Sorting of Double-Walled Carbon Nanotubes According to Their Outer Wall Electronic Type via a Gel Permeation Method
- Katherine E. Moore ,
- Moritz Pfohl ,
- Daniel D. Tune ,
- Frank Hennrich ,
- Simone Dehm ,
- Venkata Sai K. Chakradhanula ,
- Christian Kübel ,
- Ralph Krupke , and
- Benjamin S. Flavel
Abstract

In this work, we demonstrate the application of the gel permeation technique to the sorting of double-walled carbon nanotubes (DWCNTs) according to their outer wall electronic type. Our method uses Sephacryl S-200 gel and yields sorted fractions of DWCNTs with impurities removed and highly enriched in nanotubes with either metallic (M) or semiconducting (S) outer walls. The prepared fractions are fully characterized using optical absorption spectroscopy, transmission electron microscopy, and atomic force microscopy, and the entire procedure is monitored in real time using process Raman analysis. The sorted DWCNTs are then integrated into single nanotube field effect transistors, allowing detailed electronic measurement of the transconductance properties of the four unique [email protected] wall combinations of [email protected], [email protected], [email protected], and [email protected]
Results and Discussion
Figure 1

Figure 1. Cosurfactant separation of DWCNTs via gel permeation. (a) Elution profiles of the normalized G-band Raman mode intensity for DWCNTs, AD SWCNTs, and HiPco SWCNTs. The dashed lines in the DWCNT elution profile highlight bands 2 and 3, which from the absorption spectra, seen in (b) and (c), correspond to DWCNTs with metallic and semiconducting outer walls. Regions of Sii and Mii transitions are highlighted in each spectrum.
Figure 2

Figure 2. TEM analysis of the sorted DWCNTs with (a) metallic and (b) semiconducting outer walls, where diameter distributions can be seen for DWCNTs, SWCNTs, and MWCNTs. The sample number and resultant DWCNT purity are given in each case.
Figure 3

Figure 3. Transconductance measurements and corresponding false color SEM images of the four possible types of DWCNT FET: (a) [email protected], (b) [email protected], (c) [email protected], and (d) [email protected]
Conclusion
Experimental Section
Supporting Information
Supporting absorbance spectra, AFM statistics, Raman characterization, and TEM data. This material is available free of charge via the Internet at http://pubs.acs.org.
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Acknowledgment
We thank Unidym for providing DWCNT material. K.E.M acknowledges the Karlsruhe House of Young Scientists, the Playford Memorial Trust, and the Australian Microscopy and Microanalysis Research Facility (AMMRF). We are grateful to the Karlsruhe Nano Micro Facility (KNMF) for access to the TEM facilities. This research was also supported by the Bundesministerium fur Bildung und Forschung (BMBF) as administered by POF-NanoMicro. B.S.F. gratefully acknowledges support from the Deutsche Forschungsgemeinschaft’s Emmy Noether Program under Grant No. FL 834/1-1.
References
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- 26Blanch, A. J.; Quinton, J. S.; Shapter, J. G. The Role of Sodium Dodecyl Sulfate Concentration in the Separation of Carbon Nanotubes Using Gel Chromatography Carbon 2013, 60, 471– 480[Crossref], [CAS], Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXnvVarsbw%253D&md5=7ba73a20e1772b599b9b1a2c39fecb24The role of sodium dodecyl sulfate concentration in the separation of carbon nanotubes using gel chromatographyBlanch, Adam J.; Quinton, Jamie S.; Shapter, Joe G.Carbon (2013), 60 (), 471-480CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)Gel chromatog. was demonstrated as an effective method for generating sepd. fractions of metallic and semiconducting C nanotubes when starting with a heterogeneous dispersion in SDS. The influence of the surfactant concn. in this process was examd. here for chromatog. sepn. using a dextran-based gel as the stationary phase. Decreasing the concn. of SDS from 4 to 0.5 wt.% caused a gradual increase in the adsorption of semiconducting nanotubes to the gel in a species-selective manner, with low concns. of SDS (around 0.5%) found to provide the best semiconductor-metal sepn. Elution using a stepwise concn. gradient was able to produce fractions of reduced diam. population from the polydisperse HiPCO starting material, where a good correlation between the concn. of elution and local bond curvature for each nanotube species was obsd. Since bleaching of optical absorbance through protonation in the presence of dissolved O2 was found to mask the presence of nanotubes with large diams., it was deemed necessary to reverse the protonation effect through hydroxide addn. to detect these species in optical measurements of nanotube dispersions.
- 27Wallace, E. J.; Sansom, M. S. Carbon Nanotube Self-Assembly with Lipids and Detergent: A Molecular Dynamics Study Nanotechnology 2009, 20, 045101Google ScholarThere is no corresponding record for this reference.
- 28Xu, Z.; Yang, X.; Yang, Z. A Molecular Simulation Probing of Structure and Interaction for Supramolecular Sodium Dodecyl Sulfate/Single-Wall Carbon Nanotube Assemblies Nano Lett. 2010, 10, 985– 991[ACS Full Text
], [CAS], Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtlKkt7o%253D&md5=0bff721e969dc0faa124ccc9b5390b1dA Molecular Simulation Probing of Structure and Interaction for Supramolecular Sodium Dodecyl Sulfate/Single-Wall Carbon Nanotube AssembliesXu, Zhijun; Yang, Xiaoning; Yang, ZhenNano Letters (2010), 10 (3), 985-991CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Here we report a larger-scale at.-level mol. dynamics (MD) simulation for the self-assembly of sodium dodecyl sulfate (SDS) surfactant on single-walled carbon nanotube (SWNT) surfaces and the interaction between supramol. SDS/SWNT aggregates. We make an effort to address several important problems in regard to carbon nanotube dispersion/sepn. At first, the simulation provides comprehensive direct evidence for SDS self-assembly structures on carbon nanotube surfaces, which can help to clarify the relevant debate over the exact adsorption structure. We also, for the first time, simulated the potential of mean force (PMF) between two SWNTs embedded in SDS surfactant micelles. A novel unified PMF approach has been applied to reveal various cooperative interactions between the SDS/SWNT aggregates, which is different from the previous electrostatic repulsion explanation. The unique role of sodium ions revealed here provides a new microscopic understanding of the recent expts. in the electrolyte tuning of the interfacial forces on the selective fractionation of SDS surrounding SWNTs. - 29Duan, W. H.; Wang, Q.; Collins, F. Dispersion of Carbon Nanotubes with Sds Surfactants: A Study from a Binding Energy Perspective Chem. Sci. 2011, 2, 1407– 1413[Crossref], [CAS], Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXnsVyiu7Y%253D&md5=91444958c74ce9a416134ef08486f0f4Dispersion of carbon nanotubes with SDS surfactants: a study from a binding energy perspectiveDuan, Wen Hui; Wang, Quan; Collins, FrankChemical Science (2011), 2 (7), 1407-1413CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)Dispersion of carbon nanotubes with sodium dodecyl sulfate (SDS) surfactant is reported by mol. mechanics simulations from an energy perspective. The interaction energy of carbon nanotubes in a tube bundle is first calcd. to est. the force sufficient to sep. it from the bundle. The binding energy between increasing nos. of SDS mols. with a carbon nanotube is next estd. to identify the threshold no. of surfactant mols. for a possible dispersion. With the help of ultrasonication, a sufficient no. of SDS mols. are found to penetrate into an initial gap between a single tube and other nanotubes in the bundle. Owing to further congregation of the surfactants at the gap site, the gap becomes enlarged until complete dispersion. In addn. to the dispersion observation in view of the interaction and binding energy perspectives, four congregation processes were identified to reveal the aggregation morphologies of SDS surfactants on the surface of carbon nanotubes as well as the effect of diam. of a carbon nanotube on the adsorption d.
- 30Tummala, N. R.; Striolo, A. Sds Surfactants on Carbon Nanotubes: Aggregate Morphology ACS Nano 2009, 3, 595– 602[ACS Full Text
], [CAS], Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXitFKisrk%253D&md5=cc266bd3de46b9b6b20a7506afbe108bSDS surfactants on carbon nanotubes. Aggregate morphologyTummala, Naga Rajesh; Striolo, AlbertoACS Nano (2009), 3 (3), 595-602CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)Although C nanotubes have attracted enormous research interest, their practical application is still hindered, primarily, by the difficulty of sepg. them into samples monodispersed in diam., chirality, and length. Ultracentrifugating C nanotube dispersions stabilized by surfactants is a promising route for achieving the desired sepn. For further perfectioning this procedure it is necessary to know how surfactants adsorb on nanotubes of different diams., which dets. the nanotube-surfactant aggregate effective d. and the nanotube-nanotube potential of mean force. Because only limited exptl. data are available to elucidate these phenomena, we report here an extensive all-atom mol. dynamics study on the morphol. of SDS surfactant aggregates adsorbed on (6,6), (12,12), and (20,20) single walled C nanotubes at room conditions. The nanotube diam. is the primary factor that dets. the morphol. of the aggregates because of a competition between the entropic and energetic advantage encountered by the surfactants when they wrap one nanotube, and the enthalpic penalty faced during this process due to bending of the surfactant mol. The data are in qual. agreement with the neutron scattering results reported by Yurekli et al. (2004), and for the first time provide an at.-level description helpful in designing better sepn., as well as stabilization techniques for aq. C nanotube dispersions. - 31Niyogi, S.; Densmore, C. G.; Doorn, S. K. Electrolyte Tuning of Surfactant Interfacial Behavior for Enhanced Density-Based Separations of Single-Walled Carbon Nanotubes J. Am. Chem. Soc. 2008, 131, 1144– 1153Google ScholarThere is no corresponding record for this reference.
- 32Jain, R. M.; Howden, R.; Tvrdy, K.; Shimizu, S.; Hilmer, A. J.; McNicholas, T. P.; Gleason, K. K.; Strano, M. S. Polymer-Free Near-Infrared Photovoltaics with Single Chirality (6,5) Semiconducting Carbon Nanotube Active Layers Adv. Mater. 2012, 24, 4436– 4439[Crossref], [PubMed], [CAS], Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XptlSjsbs%253D&md5=e93b8454b36c58e46678c5f634d928cfPolymer-Free Near-Infrared Photovoltaics with Single Chirality (6,5) Semiconducting Carbon Nanotube Active LayersJain, Rishabh M.; Howden, Rachel; Tvrdy, Kevin; Shimizu, Steven; Hilmer, Andrew J.; McNicholas, Thomas P.; Gleason, Karen K.; Strano, Michael S.Advanced Materials (Weinheim, Germany) (2012), 24 (32), 4436-4439, S4436/1-S4436/9CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)An all-carbon photovoltaic device has been demonstrated where a film of highly purified (6,5) carbon nanotubes acts as the active photoabsorption layer. There is evidence to suggest that tight control over the electronic structure of the single-walled carbon nanotubes has enabled an open-circuit voltage higher than previously demonstrated in other single-walled carbon nanotube active layer devices. While device efficiency is limited, it is interesting to note that it is comparable to many polymer/single-walled carbon nanotube bulk heterojunction devices. Only a 20% impurity by wt. of a second chirality of semiconducting single-walled carbon nanotube (6,4) results in a more than 30 times decrease in power conversion efficiency. This study provides a foundation for future work aimed at increasing the efficiency of polymer-free all-carbon photovoltaics via several mechanisms, including active layer thickness modulation, bulk heterojunction geometries and single-walled carbon nanotube alignment.
- 33Kominkova, Z.; Vales, V.; Hersam, M. C.; Kalbac, M. Towards Quantification of the Ratio of the Single and Double Wall Carbon Nanotubes in Their Mixtures: An in Situ Raman Spectroelectrochemical Study Carbon 2014, 78, 366– 373Google ScholarThere is no corresponding record for this reference.
- 34Arnold, M. S.; Stupp, S. I.; Hersam, M. C. Enrichment of Single-Walled Carbon Nanotubes by Diameter in Density Gradients Nano Lett. 2005, 5, 713– 718[ACS Full Text
], [CAS], Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXit1Cnu7k%253D&md5=56cb8d91fe680f019bd245d88645a987Enrichment of single-walled carbon nanotubes by diameter in density gradientsArnold, Michael S.; Stupp, Samuel I.; Hersam, Mark C.Nano Letters (2005), 5 (4), 713-718CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)The bulk enrichment and sepn. of single-walled carbon nanotubes (SWNTs) by diam. has been achieved through ultracentrifugation of DNA-wrapped SWNTs in aq. d. gradients. The sepn. is identified by the visual formation of colored bands of SWNTs in the d. range of 1.11-1.17 g cm-3. The optical absorbance spectra of the sepd. SWNTs indicate that SWNTs of decreasing diam. are increasingly more buoyant. This nondestructive and scalable sepn. strategy is expected to impact the fields of mol. electronics, optoelectronics, and sensing where SWNTs of a monodisperse band gap are essential. - 35Arnold, M. S.; Green, A. A.; Hulvat, J. F.; Stupp, S. I.; Hersam, M. C. Sorting Carbon Nanotubes by Electronic Structure Using Density Differentiation Nat. Nanotechnol. 2006, 1, 60– 65[Crossref], [PubMed], [CAS], Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtFCisrvF&md5=4cc068399931940846573a7e9cf79873Sorting carbon nanotubes by electronic structure using density differentiationArnold, Michael S.; Green, Alexander A.; Hulvat, James F.; Stupp, Samuel I.; Hersam, Mark C.Nature Nanotechnology (2006), 1 (1), 60-65CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)The heterogeneity of as-synthesized single-walled carbon nanotubes (SWNTs) precludes their widespread application in electronics, optics and sensing. The authors report on the sorting of carbon nanotubes by diam., bandgap and electronic type using structure-discriminating surfactants to engineer subtle differences in their buoyant densities. Using the scalable technique of d.-gradient ultracentrifugation, the authors have isolated narrow distributions of SWNTs in which >97% are within a 0.02-nm-diam. range. Also, using competing mixts. of surfactants, the authors produced bulk quantities of SWNTs of predominantly a single electronic type. These materials were used to fabricate thin-film elec. devices of networked SWNTs characterized by either metallic or semiconducting behavior.
- 36Kim, W.-J.; Nair, N.; Lee, C. Y.; Strano, M. S. Covalent Functionalization of Single-Walled Carbon Nanotubes Alters Their Densities Allowing Electronic and Other Types of Separation J. Phys. Chem. C 2008, 112, 7326– 7331[ACS Full Text
], [CAS], Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXkslCit7s%253D&md5=59e093f76fd70c0cf5efe9d6d2e453a2Covalent Functionalization of Single-Walled Carbon Nanotubes Alters Their Densities Allowing Electronic and Other Types of SeparationKim, Woo-Jae; Nair, Nitish; Lee, Chang Young; Strano, Michael S.Journal of Physical Chemistry C (2008), 112 (19), 7326-7331CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Covalently attached functional groups can alter the densities of individual single-walled carbon nanotubes (SWNTs) in a predictable and highly controllable manner. A vol.-additivity model based on mol. group contributions can be used to est. the d. difference between 4-hydroxyphenyl-functionalized and nonfunctionalized HiPco SWNTs as approx. 98.3 kg/m3, compared with 97.9 kg/m3 measured by d.-gradient centrifugation. Conversely, the estd. d. difference between the (6,5) (0.75 nm diam.) and (9,8) (1.17 nm diam.) SWNTs is smaller at 23.4 kg/m3. Covalent functionalization can provide an effective handle to sep. particular SWNTs from a typical diam. distribution. SWNT mixts., in which metallic SWNTs have been selectively reacted, produce two distinct d. fractions corresponding to functionalized metallic and pure semiconducting SWNTs. The results were confirmed by Raman spectroscopy, where the high-d. fractions exhibit an increased disorder mode with a corresponding decrease in intensity for the low-d. fraction. This method also allows for the first independent measure of (n,m) SWNTs having different chem. conversions with functional groups, which will allow for a more rigorous anal. of SWNT chem. than is possible with uncalibrated spectroscopies such as Raman or photoluminescence. - 37Ghosh, S.; Bachilo, S. M.; Weisman, R. B. Advanced Sorting of Single-Walled Carbon Nanotubes by Nonlinear Density-Gradient Ultracentrifugation Nat. Nanotechnol. 2010, 5, 443– 450[Crossref], [PubMed], [CAS], Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXmvFWltrg%253D&md5=5e40af80c65a123388da30501dbc876cAdvanced sorting of single-walled carbon nanotubes by nonlinear density-gradient ultracentrifugationGhosh, Saunab; Bachilo, Sergei M.; Weisman, R. BruceNature Nanotechnology (2010), 5 (6), 443-450CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)Existing methods for growing single-walled carbon nanotubes produce samples with a range of structures and electronic properties, but many potential applications require pure nanotube samples. D.-gradient ultracentrifugation has recently emerged as a technique for sorting as-grown mixts. of single-walled nanotubes into their distinct (n,m) structural forms, but to date this approach is limited to samples contg. only a small no. of nanotube structures, and has often required repeated d.-gradient ultracentrifugation processing. Here, it is reported that the use of tailored nonlinear d. gradients can significantly improve d.-gradient ultracentrifugation sepns. It is shown that highly polydisperse samples of single-walled nanotubes grown by the HiPco method are readily sorted in a single step to give fractions enriched in any of ten different (n,m) species. Furthermore, minor variants of the method allow sepn. of the mirror-image isomers (enantiomers) of seven (n,m) species. Optimization of this approach was aided by the development of instrumentation that spectroscopically maps nanotube contents inside undisturbed centrifuge tubes.
- 38Wang, F.; Dukovic, G.; Brus, L. E.; Heinz, T. F. The Optical Resonances in Carbon Nanotubes Arise from Excitons Science 2005, 308, 838– 841[Crossref], [PubMed], [CAS], Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXjvVantrc%253D&md5=4b6b163c769b4ee25b5caba695c1ecd2The Optical Resonances in Carbon Nanotubes Arise from ExcitonsWang, Feng; Dukovic, Gordana; Brus, Louis E.; Heinz, Tony F.Science (Washington, DC, United States) (2005), 308 (5723), 838-841CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Optical transitions in carbon nanotubes are of central importance for nanotube characterization. They also provide insight into the nature of excited states in these one-dimensional systems. Recent work suggests that light absorption produces strongly correlated electron-hole states in the form of excitons. However, it has been difficult to rule out a simpler model in which resonances arise from the van Hove singularities assocd. with the one-dimensional bond structure of the nanotubes. Here, two-photon excitation spectroscopy bolsters the exciton picture. We found binding energies of ∼400 meV for semiconducting single-walled nanotubes with 0.8-nm diams. The results demonstrate the dominant role of many-body interactions in the excited-state properties of one-dimensional systems.
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Abstract

Figure 1

Figure 1. Cosurfactant separation of DWCNTs via gel permeation. (a) Elution profiles of the normalized G-band Raman mode intensity for DWCNTs, AD SWCNTs, and HiPco SWCNTs. The dashed lines in the DWCNT elution profile highlight bands 2 and 3, which from the absorption spectra, seen in (b) and (c), correspond to DWCNTs with metallic and semiconducting outer walls. Regions of Sii and Mii transitions are highlighted in each spectrum.
Figure 2

Figure 2. TEM analysis of the sorted DWCNTs with (a) metallic and (b) semiconducting outer walls, where diameter distributions can be seen for DWCNTs, SWCNTs, and MWCNTs. The sample number and resultant DWCNT purity are given in each case.
Figure 3

Figure 3. Transconductance measurements and corresponding false color SEM images of the four possible types of DWCNT FET: (a) [email protected], (b) [email protected], (c) [email protected], and (d) [email protected]
References
ARTICLE SECTIONSThis article references 45 other publications.
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- 12Moshammer, K.; Hennrich, F.; Kappes, M. Selective Suspension in Aqueous Sodium Dodecyl Sulfate According to Electronic Structure Type Allows Simple Separation of Metallic from Semiconducting Single-Walled Carbon Nanotubes Nano Res. 2009, 2, 599– 606[Crossref], [CAS], Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtFKnt7nJ&md5=d5da2ccf7a770ab1636846a93704450fSelective suspension in aqueous sodium dodecyl sulfate according to electronic structure type allows simple separation of metallic from semiconducting single-walled carbon nanotubesMoshammer, Kai; Hennrich, Frank; Kappes, Manfred M.Nano Research (2009), 2 (8), 599-606CODEN: NRAEB5; ISSN:1998-0124. (Springer)Both d. gradient centrifugation and gel electrophoresis have been reported to allow high throughput sepn. of metallic from semiconducting single-walled carbon nanotubes (SWNTs) when using aq. sodium dodecyl sulfate (SDS) suspensions. We show here that both methods rely on an initial dispersion-by-sonication step, which is already selective with respect to electronic structure type. The corresponding aq. SDS "starting" suspensions obtained after sonication and purifn. by simple centrifugation (70,000 g, 1 h) contain semiconducting SWNTs primarily in the form of small bundles whereas metallic SWNTs are predominantly suspended as individual tubes. D. gradient centrifugation then separates the bundles from the individual tubes on the basis of differences in their overall buoyant densities. Gel electrophoresis separates the longer bundles from the shorter individual tubes on the basis of their different mobilities. We also demonstrate that such starting suspensions can be fractionated according to electronic structure type by even simpler techniques such as size exclusion chromatog. or gel filtration, thus opening the way for simple scale-up.
- 13Liu, H.; Nishide, D.; Tanaka, T.; Kataura, H. Large-Scale Single-Chirality Separation of Single-Wall Carbon Nanotubes by Simple Gel Chromatography Nat. Commun. 2011, 2, 309[Crossref], [PubMed], [CAS], Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC3MvpslSmug%253D%253D&md5=fe1f7522d086e42af82bbd89d5a446f9Large-scale single-chirality separation of single-wall carbon nanotubes by simple gel chromatographyLiu Huaping; Nishide Daisuke; Tanaka Takeshi; Kataura HiromichiNature communications (2011), 2 (), 309 ISSN:.Monostructured single-wall carbon nanotubes (SWCNTs) are important in both scientific research and electronic and biomedical applications; however, the bulk separation of SWCNTs into populations of single-chirality nanotubes remains challenging. Here we report a simple and effective method for the large-scale chirality separation of SWCNTs using a single-surfactant multicolumn gel chromatography method utilizing one surfactant and a series of vertically connected gel columns. This method is based on the structure-dependent interaction strength of SWCNTs with an allyl dextran-based gel. Overloading an SWCNT dispersion on the top column results in the adsorption sites of the column becoming fully occupied by the nanotubes that exhibit the strongest interaction with the gel. The unbound nanotubes flow through to the next column, and the nanotubes with the second strongest interaction with the gel are adsorbed in this stage. In this manner, 13 different (n, m) species were separated. Metallic SWCNTs were finally collected as unbound nanotubes because they exhibited the lowest interaction with the gel.
- 14Liu, H.; Tanaka, T.; Urabe, Y.; Kataura, H. High-Efficiency Single-Chirality Separation of Carbon Nanotubes Using Temperature-Controlled Gel Chromatography Nano Lett. 2013, 13, 1996– 2003[ACS Full Text
], [CAS], Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXlslaitbw%253D&md5=b6489ba94fe5c6632aa0347e842c3359High-Efficiency Single-Chirality Separation of Carbon Nanotubes Using Temperature-Controlled Gel ChromatographyLiu, Huaping; Tanaka, Takeshi; Urabe, Yasuko; Kataura, HiromichiNano Letters (2013), 13 (5), 1996-2003CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)The authors report the use of temp.-controlled gel chromatog. for the high-efficiency single-chirality sepn. of single-wall C nanotubes (SWCNTs). This new method uses temp. to selectively control the interaction between the Na dodecyl sulfate (SDS)-wrapped SWCNTs and an allyl dextran-based gel. Temp. control enhances the differences in the interactions of various (n, m) SWCNTs with the gel, enabling the sepn. of high-purity (n, m) single-species in a single-step process. With this technique, the authors successfully sorted 7 (n, m) single-species including (6, 4), (6, 5), (7, 5), (8, 3), (8, 4), (7, 6), and (8, 6) from raw HiPco-SWCNTs at temps. Technique offers the advantages of tech. simplicity, low cost, and high yield, representing an important step toward the industrial-scale sepn. of single-chirality SWCNTs. - 15Tvrdy, K.; Jain, R. M.; Han, R.; Hilmer, A. J.; McNicholas, T. P.; Strano, M. S. A Kinetic Model for the Deterministic Prediction of Gel-Based Single-Chirality Single-Walled Carbon Nanotube Separation ACS Nano 2013, 7, 1779– 1789[ACS Full Text
], [CAS], Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsVentr4%253D&md5=af108d355e995a0f011c54f0102b4f54A Kinetic Model for the Deterministic Prediction of Gel-Based Single-Chirality Single-Walled Carbon Nanotube SeparationTvrdy, Kevin; Jain, Rishabh M.; Han, Rebecca; Hilmer, Andrew J.; McNicholas, Thomas P.; Strano, Michael S.ACS Nano (2013), 7 (2), 1779-1789CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)We propose a kinetic model that describes the sepn. of single-chirality semiconducting carbon nanotubes based on the chirality-selective adsorption to specific hydrogels. Exptl. elution profiles of the (7,3), (6,4), (6,5), (8,3), (8,6), (7,5), and (7,6) species are well described by an irreversible, first-order site assocn. kinetic model with a single rate const. describing the adsorption of each SWNT to the immobile gel phase. Specifically, we find first-order binding rate consts. for seven exptl. sepd. nanotubes normalized by the binding site molarity (Mθ): k7,3 = 3.5 × 10-5 Mθ-1 s-1, k6,4 = 7.7 × 10-8 Mθ-1 s-1, k8,3 = 2.3 × 10-9 Mθ-1 s-1, k6,5 = 3.8 × 10-9 Mθ-1 s-1, k7,5 = 1.9 × 10-11 Mθ-1 s-1, k8,6 = 7.7 × 10-12 Mθ-1 s-1, and k7,6 = 3.8 × 10-12 Mθ-1 s-1. These results, as well as addnl. control expts., unambiguously identify the sepn. process as a selective adsorption. Unlike certain chromatog. processes with retention time dependence, this sepn. procedure can be scaled to arbitrarily large vols., as we demonstrate. This study provides a foundation for both the mechanistic understanding of gel-based SWNT sepn. as well as the potential industrial-scale realization of single-chirality prodn. of carbon nanotubes. - 16Jain, R. M.; Tvrdy, K.; Han, R.; Ulissi, Z.; Strano, M. S. Quantitative Theory of Adsorptive Separation for the Electronic Sorting of Single-Walled Carbon Nanotubes ACS Nano 2014, 8, 3367– 3379
- 17Flavel, B. S.; Kappes, M. M.; Krupke, R.; Hennrich, F. Separation of Single-Walled Carbon Nanotubes by 1-Dodecanol-Mediated Size-Exclusion Chromatography ACS Nano 2013, 7, 3557– 3564[ACS Full Text
], [CAS], Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXltVOns7c%253D&md5=1e9164b2b43e6b1634f256fd8b3c7164Separation of Single-Walled Carbon Nanotubes by 1-Dodecanol-Mediated Size-Exclusion ChromatographyFlavel, Benjamin S.; Kappes, Manfred M.; Krupke, Ralph; Hennrich, FrankACS Nano (2013), 7 (4), 3557-3564CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)A simple, single-column, high-throughput fractionation procedure based on size-exclusion chromatog. of aq. sodium dodecyl sulfate suspensions of single-walled carbon nanotubes (SWCNTs) is presented. This procedure yields monochiral or near monochiral SWCNT fractions of semiconducting SWCNTs. Unsorted and resulting monochiral suspensions were characterized using optical absorption and photoluminescence spectroscopy. - 18Flavel, B. S.; Moore, K. E.; Pfohl, M.; Kappes, M. M.; Hennrich, F. Separation of Single-Walled Carbon Nanotubes with a Gel Permeation Chromatography System ACS Nano 2014, 8, 1817– 1826[ACS Full Text
], [CAS], Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXpt1Kqsg%253D%253D&md5=7b13191571879d6fc26779c27d611a64Separation of Single-Walled Carbon Nanotubes with a Gel Permeation Chromatography SystemFlavel, Benjamin S.; Moore, Katherine E.; Pfohl, Moritz; Kappes, Manfred M.; Hennrich, FrankACS Nano (2014), 8 (2), 1817-1826CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)A gel permeation chromatog. system is used to sep. aq. sodium dodecyl sulfate suspensions of single-walled carbon nanotubes (SWCNTs). This automated procedure requires no precentrifugation, is scalable, and is found to yield monochiral SWCNT fractions of semiconducting SWCNTs with a purity of 61-95%. Unsorted and resulting monochiral fractions are characterized using optical absorption and photoluminescence spectroscopy. - 19Moore, K. E.; Pfohl, M.; Hennrich, F.; Chakradhanula, V. S.; Kuebel, C.; Kappes, M. M.; Shapter, J. G.; Krupke, R.; Flavel, B. S. Separation of Double-Walled Carbon Nanotubes by Size Exclusion Column Chromatography ACS Nano 2014, 8, 6756– 64
- 20Miyata, Y.; Shiozawa, K.; Asada, Y.; Ohno, Y.; Kitaura, R.; Mizutani, T.; Shinohara, H. Length-Sorted Semiconducting Carbon Nanotubes for High-Mobility Thin Film Transistors Nano Res. 2011, 4, 963– 970[Crossref], [CAS], Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXht1GrtbjM&md5=bb53c2dfe4c9ad1955632205621cc59bLength-sorted semiconducting carbon nanotubes for high-mobility thin film transistorsMiyata, Yasumitsu; Shiozawa, Kazunari; Asada, Yuki; Ohno, Yutaka; Kitaura, Ryo; Mizutani, Takashi; Shinohara, HisanoriNano Research (2011), 4 (10), 963-970CODEN: NRAEB5; ISSN:1998-0000. (Springer GmbH)We have developed a process for chem. purifn. of carbon nanotubes for soln.-processable thin-film transistors (TFTs) having high mobility. Films of the purified carbon nanotubes fabricated by simple drop coating showed carrier mobilities as high as 164 cm2V-1s-1, normalized transconductances of 0.78 Sm-1, and on/off current ratios of 106. Such high performance requires the prepn. of a suspension of micrometer-long and highly purified semiconducting single-walled carbon nanotubes (SWCNTs). Our purifn. process includes length and electronic-type selective trapping of SWCNTs using recycling gel filtration with a mixt. of surfactants. The results provide an important milestone toward printed high-speed and large-area electronics with roll-to-roll and ink-jet device fabrication.
- 21Wu, J.; Xie, L.; Hong, G.; Lim, H.; Thendie, B.; Miyata, Y.; Shinohara, H.; Dai, H. Short Channel Field-Effect Transistors from Highly Enriched Semiconducting Carbon Nanotubes Nano Res. 2012, 5, 388– 394[Crossref], [CAS], Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XovFWmtr8%253D&md5=f20553c8ad3d9beee63070bbf36f5433Short channel field-effect transistors from highly enriched semiconducting carbon nanotubesWu, Justin; Xie, Liming; Hong, Guosong; Lim, Hong En; Thendie, Boanerges; Miyata, Yasumitsu; Shinohara, Hisanori; Dai, HongjieNano Research (2012), 5 (6), 388-394CODEN: NRAEB5; ISSN:1998-0000. (Springer GmbH)Semiconducting single-walled carbon nanotubes (s-SWNTs) with a purity of ∼98% have been obtained by gel filtration of arc-discharge grown SWNTs with diams. in the range 1.2-1.6 nm. Multi-laser Raman spectroscopy confirmed the presence of less than 2% of metallic SWNTs (m-SWNTs) in the s-SWNT enriched sample. Measurement of ∼50 individual tubes in Pd-contacted devices with channel length 200 nm showed on/off ratios of >104, conductances of 1.38-5.8 μS, and mobilities in the range 40-150 cm2·V/s. Short channel multi-tube devices with ∼100 tubes showed lower on/off ratios due to residual m-SWNTs, although the on-current was greatly increased relative to the devices made from individual tubes.
- 22Zhang, J.; Gui, H.; Liu, B.; Liu, J.; Zhou, C. Comparative Study of Gel-Based Separated Arcdischarge, Hipco, and Comocat Carbon Nanotubes for Macroelectronic Applications Nano Res. 2013, 6, 906– 920[Crossref], [CAS], Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhslWltbnN&md5=9b37af3b673dcf0e5bf199f4aadfd499Comparative study of gel-based separated arcdischarge, HiPCO, and CoMoCAT carbon nanotubes for macroelectronic applicationsZhang, Jialu; Gui, Hui; Liu, Bilu; Liu, Jia; Zhou, ChongwuNano Research (2013), 6 (12), 906-920CODEN: NRAEB5; ISSN:1998-0000. (Springer GmbH)Due to their excellent elec. properties and compatibility with room-temp. deposition/printing processing, high-purity single-walled semiconducting carbon nanotubes hold great potential for macroelectronic applications such as in thin-film transistors and display back-panel electronics. However, the relative advantages and disadvantages of various nanotubes for macroelectronics remains an open issue, despite the great significance. Here in this paper, we report a comparative and systematic study of three kinds of mainstream carbon nanotubes (arc-discharge, HiPCO, CoMoCAT) sepd. using low-cost gel-based column chromatog. for thin-film transistor applications, and high performance transistors-which satisfy the requirements for transistors used in active matrix org. light-emitting diode displays-have been achieved. We observe a trade-off between transistor mobility and on/off ratio depending on the nanotube diam. While arc-discharge nanotubes with larger diams. lead to high device mobility, HiPCO and CoMoCAT nanotubes with smaller diams. can provide high on/off ratios (> 106) for transistors with comparable dimensions. Furthermore, we have also compared gel-based sepd. nanotubes with nanotubes sepd. using the d. gradient ultracentrifuge (DGU) method, and find that gel-sepd. nanotubes can offer purity and thin-film transistor performance as good as DGU-sepd. nanotubes. Our approach can serve as the crit. foundation for future carbon nanotube-based thin-film macroelectronics.
- 23Araujo, P. T.; Doorn, S. K.; Kilina, S.; Tretiak, S.; Einarsson, E.; Maruyama, S.; Chacham, H.; Pimenta, M. A.; Jorio, A. Third and Fourth Optical Transitions in Semiconducting Carbon Nanotubes Phys. Rev. Lett. 2007, 98, 067401[Crossref], [PubMed], [CAS], Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXhs1Cjsr4%253D&md5=54dc1e1e48298ef8174021c0f9f42b49Third and Fourth Optical Transitions in Semiconducting Carbon NanotubesAraujo, Paulo T.; Doorn, Stephen K.; Kilina, Svetlana; Tretiak, Sergei; Einarsson, Erik; Maruyama, Shigeo; Chacham, Helio; Pimenta, Marcos A.; Jorio, AdoPhysical Review Letters (2007), 98 (6), 067401/1-067401/4CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)The authors have studied the optical transition energies of single-wall C nanotubes over broad diam. (0.7-2.3 nm) and energy (1.26-2.71 eV) ranges, using their radial breathing mode Raman spectra. The authors establish the diam. and chiral angle dependence of the poorly studied 3rd and 4th optical transitions in semiconducting tubes. Comparative anal. between the higher lying transitions and the 1st and 2nd transitions show 2 different diam. scalings. Quantum mech. calcns. explain the result showing strongly bound excitons in the 1st and 2nd transitions and a delocalized electron wave function in the 3rd transition.
- 24Bachilo, S. M.; Strano, M. S.; Kittrell, C.; Hauge, R. H.; Smalley, R. E.; Weisman, R. B. Structure-Assigned Optical Spectra of Single-Walled Carbon Nanotubes Science 2002, 298, 2361– 2366[Crossref], [PubMed], [CAS], Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD38Xps1Sjuro%253D&md5=f05d114835b594d688e9256260797213Structure-Assigned Optical Spectra of Single-Walled Carbon NanotubesBachilo, Sergei M.; Strano, Michael S.; Kittrell, Carter; Hauge, Robert H.; Smalley, Richard E.; Weisman, R. BruceScience (Washington, DC, United States) (2002), 298 (5602), 2361-2366CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Spectrofluorometric measurements on single-walled carbon nanotubes (SWNTs) isolated in aq. surfactant suspensions have revealed distinct electronic absorption and emission transitions for more than 30 different semiconducting nanotube species. By combining these fluorimetric results with resonance Raman data, each optical transition has been mapped to a specific (n,m) nanotube structure. Optical spectroscopy can thereby be used to rapidly det. the detailed compn. of bulk SWNT samples, providing distributions in both tube diam. and chiral angle. The measured transition frequencies differ substantially from simple theor. predictions. These deviations may reflect combinations of trigonal warping and excitonic effects.
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- 26Blanch, A. J.; Quinton, J. S.; Shapter, J. G. The Role of Sodium Dodecyl Sulfate Concentration in the Separation of Carbon Nanotubes Using Gel Chromatography Carbon 2013, 60, 471– 480[Crossref], [CAS], Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXnvVarsbw%253D&md5=7ba73a20e1772b599b9b1a2c39fecb24The role of sodium dodecyl sulfate concentration in the separation of carbon nanotubes using gel chromatographyBlanch, Adam J.; Quinton, Jamie S.; Shapter, Joe G.Carbon (2013), 60 (), 471-480CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)Gel chromatog. was demonstrated as an effective method for generating sepd. fractions of metallic and semiconducting C nanotubes when starting with a heterogeneous dispersion in SDS. The influence of the surfactant concn. in this process was examd. here for chromatog. sepn. using a dextran-based gel as the stationary phase. Decreasing the concn. of SDS from 4 to 0.5 wt.% caused a gradual increase in the adsorption of semiconducting nanotubes to the gel in a species-selective manner, with low concns. of SDS (around 0.5%) found to provide the best semiconductor-metal sepn. Elution using a stepwise concn. gradient was able to produce fractions of reduced diam. population from the polydisperse HiPCO starting material, where a good correlation between the concn. of elution and local bond curvature for each nanotube species was obsd. Since bleaching of optical absorbance through protonation in the presence of dissolved O2 was found to mask the presence of nanotubes with large diams., it was deemed necessary to reverse the protonation effect through hydroxide addn. to detect these species in optical measurements of nanotube dispersions.
- 27Wallace, E. J.; Sansom, M. S. Carbon Nanotube Self-Assembly with Lipids and Detergent: A Molecular Dynamics Study Nanotechnology 2009, 20, 045101Google ScholarThere is no corresponding record for this reference.
- 28Xu, Z.; Yang, X.; Yang, Z. A Molecular Simulation Probing of Structure and Interaction for Supramolecular Sodium Dodecyl Sulfate/Single-Wall Carbon Nanotube Assemblies Nano Lett. 2010, 10, 985– 991[ACS Full Text
], [CAS], Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtlKkt7o%253D&md5=0bff721e969dc0faa124ccc9b5390b1dA Molecular Simulation Probing of Structure and Interaction for Supramolecular Sodium Dodecyl Sulfate/Single-Wall Carbon Nanotube AssembliesXu, Zhijun; Yang, Xiaoning; Yang, ZhenNano Letters (2010), 10 (3), 985-991CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Here we report a larger-scale at.-level mol. dynamics (MD) simulation for the self-assembly of sodium dodecyl sulfate (SDS) surfactant on single-walled carbon nanotube (SWNT) surfaces and the interaction between supramol. SDS/SWNT aggregates. We make an effort to address several important problems in regard to carbon nanotube dispersion/sepn. At first, the simulation provides comprehensive direct evidence for SDS self-assembly structures on carbon nanotube surfaces, which can help to clarify the relevant debate over the exact adsorption structure. We also, for the first time, simulated the potential of mean force (PMF) between two SWNTs embedded in SDS surfactant micelles. A novel unified PMF approach has been applied to reveal various cooperative interactions between the SDS/SWNT aggregates, which is different from the previous electrostatic repulsion explanation. The unique role of sodium ions revealed here provides a new microscopic understanding of the recent expts. in the electrolyte tuning of the interfacial forces on the selective fractionation of SDS surrounding SWNTs. - 29Duan, W. H.; Wang, Q.; Collins, F. Dispersion of Carbon Nanotubes with Sds Surfactants: A Study from a Binding Energy Perspective Chem. Sci. 2011, 2, 1407– 1413[Crossref], [CAS], Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXnsVyiu7Y%253D&md5=91444958c74ce9a416134ef08486f0f4Dispersion of carbon nanotubes with SDS surfactants: a study from a binding energy perspectiveDuan, Wen Hui; Wang, Quan; Collins, FrankChemical Science (2011), 2 (7), 1407-1413CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)Dispersion of carbon nanotubes with sodium dodecyl sulfate (SDS) surfactant is reported by mol. mechanics simulations from an energy perspective. The interaction energy of carbon nanotubes in a tube bundle is first calcd. to est. the force sufficient to sep. it from the bundle. The binding energy between increasing nos. of SDS mols. with a carbon nanotube is next estd. to identify the threshold no. of surfactant mols. for a possible dispersion. With the help of ultrasonication, a sufficient no. of SDS mols. are found to penetrate into an initial gap between a single tube and other nanotubes in the bundle. Owing to further congregation of the surfactants at the gap site, the gap becomes enlarged until complete dispersion. In addn. to the dispersion observation in view of the interaction and binding energy perspectives, four congregation processes were identified to reveal the aggregation morphologies of SDS surfactants on the surface of carbon nanotubes as well as the effect of diam. of a carbon nanotube on the adsorption d.
- 30Tummala, N. R.; Striolo, A. Sds Surfactants on Carbon Nanotubes: Aggregate Morphology ACS Nano 2009, 3, 595– 602[ACS Full Text
], [CAS], Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXitFKisrk%253D&md5=cc266bd3de46b9b6b20a7506afbe108bSDS surfactants on carbon nanotubes. Aggregate morphologyTummala, Naga Rajesh; Striolo, AlbertoACS Nano (2009), 3 (3), 595-602CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)Although C nanotubes have attracted enormous research interest, their practical application is still hindered, primarily, by the difficulty of sepg. them into samples monodispersed in diam., chirality, and length. Ultracentrifugating C nanotube dispersions stabilized by surfactants is a promising route for achieving the desired sepn. For further perfectioning this procedure it is necessary to know how surfactants adsorb on nanotubes of different diams., which dets. the nanotube-surfactant aggregate effective d. and the nanotube-nanotube potential of mean force. Because only limited exptl. data are available to elucidate these phenomena, we report here an extensive all-atom mol. dynamics study on the morphol. of SDS surfactant aggregates adsorbed on (6,6), (12,12), and (20,20) single walled C nanotubes at room conditions. The nanotube diam. is the primary factor that dets. the morphol. of the aggregates because of a competition between the entropic and energetic advantage encountered by the surfactants when they wrap one nanotube, and the enthalpic penalty faced during this process due to bending of the surfactant mol. The data are in qual. agreement with the neutron scattering results reported by Yurekli et al. (2004), and for the first time provide an at.-level description helpful in designing better sepn., as well as stabilization techniques for aq. C nanotube dispersions. - 31Niyogi, S.; Densmore, C. G.; Doorn, S. K. Electrolyte Tuning of Surfactant Interfacial Behavior for Enhanced Density-Based Separations of Single-Walled Carbon Nanotubes J. Am. Chem. Soc. 2008, 131, 1144– 1153Google ScholarThere is no corresponding record for this reference.
- 32Jain, R. M.; Howden, R.; Tvrdy, K.; Shimizu, S.; Hilmer, A. J.; McNicholas, T. P.; Gleason, K. K.; Strano, M. S. Polymer-Free Near-Infrared Photovoltaics with Single Chirality (6,5) Semiconducting Carbon Nanotube Active Layers Adv. Mater. 2012, 24, 4436– 4439[Crossref], [PubMed], [CAS], Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XptlSjsbs%253D&md5=e93b8454b36c58e46678c5f634d928cfPolymer-Free Near-Infrared Photovoltaics with Single Chirality (6,5) Semiconducting Carbon Nanotube Active LayersJain, Rishabh M.; Howden, Rachel; Tvrdy, Kevin; Shimizu, Steven; Hilmer, Andrew J.; McNicholas, Thomas P.; Gleason, Karen K.; Strano, Michael S.Advanced Materials (Weinheim, Germany) (2012), 24 (32), 4436-4439, S4436/1-S4436/9CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)An all-carbon photovoltaic device has been demonstrated where a film of highly purified (6,5) carbon nanotubes acts as the active photoabsorption layer. There is evidence to suggest that tight control over the electronic structure of the single-walled carbon nanotubes has enabled an open-circuit voltage higher than previously demonstrated in other single-walled carbon nanotube active layer devices. While device efficiency is limited, it is interesting to note that it is comparable to many polymer/single-walled carbon nanotube bulk heterojunction devices. Only a 20% impurity by wt. of a second chirality of semiconducting single-walled carbon nanotube (6,4) results in a more than 30 times decrease in power conversion efficiency. This study provides a foundation for future work aimed at increasing the efficiency of polymer-free all-carbon photovoltaics via several mechanisms, including active layer thickness modulation, bulk heterojunction geometries and single-walled carbon nanotube alignment.
- 33Kominkova, Z.; Vales, V.; Hersam, M. C.; Kalbac, M. Towards Quantification of the Ratio of the Single and Double Wall Carbon Nanotubes in Their Mixtures: An in Situ Raman Spectroelectrochemical Study Carbon 2014, 78, 366– 373Google ScholarThere is no corresponding record for this reference.
- 34Arnold, M. S.; Stupp, S. I.; Hersam, M. C. Enrichment of Single-Walled Carbon Nanotubes by Diameter in Density Gradients Nano Lett. 2005, 5, 713– 718[ACS Full Text
], [CAS], Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXit1Cnu7k%253D&md5=56cb8d91fe680f019bd245d88645a987Enrichment of single-walled carbon nanotubes by diameter in density gradientsArnold, Michael S.; Stupp, Samuel I.; Hersam, Mark C.Nano Letters (2005), 5 (4), 713-718CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)The bulk enrichment and sepn. of single-walled carbon nanotubes (SWNTs) by diam. has been achieved through ultracentrifugation of DNA-wrapped SWNTs in aq. d. gradients. The sepn. is identified by the visual formation of colored bands of SWNTs in the d. range of 1.11-1.17 g cm-3. The optical absorbance spectra of the sepd. SWNTs indicate that SWNTs of decreasing diam. are increasingly more buoyant. This nondestructive and scalable sepn. strategy is expected to impact the fields of mol. electronics, optoelectronics, and sensing where SWNTs of a monodisperse band gap are essential. - 35Arnold, M. S.; Green, A. A.; Hulvat, J. F.; Stupp, S. I.; Hersam, M. C. Sorting Carbon Nanotubes by Electronic Structure Using Density Differentiation Nat. Nanotechnol. 2006, 1, 60– 65[Crossref], [PubMed], [CAS], Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtFCisrvF&md5=4cc068399931940846573a7e9cf79873Sorting carbon nanotubes by electronic structure using density differentiationArnold, Michael S.; Green, Alexander A.; Hulvat, James F.; Stupp, Samuel I.; Hersam, Mark C.Nature Nanotechnology (2006), 1 (1), 60-65CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)The heterogeneity of as-synthesized single-walled carbon nanotubes (SWNTs) precludes their widespread application in electronics, optics and sensing. The authors report on the sorting of carbon nanotubes by diam., bandgap and electronic type using structure-discriminating surfactants to engineer subtle differences in their buoyant densities. Using the scalable technique of d.-gradient ultracentrifugation, the authors have isolated narrow distributions of SWNTs in which >97% are within a 0.02-nm-diam. range. Also, using competing mixts. of surfactants, the authors produced bulk quantities of SWNTs of predominantly a single electronic type. These materials were used to fabricate thin-film elec. devices of networked SWNTs characterized by either metallic or semiconducting behavior.
- 36Kim, W.-J.; Nair, N.; Lee, C. Y.; Strano, M. S. Covalent Functionalization of Single-Walled Carbon Nanotubes Alters Their Densities Allowing Electronic and Other Types of Separation J. Phys. Chem. C 2008, 112, 7326– 7331[ACS Full Text
], [CAS], Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXkslCit7s%253D&md5=59e093f76fd70c0cf5efe9d6d2e453a2Covalent Functionalization of Single-Walled Carbon Nanotubes Alters Their Densities Allowing Electronic and Other Types of SeparationKim, Woo-Jae; Nair, Nitish; Lee, Chang Young; Strano, Michael S.Journal of Physical Chemistry C (2008), 112 (19), 7326-7331CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Covalently attached functional groups can alter the densities of individual single-walled carbon nanotubes (SWNTs) in a predictable and highly controllable manner. A vol.-additivity model based on mol. group contributions can be used to est. the d. difference between 4-hydroxyphenyl-functionalized and nonfunctionalized HiPco SWNTs as approx. 98.3 kg/m3, compared with 97.9 kg/m3 measured by d.-gradient centrifugation. Conversely, the estd. d. difference between the (6,5) (0.75 nm diam.) and (9,8) (1.17 nm diam.) SWNTs is smaller at 23.4 kg/m3. Covalent functionalization can provide an effective handle to sep. particular SWNTs from a typical diam. distribution. SWNT mixts., in which metallic SWNTs have been selectively reacted, produce two distinct d. fractions corresponding to functionalized metallic and pure semiconducting SWNTs. The results were confirmed by Raman spectroscopy, where the high-d. fractions exhibit an increased disorder mode with a corresponding decrease in intensity for the low-d. fraction. This method also allows for the first independent measure of (n,m) SWNTs having different chem. conversions with functional groups, which will allow for a more rigorous anal. of SWNT chem. than is possible with uncalibrated spectroscopies such as Raman or photoluminescence. - 37Ghosh, S.; Bachilo, S. M.; Weisman, R. B. Advanced Sorting of Single-Walled Carbon Nanotubes by Nonlinear Density-Gradient Ultracentrifugation Nat. Nanotechnol. 2010, 5, 443– 450[Crossref], [PubMed], [CAS], Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXmvFWltrg%253D&md5=5e40af80c65a123388da30501dbc876cAdvanced sorting of single-walled carbon nanotubes by nonlinear density-gradient ultracentrifugationGhosh, Saunab; Bachilo, Sergei M.; Weisman, R. BruceNature Nanotechnology (2010), 5 (6), 443-450CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)Existing methods for growing single-walled carbon nanotubes produce samples with a range of structures and electronic properties, but many potential applications require pure nanotube samples. D.-gradient ultracentrifugation has recently emerged as a technique for sorting as-grown mixts. of single-walled nanotubes into their distinct (n,m) structural forms, but to date this approach is limited to samples contg. only a small no. of nanotube structures, and has often required repeated d.-gradient ultracentrifugation processing. Here, it is reported that the use of tailored nonlinear d. gradients can significantly improve d.-gradient ultracentrifugation sepns. It is shown that highly polydisperse samples of single-walled nanotubes grown by the HiPco method are readily sorted in a single step to give fractions enriched in any of ten different (n,m) species. Furthermore, minor variants of the method allow sepn. of the mirror-image isomers (enantiomers) of seven (n,m) species. Optimization of this approach was aided by the development of instrumentation that spectroscopically maps nanotube contents inside undisturbed centrifuge tubes.
- 38Wang, F.; Dukovic, G.; Brus, L. E.; Heinz, T. F. The Optical Resonances in Carbon Nanotubes Arise from Excitons Science 2005, 308, 838– 841[Crossref], [PubMed], [CAS], Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXjvVantrc%253D&md5=4b6b163c769b4ee25b5caba695c1ecd2The Optical Resonances in Carbon Nanotubes Arise from ExcitonsWang, Feng; Dukovic, Gordana; Brus, Louis E.; Heinz, Tony F.Science (Washington, DC, United States) (2005), 308 (5723), 838-841CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Optical transitions in carbon nanotubes are of central importance for nanotube characterization. They also provide insight into the nature of excited states in these one-dimensional systems. Recent work suggests that light absorption produces strongly correlated electron-hole states in the form of excitons. However, it has been difficult to rule out a simpler model in which resonances arise from the van Hove singularities assocd. with the one-dimensional bond structure of the nanotubes. Here, two-photon excitation spectroscopy bolsters the exciton picture. We found binding energies of ∼400 meV for semiconducting single-walled nanotubes with 0.8-nm diams. The results demonstrate the dominant role of many-body interactions in the excited-state properties of one-dimensional systems.
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- 42Krupke, R.; Hennrich, F.; Weber, H. B.; Beckmann, D.; Hampe, O.; Malik, S.; Kappes, M. M.; v. Löhneysen, H. Contacting Single Bundles of Carbon Nanotubes with Alternating Electric Fields Appl. Phys. A: Mater. Sci. Process. 2003, 76, 397– 400[Crossref], [CAS], Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD38Xos1Whtb0%253D&md5=143f436ca599ad3989908bb6cc5ddaddContacting single bundles of carbon nanotubes with alternating electric fieldsKrupke, R.; Hennrich, F.; Weber, H. B.; Beckmann, D.; Hampe, O.; Malik, S.; Kappes, M. M.; von Loehneysen, H.Applied Physics A: Materials Science & Processing (2003), 76 (3), 397-400CODEN: APAMFC; ISSN:0947-8396. (Springer-Verlag)Single bundles of carbon nanotubes have been selectively deposited from suspensions onto sub-micron electrodes with alternating elec. fields. We show that it is possible to control the trapping of a single bundle by the use of Ag as electrode material which, unlike Au, strongly interacts with the carboxyl functionalized carbon nanotubes. Excellent alignment of the bundles between Au or Ag electrodes occurs at frequencies above 1 kHz, with superior contacts being formed with Ag electrodes.
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