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Title: Polysulfide ligand exchange on zinc sulfide nanocrystal surfaces for improved film formation

Journal Article · · Applied Surface Science

The physical and chemical properties of nanocrystals can be modified by changing the ligands attached at their surfaces. A ligand exchange procedure with ammonium polysulfides has been developed to replace the native ligands on cubic zinc sulfide nanocrystals. Several mixtures of polysulfides in formamide and other solvents were prepared with different average chain lengths and used to achieve high yield ligand exchange, as confirmed by UV–vis spectroscopy, infrared spectroscopy and X-ray photoelectron spectroscopy. The results show that polysulfide content can be increased with longer surface ligands and that the exchange process yields compositionally pure surfaces before and after high temperature anneals. X-ray diffraction and scanning electron microscopy show that, when annealed in nitrogen at 525 °C, polysulfide ligands lead to average crystal sizes 2–3 times larger than in the un-exchanged control sample. The ligand exchange procedure itself does not alter nanocrystal size. Nanocrystal inks prepared from the exchanged samples form thin films that exhibit superior grain growth, morphology, mass retention, and composition compared to the un-exchanged material. Overall, polysulfide species are demonstrated as alternative ligands for the surfaces of metal chalcogenide nanocrystals which, when incorporated in an efficient ligand-exchange procedure, can improve the quality of ZnS nanocrystal inks.

Research Organization:
Stanford Univ., CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office
Grant/Contract Number:
EE0004946
OSTI ID:
1579800
Alternate ID(s):
OSTI ID: 1254772
Journal Information:
Applied Surface Science, Vol. 359, Issue C; ISSN 0169-4332
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science

References (40)

Solar cells from colloidal nanocrystals: Fundamentals, materials, devices, and economics journal August 2009
Materials Availability Expands the Opportunity for Large-Scale Photovoltaics Deployment journal March 2009
Device Characteristics of CZTSSe Thin-Film Solar Cells with 12.6% Efficiency journal November 2013
In Situ Spectroelectrochemical Studies on the Reduction of Sulfur in Dimethyl Sulfoxide Solutions journal January 1993
Controlling surface band-bending of InP with polysulfide treatments journal January 1992
Solar Energy Conversion Toward 1 Terawatt journal April 2008
Identification and characterization of lithium polysulfides in solution in liquid ammonia journal January 1988
Formation of lithium polysulfides in aprotic media journal January 1977
Dimensional Reduction:  A Practical Formalism for Manipulating Solid Structures journal April 2001
The use of Soluble Metal-Polyselenide Complexes as Precursors to Binary and Ternary Solid Metal Selenides journal January 1990
Cubic ZnS under pressure: Optical-absorption edge, phase transition, and calculated equation of state journal November 1990
Transition Metal Polysulfide Complexes as Single-Source Precursors for Metal Sulfide Nanocrystals journal February 2010
The Zn(S,O,OH)/ZnMgO buffer in thin film Cu(In,Ga)(S,Se) 2 -based solar cells part I: Fast chemical bath deposition of Zn(S,O,OH) buffer layers for industrial application on Co-evaporated Cu(In,Ga)Se 2 and electrodeposited CuIn(S,Se) 2 solar cells: Zn(S,O,OH) CHEMICAL BATH DEPOSITION journal April 2009
Colloidal Nanocrystals with Molecular Metal Chalcogenide Surface Ligands journal June 2009
Solution-Based Synthesis and Characterization of Cu 2 ZnSnS 4 Nanocrystals journal September 2009
ZnO and ZnS Nanostructures: Ultraviolet-Light Emitters, Lasers, and Sensors journal November 2009
High-mobility ultrathin semiconducting films prepared by spin coating journal March 2004
The High-Resolution FTIR Far-Infrared Spectrum of Formamide journal January 1999
Nanocrystalline Chalcopyrite Materials (CuInS 2 and CuInSe 2 ) via Low-Temperature Pyrolysis of Molecular Single-Source Precursors journal August 2003
Oleic acid coating on the monodisperse magnetite nanoparticles journal December 2006
The effect of surface passivation on the structure of sulphur-rich PbS colloidal quantum dots for photovoltaic application journal January 2015
Direct Liquid Coating of Chalcopyrite Light-Absorbing Layers for Photovoltaic Devices journal November 2009
Metal-free Inorganic Ligands for Colloidal Nanocrystals: S2–, HS, Se2–, HSe, Te2–, HTe, TeS32–, OH, and NH2– as Surface Ligands journal July 2011
La reduction du soufre en milieu organique journal February 1976
Electrochemical reduction of sulfur in aprotic solvents journal August 1973
Polysulfido Complexes of Main Group and Transition Metals book January 2003
Reconstructing a solid-solid phase transformation pathway in CdSe nanosheets with associated soft ligands journal September 2010
Prospects of Colloidal Nanocrystals for Electronic and Optoelectronic Applications journal January 2010
Schwefelreiche spirozyklische Komplexe: [Zn(S6)2]2–, [Cd(S6)2]2–, [Hg(S6)2]2– und [Hg(S4)2]2– / Sulfur-Rich Spirocyclic Complexes: [Zn(S6)2]2-, [Cd(S6)2]2-, [Hg(S6)2]2- and [Hg(S4)2]2- journal October 1985
Raman studies of sulfur-containing anions in inorganic polysulfides. Sodium polysulfides journal August 1976
Detection of sulphur and polysulphides on electrochemically oxidized pyrite surfaces by X-ray photoelectron spectroscopy and Raman spectroscopy journal October 1990
A note on the compression of cubic ZnS journal January 1980
Thermodynamic analysis and phase equilibria calculations for the Zn-Te, Zn-Se and Zn-S systems journal April 1988
Time-Resolved In Situ Spectroelectrochemical Study on Reduction of Sulfur in N,N[sup ʹ]-Dimethylformamide journal January 2004
Luminescence in Sulfides: A Rich History and a Bright Future journal April 2010
Sustainability of photovoltaics: The case for thin-film solar cells journal December 2009
Effects of nanorod structure and conformation of fatty acid self-assembled layers on superhydrophobicity of zinc oxide surface journal December 2007
Structure of Barium Stearate Films at the Air/Water Interface Investigated by Polarization Modulation Infrared Spectroscopy and π− A Isotherms journal May 2001
Low-Cost Inorganic Solar Cells: From Ink To Printed Device journal November 2010
From Sulfur−Amine Solutions to Metal Sulfide Nanocrystals: Peering into the Oleylamine−Sulfur Black Box journal April 2011

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