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Solvent Mediated Synthesis of Metal Chalcogenides

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Solvent Mediated Synthesis of Metal Chalcogenides Solvent Mediated Synthesis of Metal Chalcogenides Graham Andrew Shaw Supervised by Dr. I. P. Parkin Presented August 2000 Christopher Ingold Laboratories, University College London This thesis is submitted in partial fulfilment of the requirements for the Degree of Doctor of Philosophy (Chemistry) ProQuest Number: U642612 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest. ProQuest U642612 Published by ProQuest LLC(2015). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code. Microform Edition © ProQuest LLC. ProQuest LLC 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 Abstract This thesis is primarily concerned with the synthesis of binary and ternary transition metal and main-group metal chalcogenides (excluding oxides) at room temperature. Bulk material was sought using both elemental combination and metathetical reactions, in either liquid ammonia or n-butylamine. In addition, solid-state metathesis reactions were employed in the synthesis of a selection of low valent transition metal chalcogenides. Elemental combination reactions at room temperature afforded a simple, reproducible single- stage preparation of a range of transition and main-group metal chalcogenides in good yield (> 90%). Products were either highly crystalline (c) or X-ray amorphous {a) in nature. In most cases, annealing the X-ray amorphous powders at 200-250 °C for 2h was found to induce sufficient crystallinity for characterisation by X-ray powder diffraction. Both binary and ternary materials were afforded by the liquid ammonia reactions - MS(a) (M = Cd, Hg, Ni, Sn), ZnE(a) (E = S, Se Te), AszSg^, Cu( 2-x)E(a) (E = S, Se, Te), NiEz («> (E = Se, Te), ME(c) (M = Pb, Tl, E = S, Se; M = Cd Hg, E = Se, Te), AgzE(c) (E = S, Se, Te), Tl( 2-x)E(c) (E = Se, Te). AgTlTe(^), Zno. 45Cdo. 55S(a), MSrEz(a) (M = Mg, Ca, Ba, Yb; E = S, Se, Te), SrxBaySzca) / CdxHgyTezca) (E(x,y) = 1.00; X = 0.25, 0.50, 0.75), EuYbE 2(a) (E = S, Se, Te), MSxSey(g) (Z(x,y) = 1.00; M = Cu, Cd), Ag 3PnSs(c) (Pn = As, Sb), CuAsS(c). Similar reaction schemes and conditions were carried out in n-butylamine, resulting in a more restricted range of binary materials - ME(c) (M = Hg, Tl, Pb, E = S, Se; M = Hg, Pb, E = Te), AgzE(c) (E = S, Se, Te), Cu( 2-x)E(c) (E = Se, Te), Cu2S(„) and As2S3(o). In some cases, elemental combination was obtained by annealing the solvent treated elements, yielding highly crystalline, homogeneous products - liquid ammonia: M2E3 (M = In, Sb, Bi; E = S, Se; GazSe3), AszTe3, BizTe3, InE (E = S, Se) and PbTe; n-butylamine: NiS, M2E3 (M = As, Sb, Bi; E = Se Te). Solid state metathetical reactions of sodium chalcogenide (NazSz or NazE where E = S, Se Te) and low valent transition metal halides MXn (n = 1 , 2 ) were carried out in evacuated ampoules at 300 °C for 48h. In each case, removal of the co-produced salt from the highly sintered, fused product mixture afforded crystalline binary chalcogenides (typically of a single phase) - MEz (M = Fe, Co, E = S, Te), NiS(z+x), ME (MnS, FeSe, SnSe and SnTe), M(i_x)E (M = Fe, Co, E = S), Ni(i.x)E (E = S, Se, Te) and AgzE (E = S, Se, Te). Analogous reactions were observed in liquid ammonia at room temperature, affording a range of amorphous {a) and crystalline (c) chalcogenide powders, with each exhibiting an aggregated structure of typically <50-100 nm. Average crystallite sizes of ca. 10-50 nm have been calculated for nanocrystalline materials. Both binary and ternary materials were obtained as single phases in high yield (> 90%) - ME(c) (M = Pb, Tl; E = S, Se), PbTe(,), AgzE(,) (E = S, Se, Te), Tl(z-x)Te(,), MS^ (M = Ni, Zn, Cd, Hg), HgE(fl) (E = Se, Te), Cu(z-x)S(a), CuE(«> (E = S, Se, Te), MzE3(a) (M = Ga, In; E = S, Se, Te), MPn(a) (M = Fe, Co, Ni; Pn = As, Sb), MzEzca) (M = Zn, Cd; Pn = As, Sb), ABEz(g) (A = Cu, Ag, B = Ga, In, E = S, Se; A = Cu, B = Sb, E = S, Se, Te), CuizSb 4Si3(a) and CuFeSz(o). 1 Index Contents Page Abstract 1 Index 2 List of Figures 5 List of Tables 7 List of abbreviations 9 Acknowledgements 10 Preface 11 CHAPTER 1 - General Introduction 12-57 1.1 Liquid ammonia as a non aqueous solvent 12-18 1.1a Structure of ammonia 12 1.1b Solvent properties of liquid ammonia and aqueous solutions 13 1.1c General reaction types in liquid ammonia 16 1.2 Chemistry of some N-based solutions 19-29 1.2a Chemistry of sulfur-ammonia solutions 19 1.2b Chalcohalides as an in situ source of chalcogen 24 1.2c Chemistry of metallo-ammonia solutions 26 1.2d Chemistry of sulfur-amine solutions 28 1.3 Synthetic routes to metal chalcogenides 30-41 1.3.1 Bulk materials 30-34 1.3.1a Self-propagating high temperature synthesis (SHS) 30 1.3.1b Solid state metathesis (SSM) 32 1.3.2 Thin film material synthesis 35-41 1.3.2a Electrodeposition 35 1.3.2b Chemical baths 36 1.3.2c Molecular Organic Chemical Vapour Deposition (MOCVD) 37 1.3.2d Single molecule precursors to MOCVD 39 Contents (contd.) Page 1.4 Nanoparticulate semiconductors 41-49 1.4.1 Electronic structure 41 1.4.2 General applications 42 1.4.3 Synthetic design 43 1.4.4 Colloidal synthesis 44 1.4.5 Synthesis through restricted reaction environments 45-47 1.4.5.1 The use of zeolites 45 1.4.5.2 The use of copolymers 46 1.4.6 Synthesis by Organometallic routes 47-49 1.4.6.1 Duel source precursors 47 1.4.6.2 Single source precursors 48 1.5 Uses of metal chalcogenides 50-53 1.5.1 Binary semiconducting films 50 1.5.2 Bulk materials 51 1.5.3 Solid solutions 52 1.5.4 Ternary semiconductors 52 1.6 Aims of this work 54-57 1.6.1 Key spectroscopic methodologies 56 CHAPTER 2 - synthesis of binary materials by elemental combination reactions in liquid ammonia 58-88 2.1 Binary chalcogenides 58 2.2 Discussion of the synthesis of binary metal chalcogenides 75 2.3 Experimental 79 2.4 Binary pnictides 85 CHAPTER 3 - synthesis of ternary materials by elemental combination reactions in liquid ammonia 89-107 3.1 Ternary chalcogenides; general synthesis and characterisation 89 3.2 Combination of soluble metals with chalcogens 90 Contents (contd.) Page 3.3 Insoluble element combination (mixed metal chalcogenides) 90 3.4 Insoluble element combination (metal mixed chalcogenides) 96 3.5 Discussion of elemental combination reactions 1 0 0 3.6 Metal mixed pnictide chalcogenides (MsPnEs / MPnEz) 103 3.7 General conclusions of elemental combination reactions in liquid ammonia 115 CHAPTER 4 - synthesis of binary materials by elemental combination reactions in n-butylamine 118-136 4.1 Synthesis and characterisation 118 4.2 Discussion of elemental reaction in n-butylamine 130 4.3 Discussion of elemental reaction in N-based solvents 132 4.4 Conclusions of reaction in n-butylamine 135 4.5 Experimental of elemental reactions in n-butylamine 135 CHAPTER 5 - synthesis of binary metal chalcogenides by solid state metathesis reactions (SSM) 137-151 5.1 Synthesis and characterisation 137 5.2 Discussion and mechanistic evaluation 144 5.3 General conclusions 148 5.4 Experimental 149 CHAPTER 6 - metathetical reactions in liquid ammonia 152-186 6 .1 General introduction 152 6 . 2 Binary chalcogenides 152 6.3 Binary pnictides (Pn = As, Sb) 161 6.4 Ternary chalcogenides 166 6.5 Conclusions of liquid ammonia metathesis (ternary materials) 181 6 . 6 Experimental 183 References 187-199 List of Figures Page Preface 1.0 Flow diagram of the fundamental objectives of this thesis 11 Chapter 1 1.1 Structure of an ammonia molecule 12 1.2 Equilibria of sulfur dissolution in liquid ammonia (Lepoutre et a l) 21 1.3 Dissociation of sulfur polyanions in liquid ammonia 23 Chapter 2 2.1 XRD spectrum of lead sulfide (PbS) 60 2.2 XPS spectrum of zinc sulfide (showing 2p sulfur peak) 61 2.3 XRD spectrum of mercury sulfide (HgS) 63 2.4 “^Sn NMR spectrum of tin sulfide product 65 2.5 XRD spectrum of silver selenide (AgjSe) 6 8 2.6 XRD spectrum of mercury selenide (HgSe) 6 8 2.7 XRD spectrum of thallium telluride (TlzTe) 71 2.8 XRD spectrum of annealed tin phosphide (Sn:P 4:3) 87 Chapter 3 3.1 XRD spectrum of CdSo sScos compared to CdS and CdSe 91 3.2 Laser Induced Fluorescence spectra obtained for CdS^Sei.* 93 3.3 XRD pattern of pre-annealed reaction product of TlrCrrXe (1:1:2) 99 3.4 XRD spectrum of silver arsenic telluride (AgsAsTeg) 111 3.5 XRD spectrum of silver antimony sulfide (AgsSbsa) 111 Chapter 4 4.1 XPS spectrum of silver telluride (AgiTe) 123 4.2 Raman spectra of a-HgS (red phase) and P-HgS (black phase) 124 4.3 XRD spectrum of mercuric sulfide (black phase) 125 4.4 XRD spectrum of annealed mercuric sulfide (black phase) 125 4.5 XRD spectrum of thallium selenide (Tl:Se 2:3) 127 4.6 XRD spectrum of copper selenide (Cu:Se 1:1) 127 List of figures (contd.) Page 4.7 XRD spectrum of annealed bismuth selenide (Bi:Se 2:5) 129 C hapter 5 5.1 XRD spectrum of washed AgzSe 139 5.2 XRD spectrum of unwashed manganese sulfide 140 5.3 XRD spectrum of unwashed FeSz 141 5.4 XRD spectrum of unwashed NiS 2 142 C hapter 6 6 .1 XRD spectra of pre-annealed lead selenide and lead telluride 154 6.2 XRD spectrum of annealed zinc sulfide, ZnS (200-250 °C) 156 6.3 XRD spectrum of annealed cadmium sulfide, CdS (200-250 °C) 156 6.4 XRD spectrum of annealed cobalt antimonide (Co:Sb 3:2) 163 6.5 XRD spectrum of annealed silver indium sulfide (AglnSz) 168 6 .
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