US20010005495A1 - Process for preparing a nanocrystalline material - Google Patents
Process for preparing a nanocrystalline material Download PDFInfo
- Publication number
- US20010005495A1 US20010005495A1 US09/043,258 US4325898A US2001005495A1 US 20010005495 A1 US20010005495 A1 US 20010005495A1 US 4325898 A US4325898 A US 4325898A US 2001005495 A1 US2001005495 A1 US 2001005495A1
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- United States
- Prior art keywords
- ion
- group
- process according
- nanocrystalline material
- cadmium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000002707 nanocrystalline material Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 73
- 230000008569 process Effects 0.000 claims abstract description 61
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 33
- 150000002500 ions Chemical class 0.000 claims description 26
- 125000000962 organic group Chemical group 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 230000003287 optical effect Effects 0.000 claims description 9
- 125000004149 thio group Chemical group *S* 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 8
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 claims description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005083 Zinc sulfide Substances 0.000 claims description 5
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 5
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 5
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 5
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 claims description 4
- -1 selenide ion Chemical class 0.000 claims description 4
- 150000004763 sulfides Chemical group 0.000 claims description 4
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 claims description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 3
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims description 3
- YRYHCNRGWVYHCG-UHFFFAOYSA-N 3H-dithiol-3-ylcarbamic acid Chemical group OC(=O)NC1SSC=C1 YRYHCNRGWVYHCG-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001449 indium ion Inorganic materials 0.000 claims description 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 2
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 13
- 239000011669 selenium Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- VQNPSCRXHSIJTH-UHFFFAOYSA-N cadmium(2+);carbanide Chemical compound [CH3-].[CH3-].[Cd+2] VQNPSCRXHSIJTH-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910005541 GaS2 Inorganic materials 0.000 description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 231100001261 hazardous Toxicity 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 235000015096 spirit Nutrition 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 3
- RHKSESDHCKYTHI-UHFFFAOYSA-N 12006-40-5 Chemical compound [Zn].[As]=[Zn].[As]=[Zn] RHKSESDHCKYTHI-UHFFFAOYSA-N 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- FSIONULHYUVFFA-UHFFFAOYSA-N cadmium arsenide Chemical compound [Cd].[Cd]=[As].[Cd]=[As] FSIONULHYUVFFA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- BVSHTEBQPBBCFT-UHFFFAOYSA-N gallium(iii) sulfide Chemical compound [S-2].[S-2].[S-2].[Ga+3].[Ga+3] BVSHTEBQPBBCFT-UHFFFAOYSA-N 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- SIXIBASSFIFHDK-UHFFFAOYSA-N indium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[In+3].[In+3] SIXIBASSFIFHDK-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- XHFGWHUWQXTGAT-UHFFFAOYSA-N n-methylpropan-2-amine Chemical compound CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MYLBTCQBKAKUTJ-UHFFFAOYSA-N 7-methyl-6,8-bis(methylsulfanyl)pyrrolo[1,2-a]pyrazine Chemical compound C1=CN=CC2=C(SC)C(C)=C(SC)N21 MYLBTCQBKAKUTJ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000004279 X-ray Guinier Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- RLECCBFNWDXKPK-UHFFFAOYSA-N bis(trimethylsilyl)sulfide Chemical compound C[Si](C)(C)S[Si](C)(C)C RLECCBFNWDXKPK-UHFFFAOYSA-N 0.000 description 1
- RGVBVVVFSXWUIM-UHFFFAOYSA-M bromo(dimethyl)sulfanium;bromide Chemical compound [Br-].C[S+](C)Br RGVBVVVFSXWUIM-UHFFFAOYSA-M 0.000 description 1
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- PNZJBDPBPVHSKL-UHFFFAOYSA-M chloro(diethyl)indigane Chemical compound [Cl-].CC[In+]CC PNZJBDPBPVHSKL-UHFFFAOYSA-M 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000005516 deep trap Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000020043 port wine Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 150000004771 selenides Chemical class 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- FKIZDWBGWFWWOV-UHFFFAOYSA-N trimethyl(trimethylsilylselanyl)silane Chemical compound C[Si](C)(C)[Se][Si](C)(C)C FKIZDWBGWFWWOV-UHFFFAOYSA-N 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/20—Methods for preparing sulfides or polysulfides, in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G11/00—Compounds of cadmium
- C01G11/02—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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Abstract
Description
- The present invention relates to a process. In particular, the present invention relates to a process for synthesising nanocrystalline materials, such as nanocrystalline CdSe.
- Nanocrystalline materials, which are sometimes referred to as nanoparticles, Q-particles, quantum dots or nanocrystallites, have been recognised as suitable systems for studying the transition from the molecular to the macrocrystalline level and have been extensively studied in the recent years.1−11
- Interest in research into new synthetic routes for semiconductor nanocrystallites is now enhanced as devices based on such materials have been fabricated.12−14 A number of synthetic methods have been reported for the preparation of a wide range of semiconductor nanoparticles.1-7,15-23
- Known processes for preparing nanocrystalline materials, such as nanocrystalline CdSe, have included arrested precipitation in micelles21 or the reaction of molecular species at high temperature in organic solvents.22−25
- In more detail, Murray et al22 report on the preparation of CdE (where E is S, Se or Te) by the pyrolysis of two organometallic reagents by injection into a hot coordinating solvent. In particular, the Murray process involves injecting a solution of (CH3)2Cd in TOP (tri-n-octylphosphine) into a hot solution of TOP containing Se (TOPSe and TOP). Alternatively, any one of (TMS)2S (bis(trimethylsilyl)sulphide), (TMS)2Se (bis(trimethylsilyl)selenide), and (BDMS)2Te (bis(tert-butyldimethylsilyl)tellurium) may be used instead of TOPSe.
- In the Murray process (CH3)2Cd is chosen as the only Cd source. Moreover, Murray et al state that (TMS)2Se or TOPSe and TOPTe are selected as chalcogen sources with TOPSe and TOPTe preferred due to their ease of preparation and their stability.
- Chemical reactions in TOPO (tri-n-octylphosphine oxide) are also described by Murray24. These processes have been used to prepare nanocrystallites of II/VI semiconductors12,13,24,25. In this instance, TOPO is used as dispersing medium and a metal source (e.g Cd(CH3)2) and a chalcogenide source (e.g. TOPSe) are injected into the hot TOPO (typically at 250° C.) to form CdSe nanocrystallites. The size distribution of the semiconductor can be controlled by the temperature of heating during the synthesis and by size selective precipitation of the final material.24,25
- A refinement of the Murray process has been proposed by Katari et al23. As with the Murray process, in the Katari process CdE is prepared by the pyrolysis of two organometallic reagents by injection into a hot coordinating solvent. In the Katari process Se is dissolved in TBP (tributylphosphine) to which (CH3)2Cd is then added. The resultant (CH3)2Cd/Se solution is then added to a heated solution of TOPO.
- As with the Murray process, in the Katari process (CH3)2Cd is chosen as the only Cd source.
- There are however problems associated with the prior art processes for preparing nanocrystalline materials. For example, both the Murray process (ibid) and the Katari process (ibid) involve the use of hazardous chemicals, in particular (CH3)2Cd. In this regard, (CH3)2Cd is toxic, volatile and extremely difficult to handle. Moreover, on exposure to air it undergoes spontaneous combustion.
- Aside from using the hazardous compound Cd(CH3)2 12,13 to prepare nanocrystalline CdSe, other workers have used the equally hazardous H2Se14 for the synthesis of the CdSe.
- The present invention seeks to overcome the problems associated with the prior art processes for making nanocrystalline materials.
- According to a first aspect of the present invention there is provided a process for preparing a nanocrystalline material comprising at least a first ion and at least a second ion different from the first ion, and wherein at least the first ion is a metal ion, the process comprising contacting a metal complex comprising the first ion and the second ion with a dispersing medium suitable to form the nanocrystalline material and wherein the dispersing medium is at a temperature which allows formation of the nanocrystalline material by pyrolysis when contacted with the metal complex.
- According to a second aspect of the present invention there is provided a nanocrystalline material obtained by the process of the present invention.
- According to a third aspect of the present invention there is provided a device comprising a nanocrystalline material obtained by the process of the present invention.
- Preferably the metal ion is a divalent metal ion or a trivalent metal ion.
- Preferably the metal ion is selected from a cadmium ion, a zinc ion, a lead ion, a mercury ion, an indium ion and a gallium ion, including combinations thereof.
- Preferably the second ion is selected from an oxide ion, a selenide ion, a sulphide group, a phosphide group or an arsenide ion, or combinations thereof.
- Preferably the second ion is or is part of a thiol-carbamate group or a selenocarbamate group.
- Preferably the second ion is or is part of a dithiol-carbamnate group or a diselenocarbamate group.
- Preferably the metal complex additionally comprises an organic group and/or thio group. The organic group can be an alkyl group or an aryl group, which may be substituted.
- Preferably the organic group is an alkyl group, which may be substituted and/or unsaturated.
- Preferably the organic group is a dialkyl group, which may be substituted and/or unsaturated, and/or wherein the thio group is a dithio group.
- Preferably the organic group is a di-C1-6alkyl group and/or the thio group is a dithio group or a diseleno group.
- Preferably the organic group is a diethyl group.
- Preferably the dispersing medium is at a temperature of 250° C. or more, preferably about from 300° C. to 350° C.
- Preferably the dispersing medium passivates the surface of the nanocrystalline material.
- Preferably the dispersing medium is TOPO, or a related coordinating medium, including combinations thereof. Another dispesing medium could be TBP.
- Preferably the nanocrystalline material comprises or is selected from any one of cadmium selenide, cadmium sulphide, zinc selenide, zinc sulphide, indium phosphide and gallium arsenide, including ternary and quaternary combinations thereof.
- Preferably the nanocrystalline material is cadmium selenide.
- Preferably the metal complex is diethyl diselenocarbamato cadmium or dithio diselenocarbamato cadmium, or related mixed alkyl complexes thereof.
- Preferably the device is an optical device.
- Preferably the device is any one of a non-linear optic device, a solar cell or an LED.
- Preferably the device is an LED.
- Preferably the device is a blue LED.
- The present invention is therefore based on the surprising finding that nanocrystalline materials can be prepared by using as a reactant a metal complex which provides at least two of the ions of the nanocrystalline material. The process of the present invention is therefore very different to the Murray process (ibid) and the Katari process (ibid) wherein in each of those processes it is necessary to use two independent sources to provide at least two of the ions of the nanocrystalline material. Thus, the use of a molecular precursor containing both elements in the present process provides an attractive route to metal selenides, especially if a large scale preparation is anticipated.
- The present invention is further advantageous over the prior art processes as it does not rely on the use of hazardous chemicals such as (CH3)2Cd.
- The present invention is further advantageous as it provides a low cost route to prepare photovoltaic materials and optoelectronic materials, preferable examples of which include non-linear optic devices, solar cells and LEDs.
- Thus the present invention shows that a single source can be used in a dispersing medium, such as TOPO, to replace the use of the hazardous metal alkyls. In a highly preferred embodiment, the present invention provides the synthesis of CdSe nanocrystallites using methyl diethyldiselenocarbamato cadmium (II) MeCddsc: [(CH3)CdSe2CN(C2H5)2]2) as a precursor. The synthetic method of this preferred embodiment is diagrammatically illustrated in FIG. 1, which makes no efforts to represent a mechanistic pathway.
- Even though the pathway shown in FIG. 1 is for the synthesis of CdSe it is to be understood that the process of the present invention is useful for preparing a series of nanocrystalline materials.
- Examples of nanocrystalline materials that can be prepared using an appropriate single molecule precursor can be represented by the general formulae A and B as shown below.
- MIIE GENERAL FORMULA A
- wherein M is Zn, Cd, Hg or a divalent transition metal; and wherein E is O, S, Se, P, or As.
- MIIII xEy GENERAL FORMULA B
- wherein M is Al, In, Ga or a trivalent transition metal; and wherein E is O, S, Se, P, or As; and wherein x and y are appropriate intergers.
- Formulae A and B also encompass related ternary systems.
- Therefore, examples of nanocrystalline materials other than cadmium selenide include cadmium sulphide, zinc selenide, zinc sulphide, indium phosphide and gallium arsenide.
- The general formula of the metal complex for use in the process of the present invention can be represented as:
- MLn FORMULA I
- wherein M represents a metal ion; L represents one or more ligands which need not be the same; n represents the valency of the metal; and wherein M is the first ion of the nanocrystalline material and at least one L provides the second ion for the nanocrystalline material.
- Typically M is a divalent metal ion or a trivalent metal ion, such as any one of cadmium, zinc, lead, mercury, indium gallium, including combinations thereof.
- Typically L is any one of an oxide ion, a selenide ion, a sulphide group, a phosphide group or an arsenide ion, or combinations thereof. More in particular L is or is part of any one of a thiol-carbamate group or a seleno-carbamate group such as a dithiol-carbamate group or a diseleno-carbamate group.
- In a preferred embodiment, at least one L is an organic group and/or a thio group. If at least one L is an organic group then preferably that organic is an alkyl group, which may be substituted and/or unsaturated, such as a C1-10 (preferably C1-6, more preferably C1-4) alkyl group, which may be substituted and/or unsaturated.
- Preferably, at least one L is a dialkyl group, which may be substituted and/or unsaturated, and/or wherein the thio group is a dithio group. Preferably, the organic group is a di-C1-6 alkyl group and/or the thio group is a dithio group or a diseleno group. In a highly preferred embodiment, at least one L is a diethyl group.
- Typical general formulae for suitable metal complexes containing at least one organic group for use as single molecule precursors in the process of the present invention are shown below as Formula II (for metals that are divalent) and as Formula III (for metals that are trivalent):
- [RII−MII−(ExCNRR1)y]z FORMULA II
- [(RII)(RIII)−MIII−(ExCNRR1)y]z FORMULA III
- wherein R, R1, RII and RIII independently represent an aryl or alkyl group as defined above, which may be substituted and/or unsaturated; MII is a divalent metal ion; MIII is a trivalent metal ion; E is any one of an oxide ion, a selenide ion, a sulphide group, a phosphide group or an arsenide ion, or combinations thereof (such as, by way of example, —O—S—); x is an integer, preferably 2; y is an integer; and z is an integer, usually 1 or 2.
- As mentioned above, a highly preferred metal complex containing at least one organic group for use as a single molecule precursor in the process of the present invention is methyl diethyldiselenocarbamato cadmium (II) (MeCddsc) wherein R is C2H5; R1 is C2H5; RII is (CH3); M is CdII; E is Se; x is 2; y is 1; and z is 2.
- However, other preferred metal complexes containing at least one organic group for use as single molecule precursors in the process of the present invention include
- M−(E2CNAlk2)n FORMULA IV
- wherein n is 2 for metals such as zinc, cadmium and lead; n is 3 for metals such as gallium or indium; E is S or Se; and A is an aryl or alkyl group, preferably ethyl; including carbamate (i.e. O-donors) thereof: and either
- RII−M−(E2CNA2)n FORMULA V
- or
- (RII)n−M−(E2CNA2) FORMULA VI
- wherein n is 1 for metals such as zinc, cadmium and lead; n is 2 for metals such as gallium or indium; E is S or Se; A is an aryl or an alkyl group, preferably ethyl; and RII is independently selected from an alkyl or aryl group as defined above, such as methyl.
- Other possible metal complexes for use as single molecule precursors in the process of the present invention include related thiolates, thiophosphinates or phosphinochalcogens and related selenium containing compounds.
- The present invention will now be described only by way of examples. In the examples, reference is made to the attached Figures wherein
- FIG. 1 is a scheme of the synthetic method of CdSe nanocrystallites using a single source;
- FIG. 2 is an optical absorption spectrum of CdSe nanocrystallites dispersed in toluene (fraction 3)—the inset shows the particle size distribution of the same sample as determined by TEM; and
- FIG. 3 is a fluorescence emission spectra of size fractionated CdSe (Xexc = 465 nm).
- 1.1 MeCddsc was synthesised by the comproportionation reaction27 between Cd(CH3)2 (Epichem) and bisdiethyldiselenocarbamato cadmium (II) in dry toluene, at room temperature, using Schlenk techniques and a nitrogen atmosphere. The TOPO (90%, Aldrich) was purified using the method described in the literature.28 The identity of MeCddsc and the purity of TOPO were checked by 1H nmr and IR spectroscopy and melting point measurements.
- 1.2 MeCddsc (0.5 mmol) was placed in 10 ml of TOP (98%, Aldrich) and the mixture formed was filtered after which was injected in 30 g of TOPO at 200° C. The temperature of the solution was then raised to 250° C. and heated for half an hour. The deep red solution that formed was allowed to cool down to 75° C. after which a large excess of dry CH3OH (BDH) was added. A flocculate precipitate formed and was isolated by centrifugation and redispersed in toluene, any insoluble material was then discarded. The toluene was pumped off under vacuum (10 −2 Torr) to give a deep red material which was washed with CH3OH. The solid was redispersed in toluene to give solutions with a Port wine red colour which remained optically clear for weeks. Size selective precipitation was performed by adding CH3OH to this solution until turbidity was observed followed by centrifugation the solid. This procedure was successively applied to the supernatant solutions obtained during the fractionation process until no optical absorption was detected.
- 1.3 The toluene solutions containing the nanocrystallites were characterised by optical absorption spectroscopy (Philips PU 8710 spectrophotometer) and fluorescence emission spectroscopy (Perkin Elmer LS50 luminescence spectrometer), at room temperature. The fluorescence spectra were normalized with the maximum set to one hundred. The X-ray powder diffraction experiments were performed using a Philips 1130 X-ray generator and a Guinier camera. Conventional transmission electron microscopy (TEM) of the nanocrystallites was performed using a JEOL-JEM 1200 EX II scanning and transmission electron microscope, operating at 100 kV, on samples deposited over carbon coated copper grids. The histogram was obtained after measuring the diameter of around300 nanoparticles shown on the TEM images. High resolution transmission electron microscopy (HRTEM) was performed using a JEOL FX 2000 instrument, operating at 200 kV, on samples deposited over carbon coated copper grids.
- 1.4 The optical absorption spectrum of a toluene solution containing nanodispersed CdSe obtained from the thermal decomposition of MeCddsc is shown in FIG. 2. The absorption edge of the spectrum is clearly blue shifted in relation to the bulk band gap of CdSe (716 nm, 1.73 eV) suggesting the presence of nanoparticles with sizes below the bulk exciton dimensions of CdSe. The maximum observed in the optical spectrum of nanodispersed CdSe has been associated with the lowest energy electronic transition occurring in the CdSe nanocrystallites.21-25
- 1.5 The emission fluorescence spectra of different size fractionated samples of CdSe are depicted in FIG. 3. The size selective precipitation is based on the fact that the largest particles are the first to precipitate, due to the stronger Van der Waals interactions, on the addition of a non-solvent to the nanodispersed material. Using this procedure it is possible to obtain initial solid fractions richer in larger particles as compared with the later fractions. The maximum of the emission band in FIG. 3 is gradually blue shifted as the size distributions become weighted of smaller dimensions particles. Such shifts on the band edge (FIG. 2) and band maximum (FIG. 3) in the absorption and emission spectra, respectively, have been reported as an evidence of quantum size effects.1-7
- 1.6 The fluorescence spectrum of
fraction 3 corresponds to the optical absorption spectrum in FIG. 2. The emission band maximum is observed at a wavelength close to the absorption edge of the optical spectrum (band edge emission); the typical red emission due to the recombination of charge carriers on deep traps located at the particles surface was not detected. These results suggest that surface coverage with TOPO molecules should have occurred on the CdSe nanocrystallites.2,24-26 The energy dispersive analysis X-ray results (EDAX) for CdSe nanocrystallites (after several washings with methanol) still show the presence of phosphorous, suggesting that the TOPO molecules are quite firmly bond to the CdSe nanocrystallites. - 1.7 The dark red powder obtained from the synthesis gave an X-ray diffraction pattern consistent with hexagonal CdSe. The TEM image of the
fraction 3 of CdSe giving the spectra in FIG. 2 and FIG. 3 was studied. The mean particle diameter of the nanocrytalline material was found to be 51.9±7.4 Angstroms. The TEM results show that the CdSe nanocrystallites are approximately spherical and close to monodispersed. On the basis of the effective mass approximation4 the excitonic peak located at 568 nm (2.18 eV) suggests the presence of CdSe nanoparticles with a diameter close to 57 Angstroms, discrepancies between the experimentally measured particle diameter and the predictions of the effective mass approximation have been reported by other authors.24 - 1.8 The crystallinity of the CdSe nanoparticles was confirmed by HRTEM. The HRTEM images showed the typical hexagonal pattern of the wurtzite structure for some of the particles in agreement with the X-ray powder diffraction results. The analysis of several images are consistent with the presence of some CdSe nanocrystallites with stacking faults. This type of defect for CdSe nanocrystallites has been reported by other authors24. Alivisatos et al.25 reported the synthesis of CdSe nanocrystallites, using a TOPO method at higher temperatures for which no stacking faults were detected.
- 2.1 Initially Me2InS2CNEt2 was prepared by a comproportionation reaction between stoichiometric amounts of tris(diethyldithiocarbarmato)indium(III) (5.7 g, 10.2 mmol) and trimethylindium (3.3 g) in toluene (40 mL). The mixture was stirred at room temperature for half an hour and then heated to 50° C. and stirred for further 10 min. On concentration, white crystals settled out from the clear solution (7.90 g, 88%), mp 84° C.
- 2.2 The compound prepared by the process of 2.1 was then used to replace MeCddsc in Section 1.2 (supra). The product, nanocrystalline indium sulphide, was then analysed using the methods outlined in Sections 1.4-1.8 (supra).
- 3.1 Initially Me2GaS2CNEt2 was prepared by a comproportionation reaction between stoichiometric amounts of tris(diethyldithiocarbarmato)gallium(III) and trimethylgallium in toluene (40 mL). The mixture was stirred at room temperature for half an hour and then heated to 50° C. and stirred for further 10 min. On concentration, crystals settled out from the solution.
- 3.2 The compound prepared by the process of 3.1 was then used to replace MeCddsc in Section 1.2 (supra). The product, nanocrystalline gallium sulphide, was then analysed using the methods outlined in Sections 1.4-1.8 (supra).
- 4.1 The precursor molecules described in Sections2.1 and 3.1 could be respectively replaced with Et2InS2CNEt2, Np2InS2CNEt2, Et2GaS2CNEt2, and Np2GaS2CNEt2. In this regard these compounds were prepared by the following general protocol, which refers to the preparation of Et2InS2CNEt, though of course the other compounds are prepared by use of similar and appropriate reactants.
- 4.2 Et2InS2CNEt2 was prepared by adding sodium diethyldithiocarbarmate (2.73 g, 15.97 mmol) to a solution of chlorodiethylindium (3.33 g, 15.97 mmol) in ether (60 mL) and stirred for 12 h at room temperature. A white solid (NaCl) formed during the reaction which was removed by filtration. The colourless filtrate containing the product was evaporated to dryness under vacuum. The solid product contained traces of salt and was dissolved in petroleum spirits (60-80° C.) and filtered. The filtrate, on concentration, gave white crystals of diethyldiethyldithiocarbamatoindium (III) (3.33 g, 65%), mp 57° C.
- 4.3 As mentioned above, Np2InS2CNEt2 was prepared in a similar manner and was obtained as a white crystalline solid (2.97 g, 70%), mp 44° C.
- 4.4 As mentioned above, Et2GaS2CNEt2 (4.51 g, 75%) and Np2GaS2CNEt2 (3.25 g. 72%), both liquids, were prepared in a similar manner.
- 4.5 The compounds of 4.1 to 4.4 were then used to replace MeCddsc in Section 1.2 (supra). The respective nanocrystalline products were then analysed using the methods outlined in Sections 1.4-1.8 (supra).
- 5.1 Initially [Zn[S2CNMe1Pr]2]2 was prepared as follows. A mixture of “zinc hydroxide” (4.77 g, 48 mmol), N-methylisopropylamine (10 ml, 96 mmol) and carbon disulphide (5.76 ml, 96 mmol) were suspended in ethanol and stirred at ca. 60° C. for 2 hours. On cooling, the reaction mixture was filtered affording a white solid which was then dried at room temperature in vacuo and recrystallised from acetone. Yield 11.7 g, 67.6%.
- 5.2 The compound prepared by the process of 5.1 was then used to replace MeCddsc in Section 1.2 (supra). The product, nanocrystalline zinc sulphide, was then analysed using the methods outlined in Sections 1.4-1.8 (supra).
- 6.1 Initially [Cd[S2CNMe1Pr]2]2 was prepared as follows. A mixture of cadmium hydroxide, N-methylisopropylamine and carbon disulphide were suspended in ethanol and stirred at ca. 60° C. for 2 hours. On cooling, the reaction mixture was filtered affording a solid which was then dried at room temperature in vacuo and recrystallised from acetone.
- 6.2 The compound prepared by the process of 6.1 was then used to replace MeCddsc in Section 1.2 (supra). The product, nanocrystalline cadmium sulphide, was then analysed using the methods outlined in Sections 1.4-1.8 (supra).
- 7.1 Initially [Zn[As2CNMe1Pr]2]2 was prepared by appropriately adapting the process of Section 5.1 (supra).
- 7.2 The compound prepared by the process of 7.1 was then used to replace MeCddsc in Section 1.2 (supra). The product, nanocrystalline zinc arsenide was then analysed using the methods outlined in Sections 1.4-1.8 (supra).
- 8.1 Initially [Cd[As2CNMe1Pr]2]2 was prepared by appropriately adapting the process of Section 6.1 (supra).
- 8.2 The compound prepared by the process of 8.1 was then used to replace MeCddsc in Section 1.2 (supra). The product, nanocrystalline cadmium arsenide was then analysed using the methods outlined in Sections 1.4-1.8 (supra).
- 9.1 The following compounds were used to replace MeCddsc in Section 1.2 (supra). The respective nanocrystalline materials were then analysed using the methods outlined in Sections 1.4-1.8 (supra).
- 9.2 The following commentary describes the preparation of (C5H11)2GaPtBu2, however the process can be appropriately adapted for the preparation of (C5H11)2IndiumPtBu2, (C5H11)2GalliunAsBu2, and (C5H11)2IndiumAsBu2.
- 9.3 To prepare (C5H11)2GaPtBu2, LiPtBu2 was initially prepared by the addition of HPtBu2(5 g, 33.4 mmol) to a stirred solution of nBuLi (14.24 cm3 of 2.5 M solution in hexanes, 35.6 mmol) diluted further with petroleum spirits (60-80° C., 50 cm3, 0° C.). The solution was left to stir overnight, concentrated, and then left to crystallise. (C5H11)2GaCl(2) (2.56 g, 10.34 mmol) was dissolved in ether (60 cm3) and stirred at 0° C. LiPtBu2 (1.57 g, 10.33 mmol) was slowly added and the mixture was allowed to reach ambient temperature. After stirring overnight, the solvent was removed under vacuum leaving a white solid. Petroleum spirits (60-80° C.) (30 cm3) were added to the solid. After decanting the supernatant, the solution was concentrated and left to crystallise at −-25° C. Colourless, triangular shaped crystals formed, yield 3.12 g, (84 %), m.p. 81° C.
- The results reported here clearly show that nanocrystalline materials such as nanocrystalline MeSe can be easily prepared from molecular compounds such as MeCddsc. Moreover, these prepared nanocrystalline materials can be used as or in high quality semiconductors.
- Other modifications of the present invention will be apparent to those skilled in the art.
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- 1996-08-09 EP EP03075248A patent/EP1334951A1/en not_active Withdrawn
- 1996-08-09 DE DE69628565T patent/DE69628565T2/en not_active Expired - Lifetime
- 1996-08-09 EP EP96927134A patent/EP0850194B1/en not_active Expired - Lifetime
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Also Published As
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DE69628565T2 (en) | 2004-04-29 |
GB9518910D0 (en) | 1995-11-15 |
EP1334951A1 (en) | 2003-08-13 |
EP0850194B1 (en) | 2003-06-04 |
DE69628565D1 (en) | 2003-07-10 |
EP0850194A1 (en) | 1998-07-01 |
WO1997010175A1 (en) | 1997-03-20 |
US6379635B2 (en) | 2002-04-30 |
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