All-inorganic Germanium nanocrystal films by cationic ligand exchange

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; Anderson, Nicholas C.; Beard, Matthew C.; Neale, Nathan R.

doi:10.1021/acs.nanolett.5b05192

All-inorganic Germanium nanocrystal films by cationic ligand exchange

Journal Article · Thu Jan 21 00:00:00 EST 2016 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.5b05192· OSTI ID:1242684

Wheeler, Lance M. ^[1]; Nichols, Asa W. ^[2]; Chernomordik, Boris D. ^[1]; Anderson, Nicholas C. ^[1]; Beard, Matthew C. ^[1]; Neale, Nathan R. ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States); West Virginia Wesleyan College, Buckhannon, WV (United States)

In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport in germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Advanced Solar Photophysics (CASP); National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC36-08GO28308; AC52-06NA25396

OSTI ID:: 1242684

Report Number(s):: NREL/JA--5900-65566

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 3 Vol. 16; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Routes to Achieving High Quantum Yield Luminescence from Gas-Phase-Produced Silicon Nanocrystals Anthony, Rebecca J.; Rowe, David J.; Stein, Matthias Advanced Functional Materials, Vol. 21, Issue 21 https://doi.org/10.1002/adfm.201100784	journal	August 2011
Water-Soluble Germanium(0) Nanocrystals: Cell Recognition and Near-Infrared Photothermal Conversion Properties Lambert, Timothy N.; Andrews, Nicholas L.; Gerung, Henry Small, Vol. 3, Issue 4 https://doi.org/10.1002/smll.200600529	journal	April 2007
Compounds of Germanium, Tin and Lead Including Biological Activity and Commercial Application: Covering the Literature from 1965 to 1968 Weiss, Richard W. Organometallic Compounds https://doi.org/10.1007/978-3-642-50290-3	book	January 1972
Synthesis and Ligand Exchange of Thiol-Capped Silicon Nanocrystals Yu, Yixuan; Rowland, Clare E.; Schaller, Richard D. Langmuir, Vol. 31, Issue 24 https://doi.org/10.1021/acs.langmuir.5b01246	journal	June 2015
Thiol-Capped Germanium Nanocrystals: Preparation and Evidence for Quantum Size Effects Muthuswamy, Elayaraja; Zhao, Jing; Tabatabaei, Katayoun Chemistry of Materials, Vol. 26, Issue 6, p. 2138-2146 https://doi.org/10.1021/cm4042154	journal	March 2014
Germanium and its Inorganic Compounds. Johnson, Otto H. Chemical Reviews, Vol. 51, Issue 3 https://doi.org/10.1021/cr60160a002	journal	December 1952
Infrared spectra of germanium sulfide, germanium disulfide, germanium oxide sulfide and germanium dioxide in solid argon Hassanzadeh, Parviz; Andrews, Lester The Journal of Physical Chemistry, Vol. 96, Issue 15 https://doi.org/10.1021/j100194a018	journal	July 1992
From Sulfur−Amine Solutions to Metal Sulfide Nanocrystals: Peering into the Oleylamine−Sulfur Black Box Thomson, Jordan W.; Nagashima, Kaz; Macdonald, Peter M. Journal of the American Chemical Society, Vol. 133, Issue 13 https://doi.org/10.1021/ja1109997	journal	April 2011
Metal-free Inorganic Ligands for Colloidal Nanocrystals: S^2–, HS^–, Se^2–, HSe^–, Te^2–, HTe^–, TeS₃^2–, OH^–, and NH^2– as Surface Ligands Nag, Angshuman; Kovalenko, Maksym V.; Lee, Jong-Soo Journal of the American Chemical Society, Vol. 133, Issue 27, p. 10612-10620 https://doi.org/10.1021/ja2029415	journal	July 2011
Ligand Exchange and the Stoichiometry of Metal Chalcogenide Nanocrystals: Spectroscopic Observation of Facile Metal-Carboxylate Displacement and Binding Anderson, Nicholas C.; Hendricks, Mark P.; Choi, Joshua J. Journal of the American Chemical Society, Vol. 135, Issue 49, p. 18536-18548 https://doi.org/10.1021/ja4086758	journal	November 2013
Ligand Bonding and Dynamics on Colloidal Nanocrystals at Room Temperature: The Case of Alkylamines on CdSe Nanocrystals Ji, Xiaohui; Copenhaver, Danis; Sichmeller, Christopher Journal of the American Chemical Society, Vol. 130, Issue 17 https://doi.org/10.1021/ja710909f	journal	April 2008
Structural, Optical, and Electrical Properties of PbSe Nanocrystal Solids Treated Thermally or with Simple Amines Law, Matt; Luther, Joseph M.; Song, Qing Journal of the American Chemical Society, Vol. 130, Issue 18 https://doi.org/10.1021/ja800040c	journal	May 2008
Colloidal Synthesis of Infrared-Emitting Germanium Nanocrystals Lee, Doh C.; Pietryga, Jeffrey M.; Robel, Istvan Journal of the American Chemical Society, Vol. 131, Issue 10, p. 3436-3437 https://doi.org/10.1021/ja809218s	journal	March 2009
Surface Chemistry Exchange of Alloyed Germanium Nanocrystals: A Pathway Toward Conductive Group IV Nanocrystal Films Ruddy, Daniel A.; Erslev, Peter T.; Habas, Susan E. The Journal of Physical Chemistry Letters, Vol. 4, Issue 3, p. 416-421 https://doi.org/10.1021/jz3020875	journal	January 2013
Tunable Band Gap Emission and Surface Passivation of Germanium Nanocrystals Synthesized in the Gas Phase Wheeler, Lance M.; Levij, Laszlo M.; Kortshagen, Uwe R. The Journal of Physical Chemistry Letters, Vol. 4, Issue 20 https://doi.org/10.1021/jz401576b	journal	September 2013
Surface Functionalization of Silicon Nanoparticles Produced by Laser-Driven Pyrolysis of Silane followed by HF−HNO ₃ Etching Li, Xuegeng; He, Yuanqing; Swihart, Mark T. Langmuir, Vol. 20, Issue 11 https://doi.org/10.1021/la036219j	journal	May 2004
Germanium Oxide Removal by Citric Acid and Thiol Passivation from Citric Acid-Terminated Ge(100) Collins, Gillian; Aureau, Damien; Holmes, Justin D. Langmuir, Vol. 30, Issue 47 https://doi.org/10.1021/la503819z	journal	November 2014
Dependence of Carrier Mobility on Nanocrystal Size and Ligand Length in PbSe Nanocrystal Solids Liu, Yao; Gibbs, Markelle; Puthussery, James Nano Letters, Vol. 10, Issue 5 https://doi.org/10.1021/nl101284k	journal	May 2010
Germanium and Silicon Nanocrystal Thin-Film Field-Effect Transistors from Solution Holman, Zachary C.; Liu, Chin-Yi; Kortshagen, Uwe R. Nano Letters, Vol. 10, Issue 7 https://doi.org/10.1021/nl101413d	journal	July 2010
High-Efficiency Silicon Nanocrystal Light-Emitting Devices Cheng, Kai-Yuan; Anthony, Rebecca; Kortshagen, Uwe R. Nano Letters, Vol. 11, Issue 5 https://doi.org/10.1021/nl2001692	journal	May 2011
Nanocrystal Inks without Ligands: Stable Colloids of Bare Germanium Nanocrystals Holman, Zachary C.; Kortshagen, Uwe R. Nano Letters, Vol. 11, Issue 5 https://doi.org/10.1021/nl200774y	journal	May 2011
A Generic Method for Rational Scalable Synthesis of Monodisperse Metal Sulfide Nanocrystals Zhang, Haitao; Hyun, Byung-Ryool; Wise, Frank W. Nano Letters, Vol. 12, Issue 11 https://doi.org/10.1021/nl303207s	journal	October 2012
Multicolor Silicon Light-Emitting Diodes (SiLEDs) Maier-Flaig, Florian; Rinck, Julia; Stephan, Moritz Nano Letters, Vol. 13, Issue 2 https://doi.org/10.1021/nl3038689	journal	January 2013
Schottky Solar Cells Based on Colloidal Nanocrystal Films Luther, Joseph M.; Law, Matt; Beard, Matthew C. Nano Letters, Vol. 8, Issue 10 https://doi.org/10.1021/nl802476m	journal	October 2008
Near-Infrared Photoluminescence Enhancement in Ge/CdS and Ge/ZnS Core/Shell Nanocrystals: Utilizing IV/II–VI Semiconductor Epitaxy Guo, Yijun; Rowland, Clare E.; Schaller, Richard D. ACS Nano, Vol. 8, Issue 8, p. 8334-8343 https://doi.org/10.1021/nn502792m	journal	July 2014
Synthesis and structures of hypervalent species of silicon and germanium: toward heptacoordination? Breliere, C.; Carre, F.; Corriu, R. J. P. Organometallics, Vol. 7, Issue 4 https://doi.org/10.1021/om00094a034	journal	April 1988
Syntheses, Structures, and Electronic Properties of the Branched Oligogermanes (Ph ₃ Ge) ₃ GeH and (Ph ₃ Ge) ₃ GeX (X = Cl, Br, I) ^† Samanamu, Christian R.; Amadoruge, Monika L.; Yoder, Claude H. Organometallics, Vol. 30, Issue 5 https://doi.org/10.1021/om101091c	journal	March 2011
Hypervalent surface interactions for colloidal stability and doping of silicon nanocrystals Wheeler, Lance M.; Neale, Nathan R.; Chen, Ting Nature Communications, Vol. 4, Article No. 2197 https://doi.org/10.1038/ncomms3197	journal	July 2013
Enhanced carrier multiplication in engineered quasi-type-II quantum dots Cirloganu, Claudiu M.; Padilha, Lazaro A.; Lin, Qianglu Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5148	journal	June 2014
Solution-processed PbS quantum dot infrared photodetectors and photovoltaics McDonald, Steven A.; Konstantatos, Gerasimos; Zhang, Shiguo Nature Materials, Vol. 4, Issue 2 https://doi.org/10.1038/nmat1299	journal	January 2005
Improved performance and stability in quantum dot solar cells through band alignment engineering Chuang, Chia-Hao M.; Brown, Patrick R.; Bulović, Vladimir Nature Materials, Vol. 13, Issue 8, p. 796-801 https://doi.org/10.1038/nmat3984	journal	May 2014
Band-like transport, high electron mobility and high photoconductivity in all-inorganic nanocrystal arrays Lee, Jong-Soo; Kovalenko, Maksym V.; Huang, Jing Nature Nanotechnology, Vol. 6, Issue 6 https://doi.org/10.1038/nnano.2011.46	journal	April 2011
The promise and challenge of nanostructured solar cells Beard, Matthew C.; Luther, Joseph M.; Nozik, Arthur J. Nature Nanotechnology, Vol. 9, Issue 12 https://doi.org/10.1038/nnano.2014.292	journal	December 2014
Metal Halide Solid-State Surface Treatment for High Efficiency PbS and PbSe QD Solar Cells Crisp, Ryan W.; Kroupa, Daniel M.; Marshall, Ashley R. Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep09945	journal	April 2015
Novel derivatives of hypervalent germanium: synthesis, structure, and stability Lermontova, El'mira Kh.; Huan, MengMeng; Churakov, Andrei V. Dalton Transactions, Issue 24 https://doi.org/10.1039/b901885a	journal	January 2009
High performance silicon nanoparticle anode in fluoroethylene carbonate-based electrolyte for Li-ion batteries Lin, Yong-Mao; Klavetter, Kyle C.; Abel, Paul R. Chemical Communications, Vol. 48, Issue 58 https://doi.org/10.1039/c2cc31712e	journal	January 2012
Silicon nanocrystals with ensemble quantum yields exceeding 60% Jurbergs, David; Rogojina, Elena; Mangolini, Lorenzo Applied Physics Letters, Vol. 88, Issue 23 https://doi.org/10.1063/1.2210788	journal	June 2006
Nonthermal plasma synthesis of size-controlled, monodisperse, freestanding germanium nanocrystals Gresback, Ryan; Holman, Zachary; Kortshagen, Uwe Applied Physics Letters, Vol. 91, Issue 9 https://doi.org/10.1063/1.2778356	journal	August 2007
Exciton dissociation and photovoltaic effect in germanium nanocrystals and poly(3-hexylthiophene) composites Sun, Baoquan; Zou, Guifu; Shen, Xiaojuan Applied Physics Letters, Vol. 94, Issue 23 https://doi.org/10.1063/1.3152997	journal	June 2009
Quantum dot Ge/TiO ₂ heterojunction photoconductor fabrication and performance Church, Carena P.; Muthuswamy, Elayaraja; Zhai, Guangmei Applied Physics Letters, Vol. 103, Issue 22 https://doi.org/10.1063/1.4826916	journal	November 2013
PbSe Nanocrystal Solids for n- and p-Channel Thin Film Field-Effect Transistors Talapin, D. V. Science, Vol. 310, Issue 5745, p. 86-89 https://doi.org/10.1126/science.1116703	journal	October 2005
Slow Electron Cooling in Colloidal Quantum Dots Pandey, A.; Guyot-Sionnest, P. Science, Vol. 322, Issue 5903 https://doi.org/10.1126/science.1159832	journal	November 2008
Colloidal Nanocrystals with Molecular Metal Chalcogenide Surface Ligands Kovalenko, M. V.; Scheele, M.; Talapin, D. V. Science, Vol. 324, Issue 5933 https://doi.org/10.1126/science.1170524	journal	June 2009
Cu2ZnSnSe4 nanocrystals capped with S2− by ligand exchange: utilizing energy level alignment for efficiently reducing carrier rec ombination Wang, Xia; Kou, Dong-Xing; Zhou, Wen-Hui Nanoscale Research Letters, Vol. 9, Issue 1 https://doi.org/10.1186/1556-276X-9-262	journal	January 2014

Cited By (3)

Large n- and p-type thermoelectric power factors from doped semiconducting single-walled carbon nanotube thin films MacLeod, Bradley A.; Stanton, Noah J.; Gould, Isaac E. Energy & Environmental Science, Vol. 10, Issue 10 https://doi.org/10.1039/c7ee01130j	journal	January 2017
Light trapping structures and plasmons synergistically enhance the photovoltaic performance of full-spectrum solar cells Qiao, Fen; Xie, Yi; He, Gang Nanoscale, Vol. 12, Issue 3 https://doi.org/10.1039/c9nr08761c	journal	January 2020
Surface coordination chemistry of germanium nanocrystals synthesized by microwave-assisted reduction in oleylamine Smock, Sara R.; Tabatabaei, Katayoon; Williams, Travis J. Nanoscale, Vol. 12, Issue 4 https://doi.org/10.1039/c9nr09233a	journal	January 2020

Similar Records

Group IV nanocrystals with ion-exchangeable surface ligands and methods of making the same

Patent · Mon Jan 08 23:00:00 EST 2018 · OSTI ID:1416730

Inorganic Chemistry Solutions to Semiconductor Nanocrystal Problems

Journal Article · Sat Mar 15 00:00:00 EDT 2014 · Coordination Chemistry Reviews · OSTI ID:1136863

Surface coordination chemistry of germanium nanocrystals synthesized by microwave-assisted reduction in oleylamine

Journal Article · Sun Jan 12 19:00:00 EST 2020 · Nanoscale · OSTI ID:1728701

Related Subjects

14 SOLAR ENERGY
77 NANOSCIENCE AND NANOTECHNOLOGY
Germanium nanocrystal
inorganic ligand
ligand exchange
plasma synthesis
quantum dots (QD)

All-inorganic Germanium nanocrystal films by cationic ligand exchange

Citation Formats

References (44)

Cited By (3)

Similar Records

Related Subjects