovskite solar cells Nat. Commun. 2014, 5, 3461 DOI: 10.1038/ncomms4461
  5. 5
    Liu, M.; Johnston, M. B.; Snaith, H. J. Efficient planar heterojunction perovskite solar cells by vapour deposition Nature 2013, 501, 395 398 DOI: 10.1038/nature12509
  6. 6
    Malinkiewicz, O.; Yella, A.; Lee, Y. H.; Espallargas, G. M.; Graetzel, M.; Nazeeruddin, M. K.; Bolink, H. J. Perovskite solar cells employing organic charge-transport layers Nat. Photonics 2013, 8, 128 132 DOI: 10.1038/nphoton.2013.341
  7. 7
    You, J. Low-temperature solution-processed perovskite solar cells with high efficiency and flexibility ACS Nano 2014, 8, 1674 1680 DOI: 10.1021/nn406020d
  8. 8
    Nie, W. High-efficiency solution-processed perovskite solar cells with millimeter-scale grains Science 2015, 347, 522 525 DOI: 10.1126/science.aaa0472
  9. 9
    Momblona, C.; Gil-Escrig, L.; Bandiello, E.; Hutter, E. M.; Sessolo, M.; Lederer, K.; Blochwitz-Nimoth, J.; Bolink, H. J. Efficient vacuum deposited pin and nip perovskite solar cells employing doped charge transport layers Energy Environ. Sci. 2016, 9, 3456 3463 DOI: 10.1039/C6EE02100J
  10. 10
    Sha, W. E. I.; Ren, X.; Chen, L.; Choy, W. C. The efficiency limit of CH3NH3PbI3 perovskite solar cells Appl. Phys. Lett. 2015, 106, 221104 DOI: 10.1063/1.4922150
  11. 11
    Wehrenfennig, C.; Eperon, G. E.; Johnston, M. B.; Snaith, H. J.; Herz, L. M. High charge carrier mobilities and lifetimes in organolead trihalide perovskites Adv. Mater. 2014, 26, 1584 1589 DOI: 10.1002/adma.201305172
  12. 12
    Wetzelaer, G. A. H.; Scheepers, M.; Sempere, A. M.; Momblona, C.; Ávila, J.; Bolink, H. J. Trap-Assisted Non-Radiative Recombination in Organic-Inorganic Perovskite Solar Cells Adv. Mater. 2015, 27, 1837 1841 DOI: 10.1002/adma.201405372
  13. 13
    Johnston, M. B.; Herz, L. M. Hybrid perovskites for photovoltaics: Charge-carrier recombination, diffusion, and radiative efficiencies Acc. Chem. Res. 2016, 49, 146 154 DOI: 10.1021/acs.accounts.5b00411
  14. 14
    Tress, W.; Marinova, N.; Inganäs, O.; Nazeeruddin, M.; Zakeeruddin, S. M.; Graetzel, M. Predicting the Open-Circuit Voltage of CH3NH3PbI3 Perovskite Solar Cells Using Electroluminescence and Photovoltaic Quantum Efficiency Spectra: the Role of Radiative and Non-Radiative Recombination Adv. Energy Mater. 2015, 5, 1400812 DOI: 10.1002/aenm.201400812
  15. 15
    Sherkar, T. S.; Momblona, C.; Gil-Escrig, L.; Bolink, H. J.; Koster, L. J. A. Improving the Performance of Perovskite Solar Cells: Insights From a Validated Device Model Adv. Energy Mater. 2017, 1602432 DOI: 10.1002/aenm.201602432
  16. 16
    Shao, Y. Grain boundary dominated ion migration in polycrystalline organic-inorganic halide perovskite films Energy Environ. Sci. 2016, 9, 1752 1759 DOI: 10.1039/C6EE00413J
  17. 17
    Cui, P.; Fu, P.; Wei, D.; Li, M.; Song, D.; Yue, X.; Li, Y.; Zhang, Z.; Li, Y.; Mbengue, J. M. Reduced surface defects of organometallic perovskite by thermal annealing for highly efficient perovskite solar cells RSC Adv. 2015, 5, 75622 75629 DOI: 10.1039/C5RA16669A
  18. 18
    Wu, X.; Trinh, M. T.; Niesner, D.; Zhu, H.; Norman, Z.; Owen, J. S.; Yaffe, O.; Kudisch, B. J.; Zhu, X.-Y. Trap states in lead iodide perovskites J. Am. Chem. Soc. 2015, 137, 2089 2096 DOI: 10.1021/ja512833n
  19. 19
    Chen, Q.; Zhou, H.; Song, T.-B.; Luo, S.; Hong, Z.; Duan, H.-S.; Dou, L.; Liu, Y.; Yang, Y. Controllable self-induced passivation of hybrid lead iodide perovskites toward high performance solar cells Nano Lett. 2014, 14, 4158 4163 DOI: 10.1021/nl501838y
  20. 20
    MacDonald, G. A.; Yang, M.; Berweger, S.; Killgore, J. P.; Kabos, P.; Berry, J. J.; Zhu, K.; DelRio, F. W. Methylammonium lead iodide grain boundaries exhibit depth-dependent electrical properties Energy Environ. Sci. 2016, 9, 3642 3649 DOI: 10.1039/C6EE01889K
  21. 21
    Yun, J. S.; Ho-Baillie, A.; Huang, S.; Woo, S. H.; Heo, Y.; Seidel, J.; Huang, F.; Cheng, Y.-B.; Green, M. A. Benefit of grain boundaries in organic-inorganic halide planar perovskite solar cells J. Phys. Chem. Lett. 2015, 6, 875 880 DOI: 10.1021/acs.jpclett.5b00182
  22. 22
    Jacobsson, T. J. Unreacted PbI2 as a Double-Edged Sword for Enhancing the Performance of Perovskite Solar Cells J. Am. Chem. Soc. 2016, 138, 10331 10343 DOI: 10.1021/jacs.6b06320
  23. 23
    de Quilettes, D. W.; Vorpahl, S. M.; Stranks, S. D.; Nagaoka, H.; Eperon, G. E.; Ziffer, M. E.; Snaith, H. J.; Ginger, D. S. Impact of microstructure on local carrier lifetime in perovskite solar cells Science 2015, 348, 683 686 DOI: 10.1126/science.aaa5333
  24. 24
    Bischak, C. G.; Sanehira, E. M.; Precht, J. T.; Luther, J. M.; Ginsberg, N. S. Heterogeneous Charge Carrier Dynamics in Organic-Inorganic Hybrid Materials: Nanoscale Lateral and Depth-Dependent Variation of Recombination Rates in Methylammonium Lead Halide Perovskite Thin Films Nano Lett. 2015, 15, 4799 4807 DOI: 10.1021/acs.nanolett.5b01917
  25. 25
    Ono, L. K.; Qi, Y. Surface and Interface Aspects of Organometal Halide Perovskite Materials and Solar Cells J. Phys. Chem. Lett. 2016, 7, 4764 4794 DOI: 10.1021/acs.jpclett.6b01951
  26. 26
    Nelson, J. The Physics of Solar Cells; Imperial College Press: London, 2003.
  27. 27
    Visoly-Fisher, I.; Cohen, S. R.; Gartsman, K.; Ruzin, A.; Cahen, D. Understanding the Beneficial Role of Grain Boundaries in Polycrystalline Solar Cells from Single-Grain-Boundary Scanning Probe Microscopy Adv. Funct. Mater. 2006, 16, 649 660 DOI: 10.1002/adfm.200500396
  28. 28
    Li, C. Grain-boundary-enhanced carrier collection in CdTe solar cells Phys. Rev. Lett. 2014, 112, 156103 DOI: 10.1103/PhysRevLett.112.156103
  29. 29
    Distefano, T.; Cuomo, J. Reduction of grain boundary recombination in polycrystalline silicon solar cells Appl. Phys. Lett. 1977, 30, 351 353 DOI: 10.1063/1.89396
  30. 30
    Gloeckler, M.; Sites, J. R.; Metzger, W. K. Grain-boundary recombination in Cu (In, Ga) Se2 solar cells J. Appl. Phys. 2005, 98, 113704 DOI: 10.1063/1.2133906
  31. 31
    Seto, J. Y. The electrical properties of polycrystalline silicon films J. Appl. Phys. 1975, 46, 5247 5254 DOI: 10.1063/1.321593
  32. 32
    Landsberg, P.; Abrahams, M. Effects of surface states and of excitation on barrier heights in a simple model of a grain boundary or a surface J. Appl. Phys. 1984, 55, 4284 4293 DOI: 10.1063/1.333038
  33. 33
    Card, H. C.; Yang, E. S. Electronic processes at grain boundaries in polycrystalline semiconductors under optical illumination IEEE Trans. Electron Devices 1977, 24, 397 402 DOI: 10.1109/T-ED.1977.18747
  34. 34
    Yin, W.-J.; Yang, J.-H.; Kang, J.; Yan, Y.; Wei, S.-H. Halide perovskite materials for solar cells: a theoretical review J. Mater. Chem. A 2015, 3, 8926 8942 DOI: 10.1039/C4TA05033A
  35. 35
    Walsh, A.; Scanlon, D. O.; Chen, S.; Gong, X.; Wei, S.-H. Self-Regulation Mechanism for Charged Point Defects in Hybrid Halide Perovskites Angew. Chem. 2015, 127, 1811 1814 DOI: 10.1002/ange.201409740
  36. 36
    Yin, W.-J.; Shi, T.; Yan, Y. Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber Appl. Phys. Lett. 2014, 104, 063903 DOI: 10.1063/1.4864778
  37. 37
    Selberherr, S. Analysis and Simulation of Semiconductor Devices; Springer-Verlag: Vienna, 1984.
  38. 38
    Eames, C.; Frost, J. M.; Barnes, P. R.; O’regan, B. C.; Walsh, A.; Islam, M. S. Ionic transport in hybrid lead iodide perovskite solar cells Nat. Commun. 2015, 6, 7497 DOI: 10.1038/ncomms8497
  39. 39
    Azpiroz, J. M.; Mosconi, E.; Bisquert, J.; de Angelis, F. Defect migration in methylammonium lead iodide and its role in perovskite solar cell operation Energy Environ. Sci. 2015, 8, 2118 2127 DOI: 10.1039/C5EE01265A
  40. 40
    Yuan, Y.; Huang, J. Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability Acc. Chem. Res. 2016, 49, 286 293 DOI: 10.1021/acs.accounts.5b00420
  41. 41
    Simmons, J.; Taylor, G. Nonequilibrium steady-state statistics and associated effects for insulators and semiconductors containing an arbitrary distribution of traps Phys. Rev. B 1971, 4, 502 DOI: 10.1103/PhysRevB.4.502
  42. 42
    Koster, L. J. A.; Smits, E. C. P.; Mihailetchi, V. D.; Blom, P. W. M. Device model for the operation of polymer/fullerene bulk heterojunction solar cells Phys. Rev. B: Condens. Matter Mater. Phys. 2005, 72, 085205 DOI: 10.1103/PhysRevB.72.085205
  43. 43
    Leijtens, T.; Stranks, S. D.; Eperon, G. E.; Lindblad, R.; Johansson, E. M.; McPherson, I. J.; Rensmo, H.; Ball, J. M.; Lee, M. M.; Snaith, H. J. Electronic properties of meso-superstructured and planar organometal halide perovskite films: charge trapping, photodoping, and carrier mobility ACS Nano 2014, 8, 7147 7155 DOI: 10.1021/nn502115k
  44. 44
    Leijtens, T.; Eperon, G. E.; Barker, A. J.; Grancini, G.; Zhang, W.; Ball, J. M.; Kandada, A. R. S.; Snaith, H. J.; Petrozza, A. Carrier trapping and recombination: the role of defect physics in enhancing the open circuit voltage of metal halide perovskite solar cells Energy Environ. Sci. 2016, 9, 3472 3481 DOI: 10.1039/C6EE01729K
  45. 45
    deQuilettes, D. W.; Zhang, W.; Burlakov, V. M.; Graham, D. J.; Leijtens, T.; Osherov, A.; Bulović, V.; Snaith, H. J.; Ginger, D. S.; Stranks, S. D. Photo-induced halide redistribution in organic-inorganic perovskite films Nat. Commun. 2016, 7, 11683 DOI: 10.1038/ncomms11683
  46. 46
    Du, M.-H. Density functional calculations of native defects in CH3NH3PbI3: effects of spin-orbit coupling and self-interaction error J. Phys. Chem. Lett. 2015, 6, 1461 1466 DOI: 10.1021/acs.jpclett.5b00199
  47. 47
    Shao, S.; Abdu-Aguye, M.; Sherkar, T. S.; Fang, H.-H.; Adjokatse, S.; Brink, G. t.; Kooi, B. J.; Koster, L.; Loi, M. A. The Effect of the Microstructure on Trap-Assisted Recombination and Light Soaking Phenomenon in Hybrid Perovskite Solar Cells Adv. Funct. Mater. 2016, 26, 8094 8102 DOI: 10.1002/adfm.201602519
  48. 48
    Uratani, H.; Yamashita, K. Charge Carrier Trapping at Surface Defects of Perovskite Solar Cell Absorbers: A First-Principles Study J. Phys. Chem. Lett. 2017, 8, 742 746 DOI: 10.1021/acs.jpclett.7b00055
  49. 49
    Sherkar, T. S.; Koster, L. J. A. Can ferroelectric polarization explain the high performance of hybrid halide perovskite solar cells? Phys. Chem. Chem. Phys. 2016, 18, 331 338 DOI: 10.1039/C5CP07117H
  50. 50
    Yuan, Y.; Li, T.; Wang, Q.; Xing, J.; Gruverman, A.; Huang, J. Anomalous photovoltaic effect in organic-inorganic hybrid perovskite solar cells Science Adv. 2017, 3, e1602164 DOI: 10.1126/sciadv.1602164
  51. 51
    Xing, G.; Mathews, N.; Sun, S.; Lim, S. S.; Lam, Y. M.; Grätzel, M.; Mhaisalkar, S.; Sum, T. C. Long-range balanced electron-and hole-transport lengths in organic-inorganic CH3NH3PbI3 Science 2013, 342, 344 347 DOI: 10.1126/science.1243167
  52. 52
    Burkhard, G. F.; Hoke, E. T.; McGehee, M. D. Accounting for interference, scattering, and electrode absorption to make accurate internal quantum efficiency measurements in organic and other thin solar cells Adv. Mater. 2010, 22, 3293 3297 DOI: 10.1002/adma.201000883
  53. 53
    Tress, W. Device Physics of Organic Solar Cells. Ph.D. thesis, TU Dresden, Dresden, Germany, 2011.
  54. 54
    Brivio, F.; Butler, K. T.; Walsh, A.; van Schilfgaarde, M. Relativistic quasiparticle self-consistent electronic structure of hybrid halide perovskite photovoltaic absorbers Phys. Rev. B: Condens. Matter Mater. Phys. 2014, 89, 155204 DOI: 10.1103/PhysRevB.89.155204
  55. 55
    Mönch, T.; Sherkar, T. S.; Koster, L. J. A.; Friederich, P.; Riede, M.; Formanek, P.; Koerner, C.; Vandewal, K.; Wenzel, W.; Leo, K. Experimental and theoretical study of phase separation in ZnPc: C 60 blends Org. Electron. 2015, 27, 183 191 DOI: 10.1016/j.orgel.2015.09.023
  56. 56
    Koster, L. J. A.; Mihailetchi, V. D.; Ramaker, R.; Blom, P. W. Light intensity dependence of open-circuit voltage of polymer: fullerene solar cells Appl. Phys. Lett. 2005, 86, 123509 123509 DOI: 10.1063/1.1889240
  57. 57
    Mandoc, M.; Kooistra, F.; Hummelen, J.; De Boer, B.; Blom, P. Effect of traps on the performance of bulk heterojunction organic solar cells Appl. Phys. Lett. 2007, 91, 263505 DOI: 10.1063/1.2821368
  58. 58
    Tvingstedt, K.; Gil-Escrig, L.; Momblona, C.; Rieder, P.; Kiermasch, D.; Sessolo, M.; Baumann, A.; Bolink, H. J.; Dyakonov, V. Removing Leakage and Surface Recombination in Planar Perovskite Solar Cells ACS Energy Letters 2017, 2, 424 430 DOI: 10.1021/acsenergylett.6b00719
  59. 59
    Snaith, H. J.; Abate, A.; Ball, J. M.; Eperon, G. E.; Leijtens, T.; Noel, N. K.; Stranks, S. D.; Wang, J. T.-W.; Wojciechowski, K.; Zhang, W. Anomalous hysteresis in perovskite solar cells J. Phys. Chem. Lett. 2014, 5, 1511 1515 DOI: 10.1021/jz500113x
  60. 60
    Tress, W.; Marinova, N.; Moehl, T.; Zakeeruddin, S. M.; Nazeeruddin, M. K.; Grätzel, M. Understanding the rate-dependent J–V hysteresis, slow time component, and aging in CH 3 NH 3 PbI 3 perovskite solar cells: the role of a compensated electric field Energy Environ. Sci. 2015, 8, 995 1004 DOI: 10.1039/C4EE03664F
  61. 61
    Unger, E. L.; Hoke, E. T.; Bailie, C. D.; Nguyen, W. H.; Bowring, A. R.; Heumüller, T.; Christoforo, M. G.; McGehee, M. D. Hysteresis and transient behavior in current-voltage measurements of hybrid-perovskite absorber solar cells Energy Environ. Sci. 2014, 7, 3690 3698 DOI: 10.1039/C4EE02465F
  62. 62
    Richardson, G.; O’Kane, S. E.; Niemann, R. G.; Peltola, T. A.; Foster, J. M.; Cameron, P. J.; Walker, A. B. Can slow-moving ions explain hysteresis in the current–voltage curves of perovskite solar cells? Energy Environ. Sci. 2016, 9, 1476 1485 DOI: 10.1039/C5EE02740C
  63. 63
    Meloni, S. Ionic polarization-induced current-voltage hysteresis in CH3NH3PbX3 perovskite solar cells Nat. Commun. 2016, 7, 10334 DOI: 10.1038/ncomms10334
  64. 64
    Calado, P.; Telford, A. M.; Bryant, D.; Li, X.; Nelson, J.; O’regan, B. C.; Barnes, P. R. Evidence for ion migration in hybrid perovskite solar cells with minimal hysteresis Nat. Commun. 2016, 7, 13831 DOI: 10.1038/ncomms13831

Cited By

ARTICLE SECTIONS
Jump To

This article is cited by 842 publications.

  1. Wei-Ting Wang, Chien-Hung Chiang, Qiang Zhang, Yijie Mu, Chun-Guey Wu, Shien-Ping Feng. Defect-Induced Dipole Moment Change of Passivators for Improving the Performance of Perovskite Photovoltaics. ACS Energy Letters 2024, 9 (6) , 2982-2989. https://doi.org/10.1021/acsenergylett.4c00839
  2. Surbhi Ramawat, Sumit Kukreti, Deep Jyoti Sapkota, Ambesh Dixit. Insight into the Microband Offset and Charge Transport Layer’s Suitability for an Efficient Inverted Perovskite Solar Cell: A Case Study for Tin-Based B-γ-CsSnI3. Energy & Fuels 2024, 38 (10) , 9011-9026. https://doi.org/10.1021/acs.energyfuels.4c00763
  3. Yanyan Peng, Dayong Jiang, Man Zhao, Mingyang Li, Haoda Li, Siyuan Li. Improving the Optoelectronic Performance of ZnO/Perovskite Ultraviolet–Visible–Near Infrared Photodetectors Using Bulk Heterojunctions. Crystal Growth & Design 2024, 24 (9) , 3649-3656. https://doi.org/10.1021/acs.cgd.3c01432
  4. Muhammad Noman, Ihsan Nawaz Khan, Affaq Qamar, Khalid AlSnaie, Hassan M. Hussein Farh. Mathematical Modeling and Optimization of Highly Efficient Nontoxic All-Inorganic CsSnGeI3-Based Perovskite Solar Cells with Oxide and Kesterite Charge Transport Layers. ACS Omega 2024, 9 (10) , 11398-11417. https://doi.org/10.1021/acsomega.3c07754
  5. Ashok Kumar Kaliamurthy, Francis Kwaku Asiam, Bommaramoni Yadagiri, Cheng Chen, Hyeong Cheol Kang, Sanjay Sandhu, Muhammad Zain Qamar, Kicheon Yoo, Jae-Joon Lee. Effect of Interfacial Polarization on the Trap Passivation and Dielectric Constant of SrF2/TiO2 for Dye-Sensitized Solar Cells. ACS Applied Energy Materials 2024, 7 (5) , 1983-1992. https://doi.org/10.1021/acsaem.3c03140
  6. Nathan Rodkey, Inma Gomar-Fernández, Federico Ventosinos, Cristina Roldan-Carmona, L. Jan Anton Koster, Henk J. Bolink. Close-Space Sublimation as a Scalable Method for Perovskite Solar Cells. ACS Energy Letters 2024, 9 (3) , 927-933. https://doi.org/10.1021/acsenergylett.3c02794
  7. Sanjay Sandhu, Md. Mahbubur Rahman, Bommaramoni Yadagiri, Ashok Kumar Kaliamurthy, Appiagyei Ewusi Mensah, Farihatun Jannat Lima, Saif Ahmed, Jongdeok Park, Manish Kumar, Jae-Joon Lee. Surface Reconstruction with Aprotic Trimethylsulfonium Iodide for Efficient and Stable Perovskite Solar Cells. ACS Applied Materials & Interfaces 2024, 16 (3) , 4169-4180. https://doi.org/10.1021/acsami.3c15520
  8. Deepak Devadiga, Ahipa Tantri Nagaraja, Dheeraj Devadiga, Muthu Selvakumar. Minireview and Perspectives of Liquid Crystals in Perovskite Solar Cells. Energy & Fuels 2024, 38 (2) , 854-868. https://doi.org/10.1021/acs.energyfuels.3c04050
  9. Ganga R. Neupane, Susanna M. Thon, Sheng Fu, Zhaoning Song, Yanfa Yan, Behrang H. Hamadani. Intensity-Modulated Photocurrent Spectroscopy Measurements of High-Efficiency Perovskite Solar Cells. The Journal of Physical Chemistry Letters 2024, 15 (1) , 290-297. https://doi.org/10.1021/acs.jpclett.3c03059
  10. Ismael Fernandez-Guillen, Vladimir S. Chirvony, Marie Kreĉmarová, Guillermo Muñoz-Matutano, Jesus Ortiga-Fibla, Ana Cros, Núria Garro, Juan F. Sánchez-Royo, Juan P Martínez-Pastor, María Carmen Asensio, Rafael Abargues, Pablo P. Boix. Boosting Photoluminescence in MAPbBr3 Single Crystals through Laser-Based Surface Modification. ACS Photonics 2023, 10 (12) , 4151-4159. https://doi.org/10.1021/acsphotonics.3c00777
  11. Seokjoo Ryu, Bumjin Gil, Beomsoo Kim, Jinhyun Kim, Byungwoo Park. Understanding the Trap Characteristics of Perovskite Solar Cells via Drive-Level Capacitance Profiling. ACS Applied Materials & Interfaces 2023, 15 (49) , 56909-56917. https://doi.org/10.1021/acsami.3c10126
  12. Xuefan Zhao, Zuolin Zhang, Yunfei Zhu, Fanbin Meng, Mengjia Li, Chenglin Wang, Wenhuan Gao, Yinsu Feng, Ru Li, Dongmei He, Jiangzhao Chen, Cong Chen. Rationally Tailoring Chiral Molecules to Minimize Interfacial Energy Loss Enables Efficient and Stable Perovskite Solar Cells Using Vacuum Flash Technology. Nano Letters 2023, 23 (23) , 11184-11192. https://doi.org/10.1021/acs.nanolett.3c03655
  13. Zhilong Chen, Hu Wang, Fenghua Li, Wenqing Zhang, Yuchuan Shao, Shuang Yang. Ultrasensitive and Robust CsPbBr3 Single-Crystal X-ray Detectors Based on Interface Engineering. ACS Applied Materials & Interfaces 2023, 15 (44) , 51370-51379. https://doi.org/10.1021/acsami.3c11409
  14. Siyu Yan, Jay B. Patel, Jae Eun Lee, Karim A. Elmestekawy, Sinclair R. Ratnasingham, Qimu Yuan, Laura M. Herz, Nakita K. Noel, Michael B. Johnston. A Templating Approach to Controlling the Growth of Coevaporated Halide Perovskites. ACS Energy Letters 2023, 8 (10) , 4008-4015. https://doi.org/10.1021/acsenergylett.3c01368
  15. Weidong Zhu, Xiaoyan Yao, Shengbin Shi, Zhongkai Zhang, Zhicheng Song, Peng Gao, Tianran Wang, Yanshuang Ba, Peng Dong. Mixed-Bromide Halide Exchange toward Efficient and Stable Carbon-Electrode CsPbBr3 Solar Cells. ACS Applied Energy Materials 2023, 6 (19) , 9798-9804. https://doi.org/10.1021/acsaem.3c00723
  16. Chuanzhou Han, Xufeng Xiao, Wenhao Zhang, Qiaojiao Gao, Jianhang Qi, Jiale Liu, Junwei Xiang, Yanjie Cheng, Jiankang Du, Cheng Qiu, Anyi Mei, Hongwei Han. Impact and Role of Epitaxial Growth in Metal Halide Perovskite Solar Cells. ACS Materials Letters 2023, 5 (9) , 2445-2463. https://doi.org/10.1021/acsmaterialslett.3c00496
  17. Partha Saha, Md. Maksudur Rahman, Chloe L. Tolbert, Caleb M. Hill. Facet-Dependent Photoelectrochemistry on Single Crystal Organic–Inorganic Halide Perovskite Electrodes. Chemical & Biomedical Imaging 2023, 1 (5) , 488-494. https://doi.org/10.1021/cbmi.3c00069
  18. Ganga Vinod Chittiboina, Abhimanyu Singareddy, Akansh Agarwal, Swasti Bhatia, Pradeep R. Nair. Intrinsic Degradation-Dependent Energy Yield Estimates for Perovskite/Silicon Tandem Solar Cells under Field Conditions. ACS Energy Letters 2023, 8 (7) , 2927-2934. https://doi.org/10.1021/acsenergylett.3c00614
  19. Jianhui Fu, Sankaran Ramesh, Jia Wei Melvin Lim, Tze Chien Sum. Carriers, Quasi-particles, and Collective Excitations in Halide Perovskites. Chemical Reviews 2023, 123 (13) , 8154-8231. https://doi.org/10.1021/acs.chemrev.2c00843
  20. Luke Grater, Mingcong Wang, Sam Teale, Suhas Mahesh, Aidan Maxwell, Yanjiang Liu, So Min Park, Bin Chen, Frédéric Laquai, Mercouri G. Kanatzidis, Edward H. Sargent. Sterically Suppressed Phase Segregation in 3D Hollow Mixed-Halide Wide Band Gap Perovskites. The Journal of Physical Chemistry Letters 2023, 14 (26) , 6157-6162. https://doi.org/10.1021/acs.jpclett.3c01156
  21. Zongyang Peng, Leyang Jin, Zhuang Zuo, Qi Qi, Shaocong Hou, Yongping Fu, Dechun Zou. Isolating the Oxygen Adsorption Defects on Sputtered Tin Oxide for Efficient Perovskite Solar Cells. ACS Applied Materials & Interfaces 2023, 15 (19) , 23518-23526. https://doi.org/10.1021/acsami.3c03679
  22. Dipankar Sahoo, Arnab Kanti Karan, Nabin Baran Manik. Influence of SWCNT on the Electrical Behavior of an Environmentally Friendly CH3NH3SnI3 Perovskite-Based Optoelectronic Schottky Device. ACS Applied Electronic Materials 2023, 5 (4) , 2203-2214. https://doi.org/10.1021/acsaelm.3c00086
  23. Rakesh R. Pradhan, Mathan K. Eswaran, Anand S. Subbiah, Aslihan Babayigit, Stefaan De Wolf, Udo Schwingenschlögl. Elucidating the Role of Contact-Induced Gap States and Passivation Molecules at Perovskite/Metal Contacts. ACS Applied Energy Materials 2023, 6 (8) , 4111-4118. https://doi.org/10.1021/acsaem.3c00292
  24. Tuhin Ghosh, Pratap Mane, Brahmananda Chakraborty, Prasana Kumar Sahoo, Debabrata Pradhan. Laterally Grown Strain-Engineered Semitransparent Perovskite Solar Cells with 16.01% Efficiency. ACS Applied Materials & Interfaces 2023, 15 (14) , 17994-18005. https://doi.org/10.1021/acsami.2c20124
  25. Zeen Zhao, Wenbin Tang, Shihua Zhang, Yecheng Ding, Xuefeng Zhao, Guoliang Yuan. Flexible Self-Powered Vertical Photodetectors Based on the [001]-Oriented CsPbBr3 Film. The Journal of Physical Chemistry C 2023, 127 (10) , 4846-4852. https://doi.org/10.1021/acs.jpcc.2c08845
  26. You Jin Park, Young In Jeon, In Seok Yang, Hyunsue Choo, Woo Seok Suh, So-Yeon Ju, Hui-Seon Kim, Jia Hong Pan, Wan In Lee. Selective Control of Novel TiO2 Nanorods: Excellent Building Blocks for the Electron Transport Layer of Mesoscopic Perovskite Solar Cells. ACS Applied Materials & Interfaces 2023, 15 (7) , 9447-9456. https://doi.org/10.1021/acsami.2c21731
  27. Yuze Li, Jia-Jiu Ye, Asma Medjahed, Dmitry Aldakov, Stéphanie Pouget, Elisabeth Djurado, Lin Xu, Peter Reiss. High Fill Factor and Reduced Hysteresis Perovskite Solar Cells Using Small-Molecule-Engineered Nickel Oxide as the Hole Transport Layer. ACS Applied Energy Materials 2023, 6 (3) , 1555-1564. https://doi.org/10.1021/acsaem.2c03434
  28. Nilesh G Saykar, Muzahir Iqbal, Mahendra Pawar, Kashinath T Chavan, Santosh K Mahapatra. Dual-Functional 3-Acetyl-2,5-dimethylthiophene Additive-Assisted Crystallization Control and Trap State Passivation for High-Performance Perovskite Solar Cells. ACS Applied Energy Materials 2022, 5 (12) , 14701-14711. https://doi.org/10.1021/acsaem.2c01881
  29. Shrabani Panigrahi, Tomás Calmeiro, Manuel J. Mendes, Hugo Águas, Elvira Fortunato, Rodrigo Martins. Observation of Grain Boundary Passivation and Charge Distribution in Perovskite Films Improved with Anti-solvent Treatment. The Journal of Physical Chemistry C 2022, 126 (45) , 19367-19375. https://doi.org/10.1021/acs.jpcc.2c05055
  30. Richard H. J. Kim, Zhaoyu Liu, Chuankun Huang, Joong-Mok Park, Samuel J. Haeuser, Zhaoning Song, Yanfa Yan, Yongxin Yao, Liang Luo, Jigang Wang. Terahertz Nanoimaging of Perovskite Solar Cell Materials. ACS Photonics 2022, 9 (11) , 3550-3556. https://doi.org/10.1021/acsphotonics.2c00861
  31. Yan Li, Siqi Li, Yujie Shen, Xue Han, Yao Li, Yingchun Yu, Meilan Huang, Xia Tao. Multifunctional Histidine Cross-Linked Interface toward Efficient Planar Perovskite Solar Cells. ACS Applied Materials & Interfaces 2022, 14 (42) , 47872-47881. https://doi.org/10.1021/acsami.2c13585
  32. Yu-Feng Chen, Zhen-Ming Luo, Chien-Hung Chiang, Chun-Guey Wu. Multifunctional Ionic Fullerene Additive for Synergistic Boundary and Defect Healing of Tin Perovskite to Achieve High-Efficiency Solar Cells. ACS Applied Materials & Interfaces 2022, 14 (41) , 46603-46614. https://doi.org/10.1021/acsami.2c12785
  33. Zhaobo Zhou, Junjie He, Thomas Frauenheim, Oleg V. Prezhdo, Jinlan Wang. Control of Hot Carrier Cooling in Lead Halide Perovskites by Point Defects. Journal of the American Chemical Society 2022, 144 (39) , 18126-18134. https://doi.org/10.1021/jacs.2c08487
  34. Jinho Yoon, Xuewen Liu, Eun-Cheol Lee. Defect Passivation via Isoxazole Doping in Perovskite Solar Cells. ACS Omega 2022, 7 (38) , 34278-34285. https://doi.org/10.1021/acsomega.2c03775
  35. Jose F. Castaneda, Jeong-Hyeok Im, Yucheng Liu, Shengzhong Liu, Nam-Gyu Park, Yong Zhang. Domain Size, Temperature, and Time Dependence of Photodegradation in MAPbI3 Probed by Raman Spectroscopy. ACS Energy Letters 2022, 7 (9) , 3095-3103. https://doi.org/10.1021/acsenergylett.2c01640
  36. Muhammad Akmal Kamarudin, Shahrir Razey Sahamir, Kohei Nishimura, Satoshi Iikubo, Kenji Yoshino, Takashi Minemoto, Qing Shen, Shuzi Hayase. Suppression of Defect and Trap Density through Dimethylammonium-Substituted Tin Perovskite Solar Cells. ACS Materials Letters 2022, 4 (9) , 1855-1862. https://doi.org/10.1021/acsmaterialslett.2c00275
  37. Anubha Agarwal, Shun Omagari, Martin Vacha. Nanoscale Structural Heterogeneity and Efficient Intergrain Charge Diffusion in a Series of Mixed MA/FA Halide Perovskite Films. ACS Energy Letters 2022, 7 (8) , 2443-2449. https://doi.org/10.1021/acsenergylett.2c01271
  38. Bowen Jin, Yidong Ming, Zihui Liang, Kai Wang, Congcong Wu. Avoid Pitfalls in Identifying Perovskite Grain Size. The Journal of Physical Chemistry Letters 2022, 13 (31) , 7236-7242. https://doi.org/10.1021/acs.jpclett.2c02060
  39. Arava Zohar, Michael Kulbak, Silver H. Turren-Cruz, Pabitra K. Nayak, Adi Kama, Anders Hagfeldt, Henry J Snaith, Gary Hodes, David Cahen. In Operando, Photovoltaic, and Microscopic Evaluation of Recombination Centers in Halide Perovskite-Based Solar Cells. ACS Applied Materials & Interfaces 2022, 14 (30) , 34171-34179. https://doi.org/10.1021/acsami.1c08675
  40. Ming Luo, Xueping Zong, Wenhua Zhang, Mengnan Hua, Zhe Sun, Mao Liang, Song Xue. A Multifunctional Fluorinated Polymer Enabling Efficient MAPbI3-Based Inverted Perovskite Solar Cells. ACS Applied Materials & Interfaces 2022, 14 (27) , 31285-31295. https://doi.org/10.1021/acsami.2c06903
  41. Yinan Lao, Yuqing Zhang, Shuang Yang, Zehao Zhang, Wenjin Yu, Bo Qu, Lixin Xiao, Zhijian Chen. Efficient Perovskite Solar Cells with Enhanced Thermal Stability by Sulfide Treatment. ACS Applied Materials & Interfaces 2022, 14 (23) , 27427-27434. https://doi.org/10.1021/acsami.2c05605
  42. Weon-Sik Chae, Sinyoung Cho, Joo-Yun Jung, Jong-Hwa Kim, Jong-Soo Lee. Multiple-Route Exciton Recombination Dynamics and Improved Stability of Perovskite Quantum Dots by Plasmonic Photonic Crystal. The Journal of Physical Chemistry Letters 2022, 13 (22) , 5040-5048. https://doi.org/10.1021/acs.jpclett.2c00735
  43. Kai Zou, Qihua Li, Jingquan Fan, Hebing Tang, Lixin Chen, Shuxia Tao, Tingting Xu, Wei Huang. Pyridine Derivatives’ Surface Passivation Enables Efficient and Stable Carbon-Based Perovskite Solar Cells. ACS Materials Letters 2022, 4 (6) , 1101-1111. https://doi.org/10.1021/acsmaterialslett.2c00123
  44. Kwang Choi, Min Ju Jeong, Seungmin Lee, Ghaida Alosaimi, Jan Seidel, Jae Sung Yun, Jun Hong Noh. Suppressing Halide Segregation in Wide-Band-Gap Mixed-Halide Perovskite Layers through Post-Hot Pressing. ACS Applied Materials & Interfaces 2022, 14 (21) , 24341-24350. https://doi.org/10.1021/acsami.2c03492
  45. Maddaka Reddeppa, Byung-Guon Park, Dong-Jin Nam, Chandrakalavathi Thota, Na-Hyun Bak, Kedhareswara Sairam Pasupuleti, Young-Heon Kim, Song-Gang Kim, Moon-Deock Kim. Photovoltaic Photodetectors Based on In2O3/InN Core–Shell Nanorods. ACS Applied Nano Materials 2022, 5 (5) , 7418-7426. https://doi.org/10.1021/acsanm.2c01410
  46. Mohamed M. Elnaggar, Lavrenty G. Gutsev, Nikita A. Emelianov, Petr M. Kuznetsov, Lyubov A. Frolova, Sergey M. Aldoshin, Pavel A. Troshin. Molecular Engineering of Polytriarylamine-Based Hole-Transport Materials for p–i–n Perovskite Solar Cells: Methyl Groups Matter. ACS Applied Energy Materials 2022, 5 (5) , 5388-5394. https://doi.org/10.1021/acsaem.1c03040
  47. Weichuan Zhang, Xianxin Wu, Jin Zhou, Bing Han, Xinfeng Liu, Yuan Zhang, Huiqiong Zhou. Pseudohalide-Assisted Growth of Oriented Large Grains for High-Performance and Stable 2D Perovskite Solar Cells. ACS Energy Letters 2022, 7 (5) , 1842-1849. https://doi.org/10.1021/acsenergylett.2c00485
  48. Xiao Zhao, Shimao Wang, Fuwei Zhuge, Yanan Song, Toru Aoki, Weiwei Dong, Mengyu Fu, Gang Meng, Zanhong Deng, Ruhua Tao, Xiaodong Fang. High-Performance Planar-Type Photodetector Based on Hot-Pressed CsPbBr3 Wafer. The Journal of Physical Chemistry Letters 2022, 13 (13) , 3008-3015. https://doi.org/10.1021/acs.jpclett.2c00089
  49. Beier Hu, Jing Zhang, Zhongli Guo, Lihua Lu, Puyang Li, Mengyu Chen, Cheng Li. Manipulating Ion Migration and Interfacial Carrier Dynamics via Amino Acid Treatment in Planar Perovskite Solar Cells. ACS Applied Materials & Interfaces 2022, 14 (13) , 15840-15848. https://doi.org/10.1021/acsami.2c01640
  50. Stener Lie, Annalisa Bruno, Lydia Helena Wong, Lioz Etgar. Semitransparent Perovskite Solar Cells with > 13% Efficiency and 27% Transperancy Using Plasmonic Au Nanorods. ACS Applied Materials & Interfaces 2022, 14 (9) , 11339-11349. https://doi.org/10.1021/acsami.1c22748
  51. Yaxin Du, Dongping Zhu, Qingbin Cai, Shuai Yuan, Guibin Shen, Pei Dong, Cheng Mu, Yi Wang, Xi-Cheng Ai. Spacer Engineering of Thiophene-Based Two-Dimensional/Three-Dimensional Hybrid Perovskites for Stable and Efficient Solar Cells. The Journal of Physical Chemistry C 2022, 126 (7) , 3351-3358. https://doi.org/10.1021/acs.jpcc.1c10210
  52. Shu Hu, Yongtao Huang, Yang Zhang, Pingyuan Yan, Heng Li, ChuanXiang Sheng. Slow Hot-Carrier-Cooling in a 2D Lead-Iodide Perovskite Film and Its Photovoltaic Device. The Journal of Physical Chemistry C 2022, 126 (5) , 2374-2382. https://doi.org/10.1021/acs.jpcc.1c09313
  53. Hongfei Chen, Hejin Yan, Yongqing Cai. Effects of Defect on Work Function and Energy Alignment of PbI2: Implications for Solar Cell Applications. Chemistry of Materials 2022, 34 (3) , 1020-1029. https://doi.org/10.1021/acs.chemmater.1c03238
  54. Lu Qiao, Wei-Hai Fang, Run Long. Dual Passivation of Point Defects at Perovskite Grain Boundaries with Ammonium Salts Greatly Inhibits Nonradiative Charge Recombination. The Journal of Physical Chemistry Letters 2022, 13 (4) , 954-961. https://doi.org/10.1021/acs.jpclett.1c04038
  55. Masoud Karimipour, Sepideh Khazraei, Byeong Jo Kim, Gerrit Boschloo, Erik M. J. Johansson. Efficiency and Stability Enhancement of Perovskite Solar Cells Utilizing a Thiol Ligand and MoS2 (100) Nanosheet Surface Modification. ACS Applied Energy Materials 2021, 4 (12) , 14080-14092. https://doi.org/10.1021/acsaem.1c02412
  56. Rongmei Zhao, Lin Xie, Rongshan Zhuang, Tai Wu, Rongjun Zhao, Linqin Wang, Licheng Sun, Yong Hua. Interfacial Defect Passivation and Charge Carrier Management for Efficient Perovskite Solar Cells via a Highly Crystalline Small Molecule. ACS Energy Letters 2021, 6 (12) , 4209-4219. https://doi.org/10.1021/acsenergylett.1c01898
  57. Tianjun Hu, Dongyu Li, Qingsong Shan, Yuhui Dong, Hengyang Xiang, Wallace C. H. Choy, Haibo Zeng. Defect Behaviors in Perovskite Light-Emitting Diodes. ACS Materials Letters 2021, 3 (12) , 1702-1728. https://doi.org/10.1021/acsmaterialslett.1c00474
  58. Tianyuan Luo, Gang Ye, Xiayan Chen, Manman Ding, Tian Ye, Chunyan Zhao, Wenfeng Zhang, Haixin Chang. Interface and Grain Boundary Passivation by PEA-SCN Double Ions via One-Step Crystal Engineering for All Air-Processed, Stable Perovskite Solar Cells. ACS Applied Energy Materials 2021, 4 (11) , 12290-12297. https://doi.org/10.1021/acsaem.1c02113
  59. Daniel D. Astridge, Jacob B. Hoffman, Fei Zhang, So Yeon Park, Kai Zhu, Alan Sellinger. Polymer Hole Transport Materials for Perovskite Solar Cells via Buchwald–Hartwig Amination. ACS Applied Polymer Materials 2021, 3 (11) , 5578-5587. https://doi.org/10.1021/acsapm.1c00891
  60. Rohit D. Chavan, Mohammad Mahdi Tavakoli, Suverna Trivedi, Daniel Prochowicz, Abul Kalam, Pankaj Yadav, Pravin H. Bhoite, Chang Kook Hong. Interface Engineering of Mesoscopic Perovskite Solar Cells by Atomic Layer Deposition of Ta2O5. ACS Applied Energy Materials 2021, 4 (10) , 10433-10441. https://doi.org/10.1021/acsaem.1c00367
  61. Xiao Zhao, Shimao Wang, Xueyan Shan, Gang Meng, Xiaodong Fang. Fabrications of Halide Perovskite Single-Crystal Slices and Their Applications in Solar Cells, Photodetectors, and LEDs. Crystal Growth & Design 2021, 21 (10) , 5983-5997. https://doi.org/10.1021/acs.cgd.1c00548
  62. M. Bidikoudi, C. Simal, E. Stathatos. Exploring the Effect of Lewis-Base Additives on the Performance and Stability of Mesoscopic Carbon-Electrode Perovskite Solar Cells. ACS Applied Energy Materials 2021, 4 (9) , 8810-8823. https://doi.org/10.1021/acsaem.1c00920
  63. Sapir Bitton, Qingzhi An, Yana Vaynzof, Nir Tessler. Spatial Distribution of Solar Cell Parameters in Multigrain Halide-Perovskite Films: A Device Model Perspective. ACS Applied Energy Materials 2021, 4 (9) , 8709-8714. https://doi.org/10.1021/acsaem.1c01415
  64. Lingyi Meng, Xiaoyan Yu, Juan Du, Junjie Shi, Can-Zhong Lu, Peng Gao. Marked Near-Infrared Response of 2D Ca3Sn2S7 Chalcogenide Perovskite via Solid and Electronic Structure Engineering. The Journal of Physical Chemistry C 2021, 125 (37) , 20241-20248. https://doi.org/10.1021/acs.jpcc.1c07037
  65. Hsin-Hsiang Huang, Hsinhan Tsai, Rathinam Raja, Shu-Ling Lin, Dibyajyoti Ghosh, Cheng-Hung Hou, Jing-Jong Shyue, Sergei Tretiak, Wei Chen, King-Fu Lin, Wanyi Nie, Leeyih Wang. Robust Unencapsulated Perovskite Solar Cells Protected by a Fluorinated Fullerene Electron Transporting Layer. ACS Energy Letters 2021, 6 (9) , 3376-3385. https://doi.org/10.1021/acsenergylett.1c01526
  66. Bhagyashree Mahesha Sachith, Takuya Okamoto, Sushant Ghimire, Tomokazu Umeyama, Yuta Takano, Hiroshi Imahori, Vasudevanpillai Biju. Long-Range Interfacial Charge Carrier Trapping in Halide Perovskite-C60 and Halide Perovskite-TiO2 Donor–Acceptor Films. The Journal of Physical Chemistry Letters 2021, 12 (35) , 8644-8651. https://doi.org/10.1021/acs.jpclett.1c01909
  67. Xiaoli Gong, Haimin Li, Ruonan Zhou, Xian Peng, Yukun Ouyang, Huxin Luo, Xingchong Liu, Jia Zhuang, Hanyu Wang, Yafei Ni, Yue Lei. Strong Electron Acceptor of a Fluorine-Containing Group Leads to High Performance of Perovskite Solar Cells. ACS Applied Materials & Interfaces 2021, 13 (34) , 41149-41158. https://doi.org/10.1021/acsami.1c07610
  68. Mei Lyu, Sungmin Park, Hyeonju Lee, Boo Soo Ma, So Hyun Park, Ki-Ha Hong, Hyungjun Kim, Taek-Soo Kim, Jun Hong Noh, Hae Jung Son, Nam-Gyu Park. Simultaneous Enhanced Efficiency and Stability of Perovskite Solar Cells Using Adhesive Fluorinated Polymer Interfacial Material. ACS Applied Materials & Interfaces 2021, 13 (30) , 35595-35605. https://doi.org/10.1021/acsami.1c05822
  69. M. Prete, M. V. Khenkin, D. Glowienka, B. R. Patil, J. S. Lissau, I. Dogan, J. L. Hansen, T. Leißner, J. Fiutowski, H.-G. Rubahn, B. Julsgaard, P. Balling, V. Turkovic, Y. Galagan, E. A. Katz, M. Madsen. Bias-Dependent Dynamics of Degradation and Recovery in Perovskite Solar Cells. ACS Applied Energy Materials 2021, 4 (7) , 6562-6573. https://doi.org/10.1021/acsaem.1c00588
  70. Leilei Gu, Shubo Wang, Yiqi Chen, Yibo Xu, Ruiyi Li, Di Liu, Xiang Fang, Xuguang Jia, Ningyi Yuan, Jianning Ding. Stable High-Performance Perovskite Solar Cells via Passivation of the Grain Boundary and Interface. ACS Applied Energy Materials 2021, 4 (7) , 6883-6891. https://doi.org/10.1021/acsaem.1c01013
  71. Chenqiang Xu, Yewei Zhang, Paifeng Luo, Jia Sun, Haisheng Wang, Ying-Wei Lu, Fei Ding, Chao Zhang, Juntao Hu. Comparative Study on TiO2 and C60 Electron Transport Layers for Efficient Perovskite Solar Cells. ACS Applied Energy Materials 2021, 4 (6) , 5543-5553. https://doi.org/10.1021/acsaem.1c00226
  72. Li Chen, Jingde Chen, Chenyue Wang, Hao Ren, Yu-Xin Luo, Kong-Chao Shen, Yanqing Li, Fei Song, Xingyu Gao, Jian-Xin Tang. High-Light-Tolerance PbI2 Boosting the Stability and Efficiency of Perovskite Solar Cells. ACS Applied Materials & Interfaces 2021, 13 (21) , 24692-24701. https://doi.org/10.1021/acsami.1c02929
  73. Tianqi Niu, Qifan Xue, Hin-Lap Yip. Molecularly Engineered Interfaces in Metal Halide Perovskite Solar Cells. The Journal of Physical Chemistry Letters 2021, 12 (20) , 4882-4901. https://doi.org/10.1021/acs.jpclett.1c00954
  74. Adriano S. Marques, Roberto M. Faria, Jilian N. Freitas, Ana F. Nogueira. Low-Temperature Blade-Coated Perovskite Solar Cells. Industrial & Engineering Chemistry Research 2021, 60 (19) , 7145-7154. https://doi.org/10.1021/acs.iecr.1c00789
  75. Unyamanee Rosungnern, Pisist Kumnorkaew, Navaphun Kayunkid, Narong Chanlek, Youyong Li, I-Ming Tang, Non Thongprong, Nopporn Rujisamphan, Thidarat Supasai. Impact of a Spun-Cast MoOx Layer on the Enhanced Moisture Stability and Performance-Limiting Behaviors of Perovskite Solar Cells. ACS Applied Energy Materials 2021, 4 (4) , 3169-3181. https://doi.org/10.1021/acsaem.0c02963
  76. Mritunjaya Parashar, Ranbir Singh, Kicheon Yoo, Jae-Joon Lee. Formation of 1-D/3-D Fused Perovskite for Efficient and Moisture Stable Solar Cells. ACS Applied Energy Materials 2021, 4 (3) , 2751-2760. https://doi.org/10.1021/acsaem.1c00028
  77. Vincent M. Le Corre, Elisabeth A. Duijnstee, Omar El Tambouli, James M. Ball, Henry J. Snaith, Jongchul Lim, L. Jan Anton Koster. Revealing Charge Carrier Mobility and Defect Densities in Metal Halide Perovskites via Space-Charge-Limited Current Measurements. ACS Energy Letters 2021, 6 (3) , 1087-1094. https://doi.org/10.1021/acsenergylett.0c02599
  78. Dongxu Lin, Xin Xu, Jiming Wang, Tiankai Zhang, Fangyan Xie, Li Gong, Jian Chen, Tingting Shi, Jifu Shi, Pengyi Liu, Weiguang Xie. Construction of an Iodine Diffusion Barrier Using Network Structure Silicone Resin for Stable Perovskite Solar Cells. ACS Applied Materials & Interfaces 2021, 13 (7) , 8138-8146. https://doi.org/10.1021/acsami.0c18009
  79. Erik O. Shalenov, Karlygash N. Dzhumagulova, Yeldos S. Seitkozhanov, Annie Ng, Constantinos Valagiannopoulos, Askhat N. Jumabekov. Insights on Desired Fabrication Factors from Modeling Sandwich and Quasi-Interdigitated Back-Contact Perovskite Solar Cells. ACS Applied Energy Materials 2021, 4 (2) , 1093-1107. https://doi.org/10.1021/acsaem.0c02120
  80. Avi Mathur, Alexander Li, Vivek Maheshwari. Nanoscale Architecture of Polymer–Organolead Halide Perovskite Films and the Effect of Polymer Chain Mobility on Device Performance. The Journal of Physical Chemistry Letters 2021, 12 (5) , 1481-1489. https://doi.org/10.1021/acs.jpclett.1c00004
  81. Tomáš Homola, Jan Pospisil, Masoud Shekargoftar, Tomáš Svoboda, Matej Hvojnik, Pavol Gemeiner, Martin Weiter, Petr Dzik. Perovskite Solar Cells with Low-Cost TiO2 Mesoporous Photoanodes Prepared by Rapid Low-Temperature (70 °C) Plasma Processing. ACS Applied Energy Materials 2020, 3 (12) , 12009-12018. https://doi.org/10.1021/acsaem.0c02144
  82. So Yeon Park, Hyung Cheoul Shim. Highly Efficient and Air-Stable Heterostructured Perovskite Quantum Dot Solar Cells Using a Solid-State Cation-Exchange Reaction. ACS Applied Materials & Interfaces 2020, 12 (51) , 57124-57133. https://doi.org/10.1021/acsami.0c17877
  83. Bo Li, Bohong Chang, Lu Pan, Zihao Li, Lin Fu, Zhubing He, Longwei Yin. Tin-Based Defects and Passivation Strategies in Tin-Related Perovskite Solar Cells. ACS Energy Letters 2020, 5 (12) , 3752-3772. https://doi.org/10.1021/acsenergylett.0c01796
  84. Lu Qiao, Wei-Hai Fang, Run Long, Oleg V. Prezhdo. Atomic Model for Alkali Metal Passivation of Point Defects at Perovskite Grain Boundaries. ACS Energy Letters 2020, 5 (12) , 3813-3820. https://doi.org/10.1021/acsenergylett.0c02136
  85. Zhelu Hu, Qingzhi An, Hengyang Xiang, Lionel Aigouy, Baoquan Sun, Yana Vaynzof, Zhuoying Chen. Enhancing the Efficiency and Stability of Triple-Cation Perovskite Solar Cells by Eliminating Excess PbI2 from the Perovskite/Hole Transport Layer Interface. ACS Applied Materials & Interfaces 2020, 12 (49) , 54824-54832. https://doi.org/10.1021/acsami.0c17258
  86. Matteo Bonomo, Babak Taheri, Luca Bonandini, Sergio Castro-Hermosa, Thomas M. Brown, Marco Zanetti, Alberto Menozzi, Claudia Barolo, Francesca Brunetti. Thermosetting Polyurethane Resins as Low-Cost, Easily Scalable, and Effective Oxygen and Moisture Barriers for Perovskite Solar Cells. ACS Applied Materials & Interfaces 2020, 12 (49) , 54862-54875. https://doi.org/10.1021/acsami.0c17652
  87. Tzu-Sen Su, Felix Thomas Eickemeyer, Michael A. Hope, Farzaneh Jahanbakhshi, Marko Mladenović, Jun Li, Zhiwen Zhou, Aditya Mishra, Jun-Ho Yum, Dan Ren, Anurag Krishna, Olivier Ouellette, Tzu-Chien Wei, Hua Zhou, Hsin-Hsiang Huang, Mounir Driss Mensi, Kevin Sivula, Shaik M. Zakeeruddin, Jovana V. Milić, Anders Hagfeldt, Ursula Rothlisberger, Lyndon Emsley, Hong Zhang, Michael Grätzel. Crown Ether Modulation Enables over 23% Efficient Formamidinium-Based Perovskite Solar Cells. Journal of the American Chemical Society 2020, 142 (47) , 19980-19991. https://doi.org/10.1021/jacs.0c08592
  88. Liang Wang, Shuzhang Yang, Qianji Han, Fengyang Yu, Xiaoyong Cai, Fengjing Liu, Chu Zhang, Tingli Ma. Bifunctional Organic Disulfide for High-Efficiency and High-Stability Planar Perovskite Solar Cells. ACS Applied Energy Materials 2020, 3 (10) , 9724-9731. https://doi.org/10.1021/acsaem.0c01329
  89. Lu Zhang, Yucheng Liu, Xilai He, Haochen Ye, Jing Leng, Xiaodong Ren, Shengye Jin, Shengzhong Liu. Cd-Doped Triple-Cation Perovskite Thin Films with a 20 μs Carrier Lifetime. The Journal of Physical Chemistry C 2020, 124 (40) , 22011-22018. https://doi.org/10.1021/acs.jpcc.0c07423
  90. Damian Głowienka, Francesco Di Giacomo, Mehrdad Najafi, Ilker Dogan, Alfredo Mameli, Fallon J. M. Colberts, Jędrzej Szmytkowski, Yulia Galagan. Effect of Different Bromine Sources on the Dual Cation Mixed Halide Perovskite Solar Cells. ACS Applied Energy Materials 2020, 3 (9) , 8285-8294. https://doi.org/10.1021/acsaem.0c00767
  91. Kun Cao, Yangfeng Cheng, Junwen Chen, Yue Huang, Mengru Ge, Jie Qian, Lihui Liu, Jing Feng, Shufen Chen, Wei Huang. Regulated Crystallization of FASnI3 Films through Seeded Growth Process for Efficient Tin Perovskite Solar Cells. ACS Applied Materials & Interfaces 2020, 12 (37) , 41454-41463. https://doi.org/10.1021/acsami.0c11253
  92. Lu Qiao, Wei-Hai Fang, Run Long, Oleg V. Prezhdo. Photoinduced Dynamics of Charge Carriers in Metal Halide Perovskites from an Atomistic Perspective. The Journal of Physical Chemistry Letters 2020, 11 (17) , 7066-7082. https://doi.org/10.1021/acs.jpclett.0c01687
  93. Zedong Lin. New Extraction Technique of In-Gap Electronic-State Spectrum Based on Time-Resolved Charge Extraction. ACS Omega 2020, 5 (34) , 21762-21767. https://doi.org/10.1021/acsomega.0c02800
  94. Tao Wang, Gang Lian, Liping Huang, Fei Zhu, Deliang Cui, Qilong Wang, Qingbo Meng, Ching-Ping Wong. MAPbI3 Quasi-Single-Crystal Films Composed of Large-Sized Grains with Deep Boundary Fusion for Sensitive Vis–NIR Photodetectors. ACS Applied Materials & Interfaces 2020, 12 (34) , 38314-38324. https://doi.org/10.1021/acsami.0c08674
  95. Jaemin Kong, Hanyu Wang, Jason A. Röhr, Zachary S. Fishman, Yuanyuan Zhou, Mingxing Li, Mircea Cotlet, Geunjin Kim, Christopher Karpovich, Francisco Antonio, Nitin P. Padture, André D. Taylor. Perovskite Solar Cells with Enhanced Fill Factors Using Polymer-Capped Solvent Annealing. ACS Applied Energy Materials 2020, 3 (8) , 7231-7238. https://doi.org/10.1021/acsaem.0c00854
  96. Shanshan Zhang, Paul E. Shaw, Guanran Zhang, Hui Jin, Meiqian Tai, Hong Lin, Paul Meredith, Paul L. Burn, Dieter Neher, Martin Stolterfoht. Defect/Interface Recombination Limited Quasi-Fermi Level Splitting and Open-Circuit Voltage in Mono- and Triple-Cation Perovskite Solar Cells. ACS Applied Materials & Interfaces 2020, 12 (33) , 37647-37656. https://doi.org/10.1021/acsami.0c02960
  97. Junseop Byeon, Jutae Kim, Ji-Young Kim, Gunhee Lee, Kijoon Bang, Namyoung Ahn, Mansoo Choi. Charge Transport Layer-Dependent Electronic Band Bending in Perovskite Solar Cells and Its Correlation to Light-Induced Device Degradation. ACS Energy Letters 2020, 5 (8) , 2580-2589. https://doi.org/10.1021/acsenergylett.0c01022
  98. Cong Chen, Zhaoning Song, Chuanxiao Xiao, Rasha A. Awni, Canglang Yao, Niraj Shrestha, Chongwen Li, Sandip Singh Bista, Yi Zhang, Lei Chen, Randy J. Ellingson, Chun-Sheng Jiang, Mowafak Al-Jassim, Guojia Fang, Yanfa Yan. Arylammonium-Assisted Reduction of the Open-Circuit Voltage Deficit in Wide-Bandgap Perovskite Solar Cells: The Role of Suppressed Ion Migration. ACS Energy Letters 2020, 5 (8) , 2560-2568. https://doi.org/10.1021/acsenergylett.0c01350
  99. Jin Young Kim, Jin-Wook Lee, Hyun Suk Jung, Hyunjung Shin, Nam-Gyu Park. High-Efficiency Perovskite Solar Cells. Chemical Reviews 2020, 120 (15) , 7867-7918. https://doi.org/10.1021/acs.chemrev.0c00107
  100. Emanuele Calabrò, Fabio Matteocci, Barbara Paci, Lucio Cinà, Luigi Vesce, Jessica Barichello, Amanda Generosi, Andrea Reale, Aldo Di Carlo. Easy Strategy to Enhance Thermal Stability of Planar PSCs by Perovskite Defect Passivation and Low-Temperature Carbon-Based Electrode. ACS Applied Materials & Interfaces 2020, 12 (29) , 32536-32547. https://doi.org/10.1021/acsami.0c05878
Load more citations
  • Abstract

    Figure 1

    Figure 1. (a) Schematics of the vacuum-deposited perovskite cells used and (b) scanning electron microscope (SEM) image of the CH3NH3PbI3 surface.

    Figure 2

    Figure 2. (a) In typical inorganic solar cells (poly-Si, CdTe), the empty neutral traps at GBs and interfaces when filled with electrons result in a weakened transport due to the potential barrier (qϕB) and the nonradiative recombination between holes and trapped electrons is strong. (b) In PSCs, it is likely that the empty traps are positively charged due to accumulated iodide vacancies (VI+) at GBs and interfaces. Therefore, when filled with electrons, the traps are neutral, electron transport is relatively unaffected, and nonradiative recombination is weak.

    Figure 3

    Figure 3. The p–i–n device skeleton showing the energy levels, interface traps (red), and GBs (dashed lines). Upon illumination, free electrons and holes are transported through the respective materials and are extracted at the electrodes.

    Figure 4

    Figure 4. (a) JV characteristics of p–i–n and n–i–p PSCs. The open symbols are experimental data for vacuum-deposited CH3NH3PbI3 solar cells. (9) The solid lines represent the simulations. (b) Normalized generation profile for the p–i–n and n–i–p (inset) solar cell as calculated using the transfer matrix model. (52)

    Figure 5

    Figure 5. Light intensity dependence of (a) VOC and (b) FF for both p–i–n and n–i–p cells. The filled symbols and lines in (a) represent experimental data and simulation, respectively. The open and filled symbols in (b) represent experimental data and simulation, respectively.

    Figure 6

    Figure 6. Simulated forward/reverse scan of p–i–n and n–i–p cells showing hysteresis in the JV curves when negative iodide ions (Xa = 4 × 1014 cm–3) are mobile. The forward scan is performed after preconditioning at −0.2 V, and the reverse scan is carried out after preconditioning at 1.2 V.

  • References

    ARTICLE SECTIONS
    Jump To

    This article references 64 other publications.

    1. 1
      Green, M. A.; Emery, K.; Hishikawa, Y.; Warta, W.; Dunlop, E. D.; Levi, D. H.; Ho-Baillie, A. W. Solar cell efficiency tables (version 49) Prog. Photovoltaics 2017, 25, 3 DOI: 10.1002/pip.2855
    2. 2
      Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells J. Am. Chem. Soc. 2009, 131, 6050 6051 DOI: 10.1021/ja809598r
    3. 3
      Stranks, S. D.; Eperon, G. E.; Grancini, G.; Menelaou, C.; Alcocer, M. J.; Leijtens, T.; Herz, L. M.; Petrozza, A.; Snaith, H. J. Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber Science 2013, 342, 341 344 DOI: 10.1126/science.1243982
    4. 4
      Edri, E.; Kirmayer, S.; Mukhopadhyay, S.; Gartsman, K.; Hodes, G.; Cahen, D. Elucidating the charge carrier separation and working mechanism of CH3NH3PbI3-xClx perovskite solar cells Nat. Commun. 2014, 5, 3461 DOI: 10.1038/ncomms4461
    5. 5
      Liu, M.; Johnston, M. B.; Snaith, H. J. Efficient planar heterojunction perovskite solar cells by vapour deposition Nature 2013, 501, 395 398 DOI: 10.1038/nature12509
    6. 6
      Malinkiewicz, O.; Yella, A.; Lee, Y. H.; Espallargas, G. M.; Graetzel, M.; Nazeeruddin, M. K.; Bolink, H. J. Perovskite solar cells employing organic charge-transport layers Nat. Photonics 2013, 8, 128 132 DOI: 10.1038/nphoton.2013.341
    7. 7
      You, J. Low-temperature solution-processed perovskite solar cells with high efficiency and flexibility ACS Nano 2014, 8, 1674 1680 DOI: 10.1021/nn406020d
    8. 8
      Nie, W. High-efficiency solution-processed perovskite solar cells with millimeter-scale grains Science 2015, 347, 522 525 DOI: 10.1126/science.aaa0472
    9. 9
      Momblona, C.; Gil-Escrig, L.; Bandiello, E.; Hutter, E. M.; Sessolo, M.; Lederer, K.; Blochwitz-Nimoth, J.; Bolink, H. J. Efficient vacuum deposited pin and nip perovskite solar cells employing doped charge transport layers Energy Environ. Sci. 2016, 9, 3456 3463 DOI: 10.1039/C6EE02100J
    10. 10
      Sha, W. E. I.; Ren, X.; Chen, L.; Choy, W. C. The efficiency limit of CH3NH3PbI3 perovskite solar cells Appl. Phys. Lett. 2015, 106, 221104 DOI: 10.1063/1.4922150
    11. 11
      Wehrenfennig, C.; Eperon, G. E.; Johnston, M. B.; Snaith, H. J.; Herz, L. M. High charge carrier mobilities and lifetimes in organolead trihalide perovskites Adv. Mater. 2014, 26, 1584 1589 DOI: 10.1002/adma.201305172
    12. 12
      Wetzelaer, G. A. H.; Scheepers, M.; Sempere, A. M.; Momblona, C.; Ávila, J.; Bolink, H. J. Trap-Assisted Non-Radiative Recombination in Organic-Inorganic Perovskite Solar Cells Adv. Mater. 2015, 27, 1837 1841 DOI: 10.1002/adma.201405372
    13. 13
      Johnston, M. B.; Herz, L. M. Hybrid perovskites for photovoltaics: Charge-carrier recombination, diffusion, and radiative efficiencies Acc. Chem. Res. 2016, 49, 146 154 DOI: 10.1021/acs.accounts.5b00411
    14. 14
      Tress, W.; Marinova, N.; Inganäs, O.; Nazeeruddin, M.; Zakeeruddin, S. M.; Graetzel, M. Predicting the Open-Circuit Voltage of CH3NH3PbI3 Perovskite Solar Cells Using Electroluminescence and Photovoltaic Quantum Efficiency Spectra: the Role of Radiative and Non-Radiative Recombination Adv. Energy Mater. 2015, 5, 1400812 DOI: 10.1002/aenm.201400812
    15. 15
      Sherkar, T. S.; Momblona, C.; Gil-Escrig, L.; Bolink, H. J.; Koster, L. J. A. Improving the Performance of Perovskite Solar Cells: Insights From a Validated Device Model Adv. Energy Mater. 2017, 1602432 DOI: 10.1002/aenm.201602432
    16. 16
      Shao, Y. Grain boundary dominated ion migration in polycrystalline organic-inorganic halide perovskite films Energy Environ. Sci. 2016, 9, 1752 1759 DOI: 10.1039/C6EE00413J
    17. 17
      Cui, P.; Fu, P.; Wei, D.; Li, M.; Song, D.; Yue, X.; Li, Y.; Zhang, Z.; Li, Y.; Mbengue, J. M. Reduced surface defects of organometallic perovskite by thermal annealing for highly efficient perovskite solar cells RSC Adv. 2015, 5, 75622 75629 DOI: 10.1039/C5RA16669A
    18. 18
      Wu, X.; Trinh, M. T.; Niesner, D.; Zhu, H.; Norman, Z.; Owen, J. S.; Yaffe, O.; Kudisch, B. J.; Zhu, X.-Y. Trap states in lead iodide perovskites J. Am. Chem. Soc. 2015, 137, 2089 2096 DOI: 10.1021/ja512833n
    19. 19
      Chen, Q.; Zhou, H.; Song, T.-B.; Luo, S.; Hong, Z.; Duan, H.-S.; Dou, L.; Liu, Y.; Yang, Y. Controllable self-induced passivation of hybrid lead iodide perovskites toward high performance solar cells Nano Lett. 2014, 14, 4158 4163 DOI: 10.1021/nl501838y
    20. 20
      MacDonald, G. A.; Yang, M.; Berweger, S.; Killgore, J. P.; Kabos, P.; Berry, J. J.; Zhu, K.; DelRio, F. W. Methylammonium lead iodide grain boundaries exhibit depth-dependent electrical properties Energy Environ. Sci. 2016, 9, 3642 3649 DOI: 10.1039/C6EE01889K
    21. 21
      Yun, J. S.; Ho-Baillie, A.; Huang, S.; Woo, S. H.; Heo, Y.; Seidel, J.; Huang, F.; Cheng, Y.-B.; Green, M. A. Benefit of grain boundaries in organic-inorganic halide planar perovskite solar cells J. Phys. Chem. Lett. 2015, 6, 875 880 DOI: 10.1021/acs.jpclett.5b00182
    22. 22
      Jacobsson, T. J. Unreacted PbI2 as a Double-Edged Sword for Enhancing the Performance of Perovskite Solar Cells J. Am. Chem. Soc. 2016, 138, 10331 10343 DOI: 10.1021/jacs.6b06320
    23. 23
      de Quilettes, D. W.; Vorpahl, S. M.; Stranks, S. D.; Nagaoka, H.; Eperon, G. E.; Ziffer, M. E.; Snaith, H. J.; Ginger, D. S. Impact of microstructure on local carrier lifetime in perovskite solar cells Science 2015, 348, 683 686 DOI: 10.1126/science.aaa5333
    24. 24
      Bischak, C. G.; Sanehira, E. M.; Precht, J. T.; Luther, J. M.; Ginsberg, N. S. Heterogeneous Charge Carrier Dynamics in Organic-Inorganic Hybrid Materials: Nanoscale Lateral and Depth-Dependent Variation of Recombination Rates in Methylammonium Lead Halide Perovskite Thin Films Nano Lett. 2015, 15, 4799 4807 DOI: 10.1021/acs.nanolett.5b01917
    25. 25
      Ono, L. K.; Qi, Y. Surface and Interface Aspects of Organometal Halide Perovskite Materials and Solar Cells J. Phys. Chem. Lett. 2016, 7, 4764 4794 DOI: 10.1021/acs.jpclett.6b01951
    26. 26
      Nelson, J. The Physics of Solar Cells; Imperial College Press: London, 2003.
    27. 27
      Visoly-Fisher, I.; Cohen, S. R.; Gartsman, K.; Ruzin, A.; Cahen, D. Understanding the Beneficial Role of Grain Boundaries in Polycrystalline Solar Cells from Single-Grain-Boundary Scanning Probe Microscopy Adv. Funct. Mater. 2006, 16, 649 660 DOI: 10.1002/adfm.200500396
    28. 28
      Li, C. Grain-boundary-enhanced carrier collection in CdTe solar cells Phys. Rev. Lett. 2014, 112, 156103 DOI: 10.1103/PhysRevLett.112.156103
    29. 29
      Distefano, T.; Cuomo, J. Reduction of grain boundary recombination in polycrystalline silicon solar cells Appl. Phys. Lett. 1977, 30, 351 353 DOI: 10.1063/1.89396
    30. 30
      Gloeckler, M.; Sites, J. R.; Metzger, W. K. Grain-boundary recombination in Cu (In, Ga) Se2 solar cells J. Appl. Phys. 2005, 98, 113704 DOI: 10.1063/1.2133906
    31. 31
      Seto, J. Y. The electrical properties of polycrystalline silicon films J. Appl. Phys. 1975, 46, 5247 5254 DOI: 10.1063/1.321593
    32. 32
      Landsberg, P.; Abrahams, M. Effects of surface states and of excitation on barrier heights in a simple model of a grain boundary or a surface J. Appl. Phys. 1984, 55, 4284 4293 DOI: 10.1063/1.333038
    33. 33
      Card, H. C.; Yang, E. S. Electronic processes at grain boundaries in polycrystalline semiconductors under optical illumination IEEE Trans. Electron Devices 1977, 24, 397 402 DOI: 10.1109/T-ED.1977.18747
    34. 34
      Yin, W.-J.; Yang, J.-H.; Kang, J.; Yan, Y.; Wei, S.-H. Halide perovskite materials for solar cells: a theoretical review J. Mater. Chem. A 2015, 3, 8926 8942 DOI: 10.1039/C4TA05033A
    35. 35
      Walsh, A.; Scanlon, D. O.; Chen, S.; Gong, X.; Wei, S.-H. Self-Regulation Mechanism for Charged Point Defects in Hybrid Halide Perovskites Angew. Chem. 2015, 127, 1811 1814 DOI: 10.1002/ange.201409740
    36. 36
      Yin, W.-J.; Shi, T.; Yan, Y. Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber Appl. Phys. Lett. 2014, 104, 063903 DOI: 10.1063/1.4864778
    37. 37
      Selberherr, S. Analysis and Simulation of Semiconductor Devices; Springer-Verlag: Vienna, 1984.
    38. 38
      Eames, C.; Frost, J. M.; Barnes, P. R.; O’regan, B. C.; Walsh, A.; Islam, M. S. Ionic transport in hybrid lead iodide perovskite solar cells Nat. Commun. 2015, 6, 7497 DOI: 10.1038/ncomms8497
    39. 39
      Azpiroz, J. M.; Mosconi, E.; Bisquert, J.; de Angelis, F. Defect migration in methylammonium lead iodide and its role in perovskite solar cell operation Energy Environ. Sci. 2015, 8, 2118 2127 DOI: 10.1039/C5EE01265A
    40. 40
      Yuan, Y.; Huang, J. Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability Acc. Chem. Res. 2016, 49, 286 293 DOI: 10.1021/acs.accounts.5b00420
    41. 41
      Simmons, J.; Taylor, G. Nonequilibrium steady-state statistics and associated effects for insulators and semiconductors containing an arbitrary distribution of traps Phys. Rev. B 1971, 4, 502 DOI: 10.1103/PhysRevB.4.502
    42. 42
      Koster, L. J. A.; Smits, E. C. P.; Mihailetchi, V. D.; Blom, P. W. M. Device model for the operation of polymer/fullerene bulk heterojunction solar cells Phys. Rev. B: Condens. Matter Mater. Phys. 2005, 72, 085205 DOI: 10.1103/PhysRevB.72.085205
    43. 43
      Leijtens, T.; Stranks, S. D.; Eperon, G. E.; Lindblad, R.; Johansson, E. M.; McPherson, I. J.; Rensmo, H.; Ball, J. M.; Lee, M. M.; Snaith, H. J. Electronic properties of meso-superstructured and planar organometal halide perovskite films: charge trapping, photodoping, and carrier mobility ACS Nano 2014, 8, 7147 7155 DOI: 10.1021/nn502115k
    44. 44
      Leijtens, T.; Eperon, G. E.; Barker, A. J.; Grancini, G.; Zhang, W.; Ball, J. M.; Kandada, A. R. S.; Snaith, H. J.; Petrozza, A. Carrier trapping and recombination: the role of defect physics in enhancing the open circuit voltage of metal halide perovskite solar cells Energy Environ. Sci. 2016, 9, 3472 3481 DOI: 10.1039/C6EE01729K
    45. 45
      deQuilettes, D. W.; Zhang, W.; Burlakov, V. M.; Graham, D. J.; Leijtens, T.; Osherov, A.; Bulović, V.; Snaith, H. J.; Ginger, D. S.; Stranks, S. D. Photo-induced halide redistribution in organic-inorganic perovskite films Nat. Commun. 2016, 7, 11683 DOI: 10.1038/ncomms11683
    46. 46
      Du, M.-H. Density functional calculations of native defects in CH3NH3PbI3: effects of spin-orbit coupling and self-interaction error J. Phys. Chem. Lett. 2015, 6, 1461 1466 DOI: 10.1021/acs.jpclett.5b00199
    47. 47
      Shao, S.; Abdu-Aguye, M.; Sherkar, T. S.; Fang, H.-H.; Adjokatse, S.; Brink, G. t.; Kooi, B. J.; Koster, L.; Loi, M. A. The Effect of the Microstructure on Trap-Assisted Recombination and Light Soaking Phenomenon in Hybrid Perovskite Solar Cells Adv. Funct. Mater. 2016, 26, 8094 8102 DOI: 10.1002/adfm.201602519
    48. 48
      Uratani, H.; Yamashita, K. Charge Carrier Trapping at Surface Defects of Perovskite Solar Cell Absorbers: A First-Principles Study J. Phys. Chem. Lett. 2017, 8, 742 746 DOI: 10.1021/acs.jpclett.7b00055
    49. 49
      Sherkar, T. S.; Koster, L. J. A. Can ferroelectric polarization explain the high performance of hybrid halide perovskite solar cells? Phys. Chem. Chem. Phys. 2016, 18, 331 338 DOI: 10.1039/C5CP07117H
    50. 50
      Yuan, Y.; Li, T.; Wang, Q.; Xing, J.; Gruverman, A.; Huang, J. Anomalous photovoltaic effect in organic-inorganic hybrid perovskite solar cells Science Adv. 2017, 3, e1602164 DOI: 10.1126/sciadv.1602164
    51. 51
      Xing, G.; Mathews, N.; Sun, S.; Lim, S. S.; Lam, Y. M.; Grätzel, M.; Mhaisalkar, S.; Sum, T. C. Long-range balanced electron-and hole-transport lengths in organic-inorganic CH3NH3PbI3 Science 2013, 342, 344 347 DOI: 10.1126/science.1243167
    52. 52
      Burkhard, G. F.; Hoke, E. T.; McGehee, M. D. Accounting for interference, scattering, and electrode absorption to make accurate internal quantum efficiency measurements in organic and other thin solar cells Adv. Mater. 2010, 22, 3293 3297 DOI: 10.1002/adma.201000883
    53. 53
      Tress, W. Device Physics of Organic Solar Cells. Ph.D. thesis, TU Dresden, Dresden, Germany, 2011.
    54. 54
      Brivio, F.; Butler, K. T.; Walsh, A.; van Schilfgaarde, M. Relativistic quasiparticle self-consistent electronic structure of hybrid halide perovskite photovoltaic absorbers Phys. Rev. B: Condens. Matter Mater. Phys. 2014, 89, 155204 DOI: 10.1103/PhysRevB.89.155204
    55. 55
      Mönch, T.; Sherkar, T. S.; Koster, L. J. A.; Friederich, P.; Riede, M.; Formanek, P.; Koerner, C.; Vandewal, K.; Wenzel, W.; Leo, K. Experimental and theoretical study of phase separation in ZnPc: C 60 blends Org. Electron. 2015, 27, 183 191 DOI: 10.1016/j.orgel.2015.09.023
    56. 56
      Koster, L. J. A.; Mihailetchi, V. D.; Ramaker, R.; Blom, P. W. Light intensity dependence of open-circuit voltage of polymer: fullerene solar cells Appl. Phys. Lett. 2005, 86, 123509 123509 DOI: 10.1063/1.1889240
    57. 57
      Mandoc, M.; Kooistra, F.; Hummelen, J.; De Boer, B.; Blom, P. Effect of traps on the performance of bulk heterojunction organic solar cells Appl. Phys. Lett. 2007, 91, 263505 DOI: 10.1063/1.2821368
    58. 58
      Tvingstedt, K.; Gil-Escrig, L.; Momblona, C.; Rieder, P.; Kiermasch, D.; Sessolo, M.; Baumann, A.; Bolink, H. J.; Dyakonov, V. Removing Leakage and Surface Recombination in Planar Perovskite Solar Cells ACS Energy Letters 2017, 2, 424 430 DOI: 10.1021/acsenergylett.6b00719
    59. 59
      Snaith, H. J.; Abate, A.; Ball, J. M.; Eperon, G. E.; Leijtens, T.; Noel, N. K.; Stranks, S. D.; Wang, J. T.-W.; Wojciechowski, K.; Zhang, W. Anomalous hysteresis in perovskite solar cells J. Phys. Chem. Lett. 2014, 5, 1511 1515 DOI: 10.1021/jz500113x
    60. 60
      Tress, W.; Marinova, N.; Moehl, T.; Zakeeruddin, S. M.; Nazeeruddin, M. K.; Grätzel, M. Understanding the rate-dependent J–V hysteresis, slow time component, and aging in CH 3 NH 3 PbI 3 perovskite solar cells: the role of a compensated electric field Energy Environ. Sci. 2015, 8, 995 1004 DOI: 10.1039/C4EE03664F
    61. 61
      Unger, E. L.; Hoke, E. T.; Bailie, C. D.; Nguyen, W. H.; Bowring, A. R.; Heumüller, T.; Christoforo, M. G.; McGehee, M. D. Hysteresis and transient behavior in current-voltage measurements of hybrid-perovskite absorber solar cells Energy Environ. Sci. 2014, 7, 3690 3698 DOI: 10.1039/C4EE02465F
    62. 62
      Richardson, G.; O’Kane, S. E.; Niemann, R. G.; Peltola, T. A.; Foster, J. M.; Cameron, P. J.; Walker, A. B. Can slow-moving ions explain hysteresis in the current–voltage curves of perovskite solar cells? Energy Environ. Sci. 2016, 9, 1476 1485 DOI: 10.1039/C5EE02740C
    63. 63
      Meloni, S. Ionic polarization-induced current-voltage hysteresis in CH3NH3PbX3 perovskite solar cells Nat. Commun. 2016, 7, 10334 DOI: 10.1038/ncomms10334
    64. 64
      Calado, P.; Telford, A. M.; Bryant, D.; Li, X.; Nelson, J.; O’regan, B. C.; Barnes, P. R. Evidence for ion migration in hybrid perovskite solar cells with minimal hysteresis Nat. Commun. 2016, 7, 13831 DOI: 10.1038/ncomms13831
  • Supporting Information

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsenergylett.7b00236.

    • Simulation details, optical data, and additional results (PDF)


    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.