WO2016046394A1 - Use of at least one binary group 15 element compound, a 13/15 semiconductor layer and binary group 15 element compounds. - Google Patents
Use of at least one binary group 15 element compound, a 13/15 semiconductor layer and binary group 15 element compounds. Download PDFInfo
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- WO2016046394A1 WO2016046394A1 PCT/EP2015/072163 EP2015072163W WO2016046394A1 WO 2016046394 A1 WO2016046394 A1 WO 2016046394A1 EP 2015072163 W EP2015072163 W EP 2015072163W WO 2016046394 A1 WO2016046394 A1 WO 2016046394A1
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- 229910052696 pnictogen Inorganic materials 0.000 title claims abstract description 203
- 150000001875 compounds Chemical class 0.000 title claims abstract description 176
- 239000004065 semiconductor Substances 0.000 title claims abstract description 161
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 75
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 58
- 125000003118 aryl group Chemical group 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 32
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 30
- 238000005019 vapor deposition process Methods 0.000 claims abstract description 27
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 3
- GKKWUSPPIQURFM-IGDGGSTLSA-N Prostaglandin E2 ethanolamide Chemical compound CCCCC[C@H](O)\C=C\[C@H]1[C@H](O)CC(=O)[C@@H]1C\C=C/CCCC(=O)NCCO GKKWUSPPIQURFM-IGDGGSTLSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 116
- 238000000034 method Methods 0.000 abstract description 47
- 238000004519 manufacturing process Methods 0.000 abstract description 37
- 230000008021 deposition Effects 0.000 abstract description 24
- 238000011109 contamination Methods 0.000 abstract description 14
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 abstract description 12
- 229910017464 nitrogen compound Inorganic materials 0.000 abstract description 8
- 150000002830 nitrogen compounds Chemical class 0.000 abstract description 8
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 62
- 239000002243 precursor Substances 0.000 description 58
- -1 nitrogenous gallium arsenide nitride Chemical class 0.000 description 48
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 35
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 28
- 238000000151 deposition Methods 0.000 description 24
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 24
- 229910052799 carbon Inorganic materials 0.000 description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 23
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 22
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 22
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 18
- 150000005840 aryl radicals Chemical class 0.000 description 18
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 18
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 18
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 15
- 229910052795 boron group element Inorganic materials 0.000 description 15
- 230000005693 optoelectronics Effects 0.000 description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000007792 addition Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 238000005229 chemical vapour deposition Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000007740 vapor deposition Methods 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 238000004679 31P NMR spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002017 high-resolution X-ray diffraction Methods 0.000 description 5
- 238000000103 photoluminescence spectrum Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 4
- 238000000927 vapour-phase epitaxy Methods 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 150000001260 acyclic compounds Chemical class 0.000 description 3
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 3
- XKLVLDXNZDIDKQ-UHFFFAOYSA-N butylhydrazine Chemical group CCCCNN XKLVLDXNZDIDKQ-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 150000001923 cyclic compounds Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 150000002429 hydrazines Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000000628 photoluminescence spectroscopy Methods 0.000 description 3
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- RSCASNFKRQQQDK-UHFFFAOYSA-N tritert-butylgallane Chemical compound CC(C)(C)[Ga](C(C)(C)C)C(C)(C)C RSCASNFKRQQQDK-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 101100110026 Danio rerio ascl1b gene Proteins 0.000 description 2
- LDCXYDSTOMCHPB-UHFFFAOYSA-N N-arsanyl-N-tert-butyl-2-methylpropan-2-amine Chemical compound C(C)(C)(C)N(C(C)(C)C)[AsH2] LDCXYDSTOMCHPB-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- QTQRGDBFHFYIBH-UHFFFAOYSA-N tert-butylarsenic Chemical compound CC(C)(C)[As] QTQRGDBFHFYIBH-UHFFFAOYSA-N 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000004834 15N NMR spectroscopy Methods 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- 229910013698 LiNH2 Inorganic materials 0.000 description 1
- 101100001347 Mus musculus Akt1s1 gene Proteins 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000066 arsane Inorganic materials 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/504—Organo-phosphines containing a P-P bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/66—Arsenic compounds
- C07F9/70—Organo-arsenic compounds
- C07F9/72—Aliphatic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/90—Antimony compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/94—Bismuth compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/0254—Nitrides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/02543—Phosphides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/02546—Arsenides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/02549—Antimonides
Definitions
- the invention concerns the use of at least one binary group 15 element compound, a 13/15 semiconductor layer and binary group 15 element compounds.
- 13/15 semiconductors such as the binary compounds gallium arsenide (GaAs) or indium phosphide (InP) and the methods to produce them are known in the state of the art.
- the representation of 13/15 semiconductors is usually achieved by deposition from the gas phase.
- Important production methods are, for instance, metal-organic chemical vapor deposition (MOCVD) and metal-organic vapor phase epitaxy (MOVPE). These methods allow the application of ultrapure layers of 13/15 semiconductor materials on a plurality of substrates. Such methods are, among other applications, used in the context of the production of light-emitting diodes, lasers, transistors and solar cells.
- MOCVD metal-organic chemical vapor deposition
- MOVPE metal-organic vapor phase epitaxy
- a gaseous mixture of the group 13 element precursor trimethylgallium (MesGa) and the group 15 element precursor arsine (ASH3) is disintegrated on a hot surface, depositing GaAs.
- the disintegration of the precursors is directly affected by the process temperature and the process pressure. Since precursors usually have relatively high disintegration temperatures, the process temperatures applied usually have to be high respectively.
- Other important process parameters are the concentration of the precursors, the concentration of the carrier gas and the reaction gas as well as the total gas flow.
- ternary 13/15 semiconductors such as nitrogenous gallium arsenide nitride (GaAsi-xN x )) (0 ⁇ x ⁇ 1) as well quaternary and other multinary 13/15 semiconductors are important as these allow further variation and sensitive adjustments of opto-electronic characteristics than binary 13/15 semiconductors due to the presence of three or four different elements, namely of one or two group 13 elements and two or three group 15 elements.
- nitrogenous multinary 13/15 semiconductors e.g. ternary Ga(Asi- x N x ) (0 ⁇ X ⁇ 1)
- three separate precursor compounds namely one group 13 element source and two group 15 element sources.
- the three precursors are mixed during the gaseous phase and disintegrated together.
- This kind of representation of multinary 13/15 semiconductors does not only involve a high synthesis effort - especially due to the production of several precursor compounds- but also requires the consideration of different disintegration temperatures, vapor pressures and the respective different diffusion rates of the various precursors, e.g. three separate precursors for the production of the ternary compound Ga(Asi-xNx) (0 ⁇ X ⁇ 1).
- the method is furthermore not very atom-efficient.
- organically substituted nitrogen compounds such as 1.1 dimethyl hydrazine.
- the disadvantage is that in addition to the desired inclusion of nitrogen there is also an undesired inclusion of carbon into the 13/15 semiconductors and/or the 13/15 semiconductor layers. Due to the carbon contamination, the opto-electronic characteristics of the 13/15 semiconductors and/or the 13/15 semiconductor layers are modified and/or impaired in an uncontrollable and irreversible way.
- the partial pressures usually required with regard to the nitrogen source are high. For example, if 1.1 dimethyl hydrazine is used as the nitrogen source, the two selected group 15 element sources, i.e.
- the known process sequences to produce ternary 13/15 semiconductors must be regarded as rather inefficient in terms of use of energy and atom efficiency, and thus as on the whole rather uneconomical.
- the invention therefore has the purpose to overcome these and other disadvantages in the state of the art and provide group 15 element compounds that are suitable for use as the educt in a process of vapor deposition, especially for the production of multinary 13/15 semiconductor compounds and/or layers.
- the group 15 element compounds to be used should be characterized by the production of multinary, homogeneous and ultrapure 13/15 semiconductors and/or layers in a combination as defined that is as atom-efficient, cost-efficient and reproducible as possible.
- a 13/15 semiconductor layer should be provided that may be produced using group 15 element compounds as intended according to the invention.
- binary group 15 element compounds are to be provided.
- Embodiments are the subject of claims 2 to 15.
- the purpose is achieved by the use of at least one binary group 15 element compound as the educt of a vapor deposition process, wherein the at least one binary group 15 element compound has the general formula of
- R 1 , R 2 , R 3 and R 4 are selected independently from one another from the group consisting of H, an alkyl radical (C1 - C10) and an aryl group, and
- - E and E' are selected independently from one another from the group consisting of N, P, As, Sb and Bi,
- E E' or E ⁇ E', and/or wherein at least one binary group 15 element compound has the general formula
- R 5 - R 6 and R 7 are selected independently from one another from the group
- - E and E' are selected independently from one another from the group consisting of N, P, As, Sb and Bi,
- the alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C6 alkyl radical and C1 to C8 aryl radical.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C4 alkyl radical and C1 to C6 aryl radical.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/ ' Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (tBu or 2- methylpropyl), cyclobutyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
- the alkyl or aryl groups can be substituted, particularly fluorinated or perfluorinated.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may, in particular, be trifluormethyl (CF 3 ) or
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), methyl (Me), isopropyl (/Pr), tert.-butyl (tBu or 2- methylpropyl).
- E and E' are different and one of E or E' is N.
- R 1 and R 2 are hydrogen (H), if R 3 and R 4 are different from hydrogen, or R 3 and R 4 are hydrogen, if R 1 and R 2 are different from hydrogen.
- E and E' are selected fromthe group consisting of N, P, As and Sb.
- the invention does not concern the use of hydrazine (H2N-NH2) and its derivatives, especially 1.1 dimethyl hydrazine and tertiary butyl hydrazine as the educt in a vapor deposition process.
- H2N-NH2 hydrazine
- These compounds are regarded as hydrazine derivatives that can be produced, starting with hydrazine by substituting one or several hydrogen atoms. This includes both acyclic and cyclic compounds, e.g. saturated tripartite compounds. Consequently, in a compound of formula (I), if E or E' is nitrogen (N), then E and E' are different from each other.
- the use according to the invention of one or several binary group 15 element compounds of the general formulas (I) and/or (II) as the educt in a vapor deposition process allows a reproducible, cost-efficient representation of multinary, homogeneous and ultrapure 13/15 semiconductor connections and/or layers of a defined combination.
- the vapor deposition process is preferably a chemical vapor deposition, and especially a metal-organic chemical vapor deposition or a metal-organic metal-organic vapor phase epitaxy (MOVPE).
- MOVPE metal-organic metal-organic vapor phase epitaxy
- the product of the vapor deposition process is preferably a 13/15 semiconductor layer.
- the group 15 element compounds used according to the invention represent single source precursors (SSP) with regard to the elements of group 15.
- the single source precursors designated according to the invention are molecules having more than one group 15 element, especially two different group 15 elements.
- the group 15 elements included in the precursor may be selected and/or combined according to the desired opto-electronic characteristics of the 13/15 semiconductor to be produced and/or to be deposited on a substrate.
- the group 15 element sources such as PH3, ASH3, tBuPH2, tBuAsh ⁇ and ⁇ 2 ⁇ - ⁇ ⁇ 2 to date used for chemical vapor deposition processes each have only one group 15 element, which means that depending on the desired combination of the multinary, i.e. more than binary 13/15 semiconductor to be produced and/or deposited, several group 15 element sources have to be provided and mixed with one another.
- the group 15 element sources of formula (I) and/or formula (II) used according to the invention advantageously include two group 15 elements each, which in most cases differ from one another.
- the advantage is the option of producing multinary 13/15 semiconductor connections and/or layers starting from the single source precursors according to the invention, without the necessity of creating a separate precursor connection for each group 15 element contained n the 13/15 semiconductor to be produced. Consequently, it is not necessary to consider various disintegration temperatures, vapor pressures and the respective varying diffusion ratios of several group 15 element sources and/or precursors in the context of planning and conducting the vapor deposition process. This makes the process particularly easy to execute in the production and/or deposition of 13/15 semiconductors.
- the use of the binary group 15 element compounds according to the invention reduces the number of resulting by-products which consequently have to be desorbed by the 13/15 semiconductor produced and/or the respective layer, which leads to an increase in the atom efficiency and the simplification of the process.
- the compounds used according to the invention have lower disintegration temperatures than the group 15 element sources such as PH3, Ash , fBuPhb, fBuAshb previously used in chemical vapor deposition processes.
- the lower disintegration temperatures can be attributed to the respective lower E-E' bonding.
- the selection may be effected from a plurality of single source precursors according to the invention, wherein the relationship of the group 15 elements that should be included in the 13/15 semiconductor to be produced can already be preset by the by the composition of the single source precursor.
- This allows the production of 13/15 semiconductor compounds and/or layers with defined, presettable opto-electronic characteristics.
- the representation of ternary 13/15 semiconductor compounds and/or layers using the group 15 element compounds according to the invention e.g. Ga(E x E'i- x ) (E ⁇ E; 0 ⁇ x ⁇ 1), is possible in a simple, atom-efficient and cost-efficient manner.
- the same is true for the production of quaternary 13/15 semiconductor compounds and/or layers, e.g.
- a particularly preferred embodiment of the binary group 15 element compounds of the general formula (I) and/or (II) according to the invention provides the selection of nitrogenous single source precursors such as fBu2As-NH2 or HN(SbfBu2)2 that have no nitrogen-bound carbon.
- These binary group 15 element sources have all the advantageous characteristics of single source precursors, such as, for example, high vapor pressure, low toxicity, simple producibility, easy handling and the existence of a good leaving group without, however, containing a nitrogen-bound carbon atom. It is possible to renounce the addition of an organically substituted nitrogen compound such as 1.1 dimethyl hydrazine as the nitrogen source. Consequently, such compounds are particularly suitable for the representation of ultrapure nitrogenous 13/15 semiconductors and/or layers.
- 13/15 semiconductors and/or 13/15 semiconductor layers are obtained with the use of the compounds according to the invention that - compared to the 13/15 semiconductors and/or 13/15 semiconductor levels produced according to the previous production methods - have a drastically reduced level of carbon content since the use of carbonic nitrogen sources is waived. Carbon contaminations possibly contained in the 13/15 semiconductors and/or 13/15
- semiconductor layers that are produced usually originate from the group 13 element source or sources that are usually organically substituted.
- the single source precursors provided according to the invention may also be used with one or several other group 15 element sources according to the invention or already known. This may be particularly advantageous in the case of nitrogenous binary group 15 element compounds of the formula (I) or (II).
- the controllable addition of one or several other group 15 element sources may influence and fine tune the nitrogen content of the 13/15 semiconductor to be produced and/or deposited deriving from the nitrogenous binary group 15 element compound. It is in particular possible to produce and/or deposit 13/15 semiconductors that have a different relation between the group 15 elements than the one that would be obtained in the case of the exclusive use of binary group 15 element compounds.
- the nitrogen content in the production of Ga(Asi- x N x ) (0 ⁇ x ⁇ 1) usually assumes a lower level than the arsenic content.
- Adding another group 15 element source such as, for example, the arsenic source fBuAshb allows for a further reduction of the nitrogen content of Ga(Asi- x N x ) (0 ⁇ X ⁇ 1) compared to the arsenic content. This may be attributed to the fact that the nitrogen atoms have to compete with the arsenic atoms from the additional arsenic source. Accordingly it is possible to vary and/or fine tune the opto-electronic characteristics of the 13/15 semiconductors to be produced and/or deposited to an even larger extent.
- the group 15 element precursors according to the invention allow the simple, secure, comparably atom-efficient and relatively energy-efficient production of a 13/15 semiconductor and/or a respective layer.
- the educt is a binary group 15 element compound of the general formula (I) and
- R 1 and R 2 are selected independently from one another from the group consisting of an alkyl radical (C1 - C10) and an aryl group, and
- R 1 and R 2 are the same or different and are selected from the group consisting of C1 to C6 alkyl radical and C1 to C8 aryl radical.
- R 1 and R 2 are the same or different and are selected from the group consisting of C1 to C4 alkyl radical and C1 to C6 aryl radical.
- R 1 and R 2 are the same or different and are selected from the group consisting of methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/ ' Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (tBu or 2-methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
- alkyl or aryl groups can be substituted. In particular, they may be fluorinated or
- R 1 and R 2 are, in particular, trifluormethyl (CF3) or pentafluorphenyl (C6F5).
- R 1 and R 2 are the same.
- R 1 and R 2 are tBu, / ' Pr, trifluormethyl or phenyl.
- E and E' are different from each other.
- E is selected from the group consisting of P, As and Sb.
- E' is selected from the group consisting of N, P and As, more specifically, E' is N .
- E is selected from the group consisting of P, As, Sb and Bi, in particular P, As and Sb, and E' is N .
- tBu can be advantageously employed as both R 1 and R 2 .
- the alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated.
- the binary group 15 element compound of the general formula (I) is preferably selected from the group consisting of fBu 2 P-NH 2 , (CF 3 )2P-NH 2 , (C 6 H 5 ) 2 P-NH 2 , fBu 2 P-AsH 2 , fBu 2 As-N H 2 , fBu 2 As- PH 2 , (C6H5) 2 As-PH 2 , fBu 2 Sb-NH 2 and fBu 2 Sb-PH 2 . All these single source precursors are suitable for the production and/or deposition of a plurality of multinary 13/15 semiconductors.
- the nitrogenous group 15 element compounds fBu 2 P-NH 2 , (CF3) 2 P-NH 2 , (C6Hs) 2 P-NH 2 , fBu 2 As-N H 2 and fBu 2 Sb-N H 2 are particularly suitable for the reproducible representation and/or deposition of ultrapure nitrogenous 13/15 semiconductor layers with drastically reduced carbon content - compared to a 13/15 semiconductor and/or 13/15 semiconductor layer produced according to known production methods - as they do not have any nitrogen- bound carbon atom. Should carbon contaminations possibly be contained in the 13/15 semiconductors and/or 13/15 semiconductor layers that are produced, they usually derive from the group 13 element source or sources that are usually organically substituted.
- a potential gallium source being e.g. trimethylgallium (MesGa), tri-tertbutylgallium (fBu3Ga) or tri-ethylgallium (EtsGa)
- the relationship of the group 15 elements that should be contained in the 13/15 semiconductor and/or the 13/15 semiconductor layer to be produced - in this case nitrogen and arsenic - is mainly preset by the composition of the single source precursor fBu2As-NH2.
- the group 15 element / group 15 element relation e.g. the relation As/N in the 13/15 semiconductor and/or the 13/15 semiconductor layer may, however, be influenced by a variation of the process parameters, e.g. the partial pressure of the binary group 15 element sources in the reactor or the process temperature.
- group 15 element compound fBu2As-NH2 In addition to the group 15 element compound fBu2As-NH2, one or several other group 15 element compounds according to the invention or already known may be used, e.g. the known non-binary group 15 element compound fBuAshb as an additional source of arsenic or the known non-binary group 15 element compound fBuPhb as a source of phosphorus.
- group 15 element compound fBu2As-NH2 as binary group 15 element compounds with the addition of one or several group 15 element compounds allows the production of
- Ga(Asi-xNx) layers (0 ⁇ x ⁇ 1) which have a lower nitrogen content compared to the exclusive use of fBu2As-NH2 as the source of nitrogen and arsenic.
- This can be attributed to the fact that the nitrogen atoms have to compete with the group 15 element atoms from the additional group 15 element source, e.g. from a source of arsenic or phosphorus.
- the combination and thus the opto-electronic characteristics of the 13/15 semiconductor and/or the 13/15 semiconductor layer may be varied and/or fine-tuned to a large degree.
- the educt is a binary group 15 element compound of the general formula (I) and
- R 1 , R 2 and R 4 are selected independently from one another from the group consisting of an alkyl radical (C1 - C10) and an aryl group, and
- R 1 , R 2 and R are the same or different and are selected from the group consisting of C1 to C6 alkyl radical and C1 to C8 aryl radical.
- R 1 , R 2 and R are the same or different and are selected from the group consisting of C1 to C4 alkyl radical and C1 to C6 aryl radical.
- R 1 , R 2 and R are the same or different and are selected from the group consisting of methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/ ' Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (tBu or 2-methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
- the alkyl or aryl groups can be substituted, particularly fluorinated or perfluorinated.
- R 1 , R 2 and R are, in particular, trifluormethyl (CF3) or pentafluorphenyl (C6F5).
- R 1 , R 2 and R are the same.
- R 1 , R 2 and R are, independently of each other, Me, tBu, / ' Pr, trifluormethyl or phenyl.
- E and E' are different.
- E is selected from the group consisting of As and Sb.
- E' is selected from the group consisting of N, P, Sb and Bi.
- the alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated.
- the binary group 15 element compound of the general formula (I) is preferably selected from the group consisting of fBu 2 As-PHMe, fBu 2 Sb-NHfBu, fBu 2 Sb-PHfBu and fBu 2 Sb-NH/Pr. These single source precursors may be used for the reproducible representation and/or deposition of various homogeneous, definable 13/15 semiconductors.
- the educt is a binary group 15 element compound with the general formula (I), and R 1 , R 2 , R 3 and R 4 have been independently selected from the group consisting of an alkyl radical (C1 - C10) and an aryl group.
- the alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or
- the binary group 15 element compound of the general formula (I) is preferably selected from the group consisting of Me 2 As-AsMe 2 , fBu 2 Sb-NMe 2 , /Pr 2 Sb-PMe 2 , Et 2 Sb-NMe 2 , Et 2 Sb-P(C 6 H 5 ) 2 , fBu 2 Bi-PfBu 2 and fBu 2 Bi-AsfBu 2 .
- the binary group 15 element compound of the general formula (II) is preferably selected from the group consisting of HP(AsfBu2)2 and HN(SbfBu2)2. Both single source precursors are suitable for the reproducible representation and/or deposition of homogeneous, defined and ultrapure 13/15 semiconductors.
- the binary group 15 element compound HN(SbfBu2)2 is particularly suitable for the reproducible manufacture of nitrogenous 13/15 semiconductors and/or 13/15 semiconductor layers of the defined composition. It is particularly advantageous that 13/15 semiconductors and/or 13/15 semiconductor layers are obtained with the use of the binary group 15 element compounds according to the invention that - compared to the 13/15 semiconductors and/or 13/15 semiconductor levels produced according to the previous production methods - have a drastically reduced level of carbon content since the use of carbonic nitrogen sources is waived. Should carbon contaminations possibly be contained in the 13/15 semiconductors and/or 13/15 semiconductor layers that are produced, they usually derive from the group 13 element source or sources that are usually organically substituted.
- the educt is a binary group 15 element compound of the general formula (II) and
- R 5 is selected from the group consisting of an alkyl radical (C1 - C10) and an aryl group, and
- R 5 is selected from the group consisting of C1 to C6 alkyl radical and C1 to C8 aryl radical.
- R 5 is selected from the group consisting of C1 to C4 alkyl radical and C1 to C6 aryl radical.
- R 5 is selected from the group consisting of methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/ ' Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (tBu or 2-methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
- alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated.
- R 5 may be selected from the group consisting of trifluormethyl (CF3) or
- R 5 may be selected from Me, tBu, trifluormethyl or phenyl.
- E is selected from the group consisting of P and As. In yet another specific embodiment, E' is N.
- the binary group 15 element compound of the general formula (II) is preferably selected from the group consisting of fBuP(NH 2 )2, fBuAs(NH 2 )2 and (C6H 5 )P(NH 2 )2.
- group 15 element sources are suitable for the reproducible representation and/or deposition of nitrogenous, homogeneous, ultrapure 13/15 semiconductors of the defined combination. It is particularly advantageous that 13/15 semiconductors and/or 13/15 semiconductor layers obtained with the use of the binary group 15 element compounds according to the invention that - compared to the 13/15 semiconductors and/or 13/15 semiconductor levels produced according to the previous production methods - have a drastically reduced level of carbon content since the use of carbonic nitrogen sources is waived. Carbon contaminations possibly contained in the 13/15 semiconductors and/or 13/15 semiconductor layers that are produced usually originate from the group 13 element source or sources that are usually organically substituted.
- the educt is a binary group 15 element compound of the general formula (I I) and
- R 5 and R 7 are selected independently from one another from the group consisting of an alkyl radical (C1 - C10) and an aryl group, and
- R 5 and R 7 are the same or different and are selected from the group consisting of C1 to C6 alkyl radical and C1 to C8 aryl radical.
- R 5 and R 7 are the same or different and are selected from the groups consisting of C1 to C4 alkyl radical and C1 to C6 aryl radical.
- R 5 and R 7 are the same or different and are selected from the group consisting of methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (n u), isobutyl (/ ' Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (tBu or 2-methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
- R 5 and R 7 are, in particular, trifluormethyl (CF3) or pentafluorophenyl (C6F5).
- R 5 and R 7 are different.
- R 5 and R 7 may be selected from Me, Et, nBu, tBu, trifluormethyl or phenyl.
- E is selected from the group consisting of P, As and Sb and more specifically, may be P.
- E' is selected from the group consisting of N, P and As and more specifically is As.
- the alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated.
- the binary group 15 element compound of the general formula (I I) is preferably selected from the group consisting of nBuP(AsHMe)2 and (C6Hs)P(AsHMe)2. Both single source precursors are suitable for the reproducible production of homogeneous, defined and ultrapure 13/15 semiconductors and/or layers.
- the educt is a binary group 15 element compound of the general formula (I I) and
- R 6 and R 7 are selected from the group consisting of an alkyl radical (C1 - C10) and an aryl group, Specifically, R 6 and R 7 are selected from the group consisting of C1 to C6 alkyl radical and C1 to C8 aryl radical. In particular, R 6 and R 7 are selected from the group consisting of C1 to C4 alkyl radical and C1 to C6 aryl radical.
- R 6 and R 7 are selected from the group consisting of methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/ ' Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (tBu or 2-methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
- the alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated.
- R 6 and R 7 may be selected from the group consisting of trifluormethyl (CF3) or pentafluorphenyl (C6F5). In a specific embodiment, R 6 and R 7 are the same. In specific embodiments, R 6 and R 7 are may be selected from Me, tBu or phenyl.
- E is selected from the group consisting of P and As. In yet another specific embodiment, E' is N.
- the binary group 15 element compound of the general formula (II) is preferably selected from the group consisting of HP(AsfBu 2 ) 2 , HN(SbfBu 2 ) 2 , HP(N(fBu) 2 ) 2 , HAs(N(fBu) 2 ) 2 and
- the educt is a binary group 15 element compound with the general formula (II), and R 5 , R 6 and R 7 are independently selected from the group consisting of an alkyl radical (C1 - C10) and an aryl group.
- the alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated.
- the binary group 15 element compound of the general formula (II) is preferably selected from the group consisting of fBuAs(NMe 2 ) 2 , m-F 3 CC6H As(NMe 2 ) 2 and tBuAs(PMe 2 ) 2 . All of these compounds are suitable for the reproducible generation and/or deposition of a plurality of homogeneous multinary 13/15 semiconductors of defined combination.
- the use of the group 15 element compounds as educt in a vapor deposition process as described above does also encompass a method for vapor deposition, wherein a compound of formula (I) or formula (II) is employed as an educt.
- a 13/15 semiconductor layer can be produced by this method for vapor deposition, using at least one binary group 15 element compound as the educt in a vapor deposition process according to one of the embodiments specified above.
- the method for vapor deposition wherein a compound of formula (I) or formula (II) is employed as an educt, which is encompassed by the use of the group 15 element compounds of formula (I) or formula (II) as educt in a vapor deposition process as described above may comprise the steps of
- the method for vapor deposition wherein a compound of formula (I) or formula (II) is employed as an educt, which is encompassed by the use of the group 15 element compounds of formula (I) or formula (II) as educt in a vapor deposition process as described above may comprise the steps of
- group 15 element compounds of formula (I) or formula (II) can be all compounds described generically or specifically in various embodiments above and are, generally speaking, compounds according to the general formula
- R 1 , R 2 , R 3 and R 4 are selected independently from one another from the group
- - E and E' are selected independently from one another from the group consisting of P, As, Sb and Bi,
- R 5 , R 6 , and R 7 are selected independently from one another from the group consisting of H, an alkyl radical (C1 - C10) and an aryl group,
- - E is selected from the group consisting of N, P, As, Sb and Bi, and
- - E' is selected from the group consisting of P, As, Sb and Bi,
- Hydrazine H2N-NH2
- its derivatives are not the subject matter of the invention.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C6 alkyl radical and C1 to C8 aryl radical.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C4 alkyl radical and C1 to C6 aryl radical.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/ ' Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (t u or 2- methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
- alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be, in particular, trifluormethyl (CF 3 ) or
- R 1 and R 2 are hydrogen (H), if R 3 and R 4 are different from hydrogen, or R 3 and R 4 are hydrogen, if R 1 and R 2 are different from hydrogen.
- the invention does not concern the use of hydrazine (H2N-NH2) and its derivatives, especially 1.1 dimethyl hydrazine and tertiary butyl hydrazine as the educt in a vapor deposition process.
- hydrazine H2N-NH2
- hydrazine derivatives that can be produced, starting with hydrazine by substituting one or several hydrogen atoms.
- This includes both acyclic and cyclic compounds, e.g. saturated tripartite compounds. Consequently, in a compound of formula (I), if E or E' is nitrogen (N), then E and E' are different from each other.
- the group 15 element compounds used according to the invention represent single source precursors (SSP) with regard to the elements of group 15.
- the single source precursors provided according to the invention each have more than one group 15 element, wherein these are two different group 15 elements.
- the group 15 elements included in the precursor may be selected or combined according to the characteristics, especially the opto-electronic characteristics that the 13/15 semiconductor that is to be produced and/or deposited on a substrate should have.
- the group 15 element compound of formula (I) or formula (II) may be employed as single compound, as a mixture with each other or with other group 15 compounds which are not subject of this patent application, such as PH3, Ashb, fBuPhb, fBuAshb and Me 2 NNH 2 .
- Suitable group 13 compounds are, for example, trimethyl indium (Me3ln) trimethyl gallium (MesGa), tri-tertbutyl gallium (fBu3Ga) or triethyl gallium (EbGa).
- Exposing both the group 15 element compound or compounds of formula (I) or formula (I I) and the group 13 compound or compounds to conditions suitable for deposition of a 13/15 semiconductor layer is generally known in the art as repeatable vapor deposition processes, like a chemical vapor deposition process, such as methods known as metal-organic chemical vapor deposition (MOCVD) or metal-organic vapor phase epitaxy (MOVPE), which usually yield in deposition of layers that are characterized by being homogeneous, defined and ultrapure.
- MOCVD metal-organic chemical vapor deposition
- MOVPE metal-organic vapor phase epitaxy
- a potential gallium source being e.g. trimethylgallium (MesGa), tri-tertbutylgallium (fBu3Ga) or tri-ethylgallium (EtsGa)
- the relationship of the group 15 elements that should be contained in the 13/15 semiconductor and/or the 13/15 semiconductor layer to be produced - in this case nitrogen and arsenic - is mainly preset by the composition of the single source precursor fBu2As-NH2.
- the group 15 element / group 15 element relation e.g. the relation As/N in the 13/15 semiconductor and/or the 13/15 semiconductor layer may, however, be influenced by a variation of the process parameters, e.g. the partial pressure of the binary group 15 element sources in the reactor or the process temperature.
- group 15 element compound fBu2As-NH2 In addition to the group 15 element compound fBu2As-NH2, one or several other group 15 element compounds according to the invention or already known may be used, e.g. the known non-binary group 15 element compound fBuAshb as an additional source of arsenic or the known non-binary group 15 element compound fBuPhb as a source of phosphorus.
- group 15 element compound fBu2As-NH2 as binary group 15 element compounds with the addition of one or several group 15 element compounds allows the production of
- Ga(Asi-xNx) layers (0 ⁇ x ⁇ 1) which have a lower nitrogen content compared to the exclusive use of fBu2As-NH2 as the source of nitrogen and arsenic.
- This can be attributed to the fact that the nitrogen atoms have to compete with the group 15 element atoms from the additional group 15 element source, e.g. from a source of arsenic or phosphorus.
- the combination and thus the opto-electronic characteristics of the 13/15 semiconductor and/or the 13/15 semiconductor layer may be varied and/or fine-tuned to a large degree.
- This purpose is furthermore met by a 13/15 semiconductor layer that is producible in a vapor deposition process using at least one binary group 15 element compound as the educt in a vapor deposition process according to one of the embodiment examples described above.
- R 1 , R 2 , R 3 and R 4 are selected independently from one another from the group
- - E and E' are selected independently from one another from the group consisting of N, P, As, Sb and Bi,
- E E' or E ⁇ E', and/or wherein at least one binary group 15 element compound has the general formula
- R 5 - R 6 and R 7 are selected independently from one another from the group
- - E and E' are selected independently from one another from the group consisting of N, P, As, Sb and Bi,
- E E' or E ⁇ E'
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C6 alkyl radical and C1 to C8 aryl radical.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C4 alkyl radical and C1 to C6 aryl radical.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/ ' Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (t u or 2- methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
- alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be, in particular, trifluormethyl (CF 3 ) or
- the invention does not concern the use of hydrazine (H2N-NH2) and its derivatives, especially 1.1 dimethyl hydrazine and tertiary butyl hydrazine as the educt in a vapor deposition process.
- hydrazine H2N-NH2
- 1.1 dimethyl hydrazine and tertiary butyl hydrazine as the educt in a vapor deposition process.
- hydrazine derivatives that can be produced, starting with hydrazine by substituting one or several hydrogen atoms.
- the 13/15 semiconductor layer according to the invention produced in a repeatable vapor deposition process, preferably in a chemical vapor deposition, especially in a metal-organic chemical vapor deposition (MOCVD) or a metal-organic vapor phase epitaxy (MOVPE) is characterized by being homogeneous, defined and ultrapure.
- MOCVD metal-organic chemical vapor deposition
- MOVPE metal-organic vapor phase epitaxy
- the composition of the single source precursor mainly determines, especially by means of the respective selection of the binary group 15 elements, the relationship of the group 15 elements to be contained in the 13/15 semiconductor layer.
- the single source precursors provided according to the invention may also be used with one or several other group 15 element sources according to the invention or already known. This may be particularly advantageous in the case of nitrogenous binary group 15 element compounds of the formula (I) or (II).
- a controllable addition of one or several other group 15 element sources according to the invention or already known may influence and fine tune the nitrogen content of the 13/15 semiconductor to be produced and/or deposited deriving from the nitrogenous binary group 15 element compound. It is in particular possible to produce or deposit 13/15
- the semiconductors that do not feature the group 15 elements contained in the binary nitrogenous group 15 element compound at the same ratio that is mainly preset by the composition of the single source precursor.
- the only source of arsenic is, for example, the binary group 15 element compound fBu2As-NH2
- the relationship of the group 15 elements that should be contained in the 13/15 semiconductor and/or the 13/15 semiconductor layer to be produced and/or deposited - in this case nitrogen and arsenic - is mainly prescribed by the composition of the single source precursor fBu2As-NH2.
- the group 15 element / group 15 element relation e.g.
- the relation As/N in the 13/15 semiconductor to be produced and/or the 13/15 semiconductor layer to be deposited may, however, be influenced by a variation of the process parameters, e.g. the partial pressure of the binary group 15 element sources in the reactor or the process temperature.
- the group 15 element compound fBu2As-NH2 one or several other group 15 element compounds according to the invention or already known may be used, e.g. the known non-binary group 15 element compound fBuAshb as an additional source of arsenic or the known non-binary group 15 element compound fBuPhb as a source of phosphorus.
- fBu2As-NH2 is used as the binary group 15 element compound with the addition of one or several group 15 element compounds, it is possible to create Ga(Asi- x N x ) layers (0 ⁇ x ⁇ 1), which - compared with the exclusive use of fBu2As-NH2 as the source of nitrogen and arsenic - have a lower nitrogen content.
- This can be attributed to the fact that the nitrogen atoms have to compete with the group 15 element atoms from the additional group 15 element source, e.g. from a source of arsenic or phosphorus. Accordingly it is possible to vary and/or fine tune the opto-electronic characteristics of the 13/15 semiconductors to be produced and/or deposited to an even larger extent.
- binary group 15 element sources as provided according to the invention allows the representation of multinary 13/15 semiconductor layers at relatively low process temperatures, which contributes to an improvement of the energy efficiency and thus in general to process optimization.
- the process is particularly easy and safe in execution, as well as atom- and energy-efficient and therefore, on the whole, cost-efficient.
- the purpose is further met by the binary group 15 element compounds according to the general formula
- R 1 , R 2 , R 3 and R 4 are selected independently from one another from the group consisting of H, an alkyl radical (C1 - C10) and an aryl group, and
- - E and E' are selected independently from one another from the group consisting of P, As, Sb and Bi,
- R 5 , R 6 , and R 7 are selected independently from one another from the group consisting of H, an alkyl radical (C1 - C10) and an aryl group,
- - E is selected from the group consisting of N, P, As, Sb and Bi, and
- - E' is selected from the group consisting of P, As, Sb and Bi,
- Hydrazine H2N-NH2
- its derivatives are not the subject matter of the invention.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C6 alkyl radical and C1 to C8 aryl radical.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C4 alkyl radical and C1 to C6 aryl radical.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of hydrogen (H), methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/ ' Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (t u or 2- methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
- alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be, in particular, trifluormethyl (CF 3 ) or
- the group 15 element compounds used according to the invention represent single source precursors (SSP) with regard to the elements of group 15. This means that the single source precursors provided according to the invention each have more than one group 15 element, wherein these are two different group 15 elements.
- the group 15 elements included in the precursor may be selected or combined according to the characteristics, especially the opto-electronic characteristics that the 13/15 semiconductor that is to be produced and/or deposited on a substrate should have.
- the group 15 element sources such as PH3, Ashb, fBuPhb, fBuAshb and ⁇ 2 ⁇ 2 used until now for chemical vapor deposition processes each have only one group 15 element, which means that depending on the desired combination of the 13/15 semiconductor to be produced and/or deposited, several group 15 element sources have to be provided and mixed with one another.
- the group 15 element sources of formula (I) and/or (II) used according to the invention advantageously include two group 15 elements that differ from one another. Accordingly, the advantage is the option of producing multinary 13/15 semiconductor connections and/or layers starting from the single source precursors according to the invention, without the necessity of creating a separate precursor connection for each group 15 element contained in the 13/15 semiconductor to be produced.
- the use of the binary group 15 element compounds according to the invention reduces the number of resulting by-products which consequently have to be desorbed by the 13/15 semiconductor produced and/or the respective layer, which leads to an increase in the atom efficiency and the simplification of the process.
- the compounds according to the invention have lower disintegration temperatures than the group 15 element sources such as PH3, ASH3, fBuPhb, fBuAshb previously used in chemical vapor deposition processes. Furthermore, the group 15 element precursors according to the invention are not toxic compared to phosphine (PH3) and arsine (ASH3). With the use of the group 15 element precursors according to the invention, the vapor deposition process may be conducted at relatively low process temperatures in a comparably energy- and thus cost- efficient way, as well as in a safe, healthy and environmentally-friendly manner. The selection may be effected from a plurality of single source precursors according to the invention, wherein the relationship of the group 15 elements that should be included in the 13/15 semiconductor to be produced is already preset substantially indicated by the
- these compounds are nitrogenous single source precursors such as fBu2As-NH2 or HN(SbfBu2)2 that have no nitrogen-bound carbon.
- These binary group 15 element sources have all the advantageous characteristics of single source precursors, such as, for example, high vapor pressure, low toxicity, simple producibility, easy handling and the existence of a good leaving group without, however, containing a nitrogen-bound carbon atom. It is possible to renounce the addition of an organically substituted nitrogen compound such as 1.1 dimethyl hydrazine as the nitrogen source. Consequently, such compounds are particularly suitable for the representation of ultrapure nitrogenous 13/15 semiconductors and/or layers.
- 13/15 semiconductors and/or 13/15 semiconductor layers are obtained with the use of the compounds according to the invention that - compared to the 13/15 semiconductors and/or 13/15 semiconductor levels produced according to the previous production methods - have a drastically reduced level of carbon content since the use of carbonic nitrogen sources is waived. Should carbon contaminations possibly be contained in the 13/15
- the single source precursors provided according to the invention may also be used with one or several other group 15 element sources according to the invention or already known. This may be particularly advantageous in the case of nitrogenous binary group 15 element compounds of the formula (I) or (II).
- the controllable addition of one or several other group 15 element sources may influence and fine tune the nitrogen content of the 13/15 semiconductor to be produced and/or deposited deriving from the nitrogenous binary group 15 element compound. It is in particular possible to produce or deposit 13/15 semiconductors that do not feature the group 15 elements contained in the binary nitrogenous group 15 element compound at the same ratio that is mainly preset by the composition of the single source precursor. Accordingly it is possible to vary and/or fine tune the opto-electronic characteristics of the 13/15 semiconductors to be produced and/or deposited to an even larger extent.
- the group 15 element precursors according to the invention allow the simple, secure, comparably atom-efficient and relatively energy-efficient production of a 13/15 semiconductor and/or a respective layer.
- Fig. 1 High-resolution X-ray diffraction profiles of Ga(Asi- x N x )/GaAs multiple quantum well structures produced using DTBAA (red graph) and/or using DTBAA and TBAs (black graph) and
- Fig. 2 Photoluminescence spectra of Ga(Asi- x N x )/GaAs multiple quantum well structures produced using DTBAA (red graph) and/or using DTBAA and TBAs (black graph).
- a continuous N H3 stream of gas is introduced into a solution of fBu2AsCI (4.0 g) in 50 ml diethyl ether for two hours at 20°C.
- the NH 4 CI sediment that occurs is subsequently removed by filtration.
- the solvent is then distilled from the filtrate and the residue is then subjected to precision distillation in a vacuum.
- the resulting compound is fBu2As-NH2 at a pressure of 0.002 kPa (0.02 mbar) and a temperature of 40°C with a yield of 60%.
- the compound fBu2Sb-PH2 is produced as an orange colored oil, which quickly disintegrates at room temperature, generating fBuPH 2 , PH 3 , (fBuSb) and (fBu 2 Sb)2PH, which therefore has to be stored at -80°C.
- NC(CH 3 ) 3 ); 50.94 (s, NC(CH 3 ) 3 ) ppm.
- Example 6 Preparation of fBu2Sb-PHfBu 1.55 g fBu2SbCI (5.71 mmol) is suspended in 50 ml n-pentane. 0.55 g fBuPHLi (5.71 mmol) are added at -20°C, which creates a yellow solution that is stirred overnight. The solids are separated by centrifugation, and the solvent removed under a high vacuum. The result is 1.62 g of the compound fBu2Sb-PHfBu (yield 87%) as a yellow oil.
- IR v (cm "1 ) 2989.33 (w), 2936.72 (s), 2891.75 (s), 2858.39 (s), 2707.05 (w), 2307.53 (m, P-H), 1469.31 (s), 1458.99 (s) 1386.10 (m), 1360.88 (s), 1260.28 (w), 1172.56 (s), 1025.56 (m), 1014.16 (m), 932.42 (w), 862.72 (w), 809.16 (s), 760.77 (w), 690.99 (w), 584.61 (w), 566.72 (w), 497.30 (w), 461.05 (w), 410.82 (w).
- DTBAA Di-tertbutyl amino arsane
- DTBAA Di-tertbutyl amino arsane
- the characterization of the Ga(Asi-xN x ) layers(0 ⁇ x ⁇ 1) was firstly obtained by X-ray diffraction (XRD), and secondly by photoluminescence spectroscopy.
- XRD X-ray diffraction
- a commercially available diffractometer by XRD X-ray diffraction
- Panalytical Panalytical (Panalytical XPert Pro) was used in the X-ray diffraction, ⁇ -2 ⁇ measurements were conducted in a high-resolution Eulerian cradle. X-rays were made around the (004) GaAs peak. The recording of the photoluminescence spectra was conducted with the 514 nm line of a cw-Ar ion laser (Coherent Inc) used for excitation. Room temperature
- Fig. 1 shows high-resolution X-ray diffraction profiles of Ga(Asi -x N x )/GaAs multiple quantum well structures with 0 ⁇ x ⁇ 1.
- the red color indicates the high-resolution X-ray diffraction profile of the Ga(Asi -x N x )/GaAs multiple quantum well structure that was generated by the exclusive use of the binary group 15 element compound DTBAA as provided according to the invention as the arsenic and nitrogen source.
- the black color indicates the high-resolution X- ray diffraction profile of the Ga(Asi-xN x )/GaAs multiple quantum well structure that was generated by using DTBAA with TBAs additions.
- process parameters such as, for example, process pressure and temperature, it is possible to also generate higher levels of nitrogen content when only DTBAA is used as the group 15 element precursor.
- Fig. 2 shows photoluminescence spectra of the Ga(Asi- x N x )/GaAs multiple quantum well structures from the first and second experiments. The red color indicates the
- the two peaks in the red and black graphs of Fig. 2 that are both at low energy values can be attributed to the nitrogenous quantum well (red graph: approx. 1.225 eV; black graph: approx. 1.375 eV).
- the peak at approx. 1.425 eV derives from the GaAs substrate used.
- the inclusion of nitrogen into the GaAs structure and thus the generation of Ga(Asi -x N x ) (0 ⁇ x ⁇ 1) can be clearly recognized in the case of both experiments by the additional, red-shifted emission - compared to pure GaAs.
- MOVPE therefore leads to the desired deposition of the 13/15 semiconductor Ga(Asi -x N x ), with 0 ⁇ X ⁇ 1.
- the result with regard to the nitrogen inclusion is better than when a mixture of the two group 15 element precursors DTBM and TBAs is used. This is due to the fact that when a mixture of DTBM and TBAs is used, the nitrogen atoms have to compete with the arsenic atoms resulting from the additional arsenic source TBAs, which leads to the result of an overall lower nitrogen content in the desired 13/15 semiconductor Ga(Asi- x N x ) (0 ⁇ x ⁇ 1).
- the nitrogen content of the 13/15 semiconductor Ga(Asi-xNx) (0 ⁇ X ⁇ 1) may be influenced and fine tuned by the specific and controlled addition of one or several other group 15 element sources, either according to the invention or already known - as for example in this case the additional, non-binary arsenic source TBAs.
- the As/N ratio in the 13/15 semiconductor Ga(Asi- x N x ) (0 ⁇ x ⁇ 1) to be produced may therefore, for example, be influenced by the variation of the partial pressures of the binary group 15 element source DTBAA and TBAs in the reactor.
- the process temperature may be modified.
- the combination and, subsequently, the opto-electronic characteristics of the 13/15 semiconductor and/or the 13/15 semiconductor layers may be varied and/or fine-tuned to a large degree.
- an organically substituted nitrogen compound such as 1.1 di-methylhydrazine as the nitrogen source may be waived completely, which drastically reduces nitrogen contaminations - compared to the 13/15 semiconductors and/or 13/15 semiconductor layers produced with the known production methods. Should carbon contaminations possibly be contained in the 13/15 semiconductors and/or 13/15 semiconductor layers that are produced, they usually derive from the group 13 element source or sources that are usually organically substituted.
- the use of the binary group 15 element compound DTBAA according to the invention - without the addition of an organically substituted nitrogen compound as the nitrogen source - allows the production of a defined, ultrapure Ga(Asi- x N x ) layer (0 ⁇ x ⁇ 1) with selectable opto-electronic characteristics.
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Abstract
The invention provides the use of at least one binary group 15 element compound of the general formula R1R2E-E'R3R4 (I) or R5E(E'R6R7)2 (II) as the educt in a vapor deposition process. In this case, R1, R2, R3 and R4 are independently selected from the group consisting of H, an alkyl radical (C1 - C10) and an aryl group, and E and E' are independently selected from the group consisting of N, P, As, Sb and Bi. This use excludes hydrazine and its derivatives. The binary group 15 element compounds according to the invention allow the realization of a reproducible production and/or deposition of multinary, homogeneous and ultrapure 13/15 semiconductors of a defined combination at relatively low process temperatures. This makes it possible to completely waive the use of an organically substituted nitrogen compound such as 1.1 dimethyl hydrazine as the nitrogen source, which drastically reduces nitrogen contaminations - compared to the 13/15 semiconductors and/or 13/15 semiconductor layers produced with the known production methods.
Description
Use of at least one binary group 15 element compound, a 13/15 semiconductor layer and binary group 15 element compounds.
The invention concerns the use of at least one binary group 15 element compound, a 13/15 semiconductor layer and binary group 15 element compounds.
13/15 semiconductors such as the binary compounds gallium arsenide (GaAs) or indium phosphide (InP) and the methods to produce them are known in the state of the art. The representation of 13/15 semiconductors is usually achieved by deposition from the gas phase. Important production methods are, for instance, metal-organic chemical vapor deposition (MOCVD) and metal-organic vapor phase epitaxy (MOVPE). These methods allow the application of ultrapure layers of 13/15 semiconductor materials on a plurality of substrates. Such methods are, among other applications, used in the context of the production of light-emitting diodes, lasers, transistors and solar cells.
For example, for the representation of the binary 13/15 semiconductor GaAs, a gaseous mixture of the group 13 element precursor trimethylgallium (MesGa) and the group 15 element precursor arsine (ASH3) is disintegrated on a hot surface, depositing GaAs. The disintegration of the precursors is directly affected by the process temperature and the process pressure. Since precursors usually have relatively high disintegration temperatures, the process temperatures applied usually have to be high respectively. Other important process parameters are the concentration of the precursors, the concentration of the carrier gas and the reaction gas as well as the total gas flow.
In addition to binary 13/15 semiconductors such as GaAs, ternary 13/15 semiconductors such as nitrogenous gallium arsenide nitride (GaAsi-xNx)) (0 < x < 1) as well quaternary and other multinary 13/15 semiconductors are important as these allow further variation and sensitive adjustments of opto-electronic characteristics than binary 13/15 semiconductors due to the presence of three or four different elements, namely of one or two group 13 elements and two or three group 15 elements.
The production of nitrogenous multinary 13/15 semiconductors, e.g. ternary Ga(Asi-xNx) (0 < X < 1), has so far been achieved by using three separate precursor compounds, namely one group 13 element source and two group 15 element sources. The three precursors are mixed during the gaseous phase and disintegrated together. This kind of representation of multinary 13/15 semiconductors does not only involve a high synthesis effort - especially due to the production of several precursor compounds- but also requires the consideration of different
disintegration temperatures, vapor pressures and the respective different diffusion rates of the various precursors, e.g. three separate precursors for the production of the ternary compound Ga(Asi-xNx) (0 < X < 1). The method is furthermore not very atom-efficient. Usually organically substituted nitrogen compounds are used, such as 1.1 dimethyl hydrazine. The disadvantage is that in addition to the desired inclusion of nitrogen there is also an undesired inclusion of carbon into the 13/15 semiconductors and/or the 13/15 semiconductor layers. Due to the carbon contamination, the opto-electronic characteristics of the 13/15 semiconductors and/or the 13/15 semiconductor layers are modified and/or impaired in an uncontrollable and irreversible way. Furthermore, the partial pressures usually required with regard to the nitrogen source are high. For example, if 1.1 dimethyl hydrazine is used as the nitrogen source, the two selected group 15 element sources, i.e. 1.1 dimethyl hydrazine and another group 15 element source must be present in a molar relationship to each other that is between 10: 1 and 100: 1. The nitrogen percentage thus achieved in the 13/15 semiconductor is, however, only 1-10% which negatively affects the efficiency of the method.
Examples and further details regarding vapor deposition of multinary 13/15 semiconductors on the basis of organically substituted group 15 element compounds such as fBuAshb, fBu2AsH , fBu3As, Et2fl3uAs, Et2/'PrAs, fBusP, fBuPhb are found in the respective literature, for example:
• H. Protzmann, F. Hohnsdorf, Z. Spika, W. Stolz, E. O. Gobel, M. Muller, J. Lorberth, J.
Crystal Growth 1997, 170, 155-160.
• G. Zimmermann, Z. Spika, T. Marschner, B. Spill, W. Stolz, E. O. Gobel, P. Gimmnich, J.
Lorberth, A. Greiling, A. Salzmann, J. Crystal Growth 1994, 145, 512-519.
• J. Komeno, J. Crystal Growth 1994, 145, 468-472.
• M. Horita, M. Suzuki, Y. Matsushima, J. Crystal Growth 1992, 124, 123-128.
• K. Volz, J. Koch, F. Hohnsdorf, B. Kunert, W. Stolz, J. Crystal Growth 2009, 311 , 2418-2426.
• K. Volz, T. Torunski, B. Kunert, O. Rubel, S. Nau, S. Reinhard, W. Stolz, J. Crystal Growth 2004, 272, 739-747.
The known process sequences to produce ternary 13/15 semiconductors must be regarded as rather inefficient in terms of use of energy and atom efficiency, and thus as on the whole rather uneconomical. The invention therefore has the purpose to overcome these and other disadvantages in the state of the art and provide group 15 element compounds that are suitable for use as the educt in a process of vapor deposition, especially for the production of multinary 13/15 semiconductor compounds and/or layers.
The group 15 element compounds to be used should be characterized by the production of multinary, homogeneous and ultrapure 13/15 semiconductors and/or layers in a combination as defined that is as atom-efficient, cost-efficient and reproducible as possible. Furthermore, a 13/15 semiconductor layer should be provided that may be produced using group 15 element compounds as intended according to the invention. In addition, binary group 15 element compounds are to be provided.
The main characteristics of the invention are listed in claim 1 , claim 16 or claim 17.
Embodiments are the subject of claims 2 to 15.
The purpose is achieved by the use of at least one binary group 15 element compound as the educt of a vapor deposition process, wherein the at least one binary group 15 element compound has the general formula of
R1R2E-E'R3R4 (I), wherein
- R1, R2, R3 and R4 are selected independently from one another from the group consisting of H, an alkyl radical (C1 - C10) and an aryl group, and
- E and E' are selected independently from one another from the group consisting of N, P, As, Sb and Bi,
wherein E = E' or E≠ E', and/or wherein at least one binary group 15 element compound has the general formula
R5E(E'R6R7)2 (II), wherein
- R5, R6 and R7 are selected independently from one another from the group
consisting of H, an alkyl radical (C1 - C10) and an aryl group, and
- E and E' are selected independently from one another from the group consisting of N, P, As, Sb and Bi,
wherein E = E' or E≠ E.
The alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated.
Specifically, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C6 alkyl radical and C1 to C8 aryl radical. In particular, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C4 alkyl radical and C1 to C6 aryl radical.
More specifically, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/'Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (tBu or 2- methylpropyl), cyclobutyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
The alkyl or aryl groups can be substituted, particularly fluorinated or perfluorinated. In this case, R1, R2, R3, R4, R5, R6 and R7 may, in particular, be trifluormethyl (CF3) or
pentafluorphenyl (C6F5).
Most specifically, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), methyl (Me), isopropyl (/Pr), tert.-butyl (tBu or 2- methylpropyl). In a specific embodiment, E and E' are different and one of E or E' is N. In another specific embodiment of a compound of formula (I), R1 and R2 are hydrogen (H), if R3 and R4 are different from hydrogen, or R3 and R4 are hydrogen, if R1 and R2 are different from hydrogen.
In another embodiment, E and E' are selected fromthe group consisting of N, P, As and Sb. The invention does not concern the use of hydrazine (H2N-NH2) and its derivatives, especially 1.1 dimethyl hydrazine and tertiary butyl hydrazine as the educt in a vapor deposition process. These compounds are regarded as hydrazine derivatives that can be produced, starting with hydrazine by substituting one or several hydrogen atoms. This includes both acyclic and cyclic compounds, e.g. saturated tripartite compounds. Consequently, in a compound of formula (I), if E or E' is nitrogen (N), then E and E' are different from each other.
The use according to the invention of one or several binary group 15 element compounds of the general formulas (I) and/or (II) as the educt in a vapor deposition process allows a reproducible, cost-efficient representation of multinary, homogeneous and ultrapure 13/15 semiconductor connections and/or layers of a defined combination. The vapor deposition process is preferably a chemical vapor deposition, and especially a metal-organic chemical vapor deposition or a metal-organic metal-organic vapor phase epitaxy (MOVPE). The product of the vapor deposition process is preferably a 13/15 semiconductor layer. The group 15 element compounds used according to the invention represent single source precursors (SSP) with regard to the elements of group 15. The single source precursors designated according to the invention are molecules having more than one group 15 element, especially two different group 15 elements. The group 15 elements included in the precursor
may be selected and/or combined according to the desired opto-electronic characteristics of the 13/15 semiconductor to be produced and/or to be deposited on a substrate.
The group 15 element sources such as PH3, ASH3, tBuPH2, tBuAsh^ and Μβ2Ν-Ν Η2 to date used for chemical vapor deposition processes each have only one group 15 element, which means that depending on the desired combination of the multinary, i.e. more than binary 13/15 semiconductor to be produced and/or deposited, several group 15 element sources have to be provided and mixed with one another. In contrast to that, the group 15 element sources of formula (I) and/or formula (II) used according to the invention advantageously include two group 15 elements each, which in most cases differ from one another.
Accordingly, the advantage is the option of producing multinary 13/15 semiconductor connections and/or layers starting from the single source precursors according to the invention, without the necessity of creating a separate precursor connection for each group 15 element contained n the 13/15 semiconductor to be produced. Consequently, it is not necessary to consider various disintegration temperatures, vapor pressures and the respective varying diffusion ratios of several group 15 element sources and/or precursors in the context of planning and conducting the vapor deposition process. This makes the process particularly easy to execute in the production and/or deposition of 13/15 semiconductors.
Furthermore, the use of the binary group 15 element compounds according to the invention reduces the number of resulting by-products which consequently have to be desorbed by the 13/15 semiconductor produced and/or the respective layer, which leads to an increase in the atom efficiency and the simplification of the process. The compounds used according to the invention have lower disintegration temperatures than the group 15 element sources such as PH3, Ash , fBuPhb, fBuAshb previously used in chemical vapor deposition processes. In the case of the group 15 element compounds with E=E' to be used according to the invention, the lower disintegration temperatures can be attributed to the respective lower E-E' bonding. Furthermore, it is possible to do without the very toxic group 15 element precursors such as, for example, phosphine (PH3) and arsine (Ash ). This makes the vapor deposition process comparably energy-saving and thus cost-efficient at low process temperatures as well a process that may be executed in a safe, healthy and environmentally friendly way.
The selection may be effected from a plurality of single source precursors according to the invention, wherein the relationship of the group 15 elements that should be included in the 13/15 semiconductor to be produced can already be preset by the by the composition of the single source precursor. This allows the production of 13/15 semiconductor compounds and/or layers with defined, presettable opto-electronic characteristics. For example, the representation of ternary 13/15
semiconductor compounds and/or layers using the group 15 element compounds according to the invention, e.g. Ga(ExE'i-x) (E≠ E; 0 < x < 1), is possible in a simple, atom-efficient and cost-efficient manner. The same is true for the production of quaternary 13/15 semiconductor compounds and/or layers, e.g. Ganlni-nExE'i-x (E≠ E; 0 < x < 1) and Ga(Asi-(x+y)NxPy) (0 < x < 1 and 0 < y < 1).
A particularly preferred embodiment of the binary group 15 element compounds of the general formula (I) and/or (II) according to the invention provides the selection of nitrogenous single source precursors such as fBu2As-NH2 or HN(SbfBu2)2 that have no nitrogen-bound carbon. These binary group 15 element sources have all the advantageous characteristics of single source precursors, such as, for example, high vapor pressure, low toxicity, simple producibility, easy handling and the existence of a good leaving group without, however, containing a nitrogen-bound carbon atom. It is possible to renounce the addition of an organically substituted nitrogen compound such as 1.1 dimethyl hydrazine as the nitrogen source. Consequently, such compounds are particularly suitable for the representation of ultrapure nitrogenous 13/15 semiconductors and/or layers. It is particularly advantageous that 13/15 semiconductors and/or 13/15 semiconductor layers are obtained with the use of the compounds according to the invention that - compared to the 13/15 semiconductors and/or 13/15 semiconductor levels produced according to the previous production methods - have a drastically reduced level of carbon content since the use of carbonic nitrogen sources is waived. Carbon contaminations possibly contained in the 13/15 semiconductors and/or 13/15
semiconductor layers that are produced usually originate from the group 13 element source or sources that are usually organically substituted.
The single source precursors provided according to the invention may also be used with one or several other group 15 element sources according to the invention or already known. This may be particularly advantageous in the case of nitrogenous binary group 15 element compounds of the formula (I) or (II). The controllable addition of one or several other group 15 element sources may influence and fine tune the nitrogen content of the 13/15 semiconductor to be produced and/or deposited deriving from the nitrogenous binary group 15 element compound. It is in particular possible to produce and/or deposit 13/15 semiconductors that have a different relation between the group 15 elements than the one that would be obtained in the case of the exclusive use of binary group 15 element compounds. For example, the nitrogen content in the production of Ga(Asi-xNx) (0 < x < 1) usually assumes a lower level than the arsenic content. Adding another group 15 element source such as, for example, the arsenic source fBuAshb allows for a further reduction of the nitrogen content of Ga(Asi-xNx) (0 < X < 1) compared to the arsenic content. This may be attributed to the fact that the nitrogen atoms have to compete with the arsenic atoms from the additional arsenic source. Accordingly it is possible to vary and/or fine tune the opto-electronic characteristics of the 13/15 semiconductors to be produced and/or deposited to an even larger extent.
On the whole, it is possible to realize a reproducible and/or deposition of multinary, homogeneous and ultrapure 13/15 semiconductors of a defined combination at relatively low process temperatures, starting from the binary group 15 element compounds according to the invention. The group 15 element precursors according to the invention allow the simple, secure, comparably atom-efficient and relatively energy-efficient production of a 13/15 semiconductor and/or a respective layer.
In one advantageous embodiment of the use according to the invention, the educt is a binary group 15 element compound of the general formula (I) and
- R1 and R2 are selected independently from one another from the group consisting of an alkyl radical (C1 - C10) and an aryl group, and
- R3 = R4 = H.
Specifically, R1 and R2 are the same or different and are selected from the group consisting of C1 to C6 alkyl radical and C1 to C8 aryl radical. In particular, R1 and R2 are the same or different and are selected from the group consisting of C1 to C4 alkyl radical and C1 to C6 aryl radical. More specifically, R1 and R2 are the same or different and are selected from the group consisting of methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/'Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (tBu or 2-methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
The alkyl or aryl groups can be substituted. In particular, they may be fluorinated or
perfluorinated. In this case, R1 and R2 are, in particular, trifluormethyl (CF3) or pentafluorphenyl (C6F5). In particular, R1 and R2 are the same. In specific embodiments, R1 and R2 are tBu, /'Pr, trifluormethyl or phenyl. In another specific embodiment, E and E' are different from each other. In another specific embodiment, E is selected from the group consisting of P, As and Sb. In yet another specific embodiment, E' is selected from the group consisting of N, P and As, more specifically, E' is N . In a further specific embodiment, E is selected from the group consisting of P, As, Sb and Bi, in particular P, As and Sb, and E' is N . In this embodiment, tBu can be advantageously employed as both R1 and R2.
The alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated. The binary group 15 element compound of the general formula (I) is preferably selected from the group consisting of fBu2P-NH2, (CF3)2P-NH2, (C6H5)2P-NH2, fBu2P-AsH2, fBu2As-N H2, fBu2As- PH2, (C6H5)2As-PH2, fBu2Sb-NH2 and fBu2Sb-PH2. All these single source precursors are suitable for the production and/or deposition of a plurality of multinary 13/15 semiconductors. The nitrogenous group 15 element compounds fBu2P-NH2, (CF3)2P-NH2, (C6Hs)2P-NH2, fBu2As-N H2 and fBu2Sb-N H2 are particularly suitable for the reproducible representation and/or deposition of ultrapure nitrogenous 13/15 semiconductor layers with drastically
reduced carbon content - compared to a 13/15 semiconductor and/or 13/15 semiconductor layer produced according to known production methods - as they do not have any nitrogen- bound carbon atom. Should carbon contaminations possibly be contained in the 13/15 semiconductors and/or 13/15 semiconductor layers that are produced, they usually derive from the group 13 element source or sources that are usually organically substituted.
The binary group 15 element compound fBu2As-NH2 (DTBAA = Di-tertbutylaminoarsan) may, for example, be used as a source or nitrogen and arsenic for the synthesis of Ga(Asi-xNx) layers (0 < X < 1), with a potential gallium source being e.g. trimethylgallium (MesGa), tri-tertbutylgallium (fBu3Ga) or tri-ethylgallium (EtsGa), and the deposition may occur on GaAs as the substrate. This makes it possible to waive the use of an organically substituted nitrogen compound such as 1.1 dimethyl hydrazine as the nitrogen source, which drastically reduces nitrogen contaminations - compared to the 13/15 semiconductors and/or 13/15 semiconductor layers produced with the known production methods. Any carbon contaminations possibly contained in the 13/15 semiconductors and/or 13/15 semiconductor layers that are produced usually derive from the group 13 element source or sources that are normally organically substituted.
In as much as the only source of arsenic is the binary group 15 element compound fBu2As-NH2, the relationship of the group 15 elements that should be contained in the 13/15 semiconductor and/or the 13/15 semiconductor layer to be produced - in this case nitrogen and arsenic - is mainly preset by the composition of the single source precursor fBu2As-NH2. The group 15 element / group 15 element relation, e.g. the relation As/N in the 13/15 semiconductor and/or the 13/15 semiconductor layer may, however, be influenced by a variation of the process parameters, e.g. the partial pressure of the binary group 15 element sources in the reactor or the process temperature. In addition to the group 15 element compound fBu2As-NH2, one or several other group 15 element compounds according to the invention or already known may be used, e.g. the known non-binary group 15 element compound fBuAshb as an additional source of arsenic or the known non-binary group 15 element compound fBuPhb as a source of phosphorus. The use of fBu2As-NH2 as binary group 15 element compounds with the addition of one or several group 15 element compounds allows the production of
Ga(Asi-xNx) layers (0 < x < 1) which have a lower nitrogen content compared to the exclusive use of fBu2As-NH2 as the source of nitrogen and arsenic. This can be attributed to the fact that the nitrogen atoms have to compete with the group 15 element atoms from the additional group 15 element source, e.g. from a source of arsenic or phosphorus. On the whole, the combination and thus the opto-electronic characteristics of the 13/15 semiconductor and/or the 13/15 semiconductor layer may be varied and/or fine-tuned to a large degree.
ln another embodiment of the use according to the invention, the educt is a binary group 15 element compound of the general formula (I) and
- R1 , R2 and R4 are selected independently from one another from the group consisting of an alkyl radical (C1 - C10) and an aryl group, and
- R3 = H.
Specifically, R1 , R2 and R are the same or different and are selected from the group consisting of C1 to C6 alkyl radical and C1 to C8 aryl radical. In particular, R1 , R2 and R are the same or different and are selected from the group consisting of C1 to C4 alkyl radical and C1 to C6 aryl radical. More specifically, R1 , R2 and R are the same or different and are selected from the group consisting of methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/'Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (tBu or 2-methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
The alkyl or aryl groups can be substituted, particularly fluorinated or perfluorinated. In this case, R1 , R2 and R are, in particular, trifluormethyl (CF3) or pentafluorphenyl (C6F5). In one embodiment, R1 , R2 and R are the same. In specific embodiments, R1 , R2 and R are, independently of each other, Me, tBu, /'Pr, trifluormethyl or phenyl.
In a specific embodiment, E and E' are different. In another specific embodiment, E is selected from the group consisting of As and Sb. In yet another specific embodiment, E' is selected from the group consisting of N, P, Sb and Bi.
Even more specifically, if E' is Sb or Bi, then R4 is tBu.
The alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated. The binary group 15 element compound of the general formula (I) is preferably selected from the group consisting of fBu2As-PHMe, fBu2Sb-NHfBu, fBu2Sb-PHfBu and fBu2Sb-NH/Pr. These single source precursors may be used for the reproducible representation and/or deposition of various homogeneous, definable 13/15 semiconductors.
Another embodiment of the use according to the invention provides that the educt is a binary group 15 element compound with the general formula (I), and R1 , R2, R3 and R4 have been independently selected from the group consisting of an alkyl radical (C1 - C10) and an aryl group. The alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or
perfluorinated. The binary group 15 element compound of the general formula (I) is preferably selected from the group consisting of Me2As-AsMe2, fBu2Sb-NMe2, /Pr2Sb-PMe2, Et2Sb-NMe2, Et2Sb-P(C6H5)2, fBu2Bi-PfBu2 and fBu2Bi-AsfBu2.
These compounds are all suitable for the reproducible generation and/or deposition of a plurality of homogeneous multinary 13/15 semiconductors of defined combination.
ln another embodiment of the use according to the invention, the educt is a binary group 15 element compound of the general formula (II) and R5 = H. In this case, the binary group 15 element compound of the general formula (II) is preferably selected from the group consisting of HP(AsfBu2)2 and HN(SbfBu2)2. Both single source precursors are suitable for the reproducible representation and/or deposition of homogeneous, defined and ultrapure 13/15 semiconductors. The binary group 15 element compound HN(SbfBu2)2 is particularly suitable for the reproducible manufacture of nitrogenous 13/15 semiconductors and/or 13/15 semiconductor layers of the defined composition. It is particularly advantageous that 13/15 semiconductors and/or 13/15 semiconductor layers are obtained with the use of the binary group 15 element compounds according to the invention that - compared to the 13/15 semiconductors and/or 13/15 semiconductor levels produced according to the previous production methods - have a drastically reduced level of carbon content since the use of carbonic nitrogen sources is waived. Should carbon contaminations possibly be contained in the 13/15 semiconductors and/or 13/15 semiconductor layers that are produced, they usually derive from the group 13 element source or sources that are usually organically substituted.
In another embodiment of the use according to the invention, the educt is a binary group 15 element compound of the general formula (II) and
- R5 is selected from the group consisting of an alkyl radical (C1 - C10) and an aryl group, and
- R6 = R7 = H.
Specifically, R5 is selected from the group consisting of C1 to C6 alkyl radical and C1 to C8 aryl radical. In particular, R5 is selected from the group consisting of C1 to C4 alkyl radical and C1 to C6 aryl radical. More specifically, R5 is selected from the group consisting of methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/'Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (tBu or 2-methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
The alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated. In this case, R5 may be selected from the group consisting of trifluormethyl (CF3) or
pentafluorphenyl (C6F5). In specific embodiments, R5 may be selected from Me, tBu, trifluormethyl or phenyl.
In another specific embodiment, E is selected from the group consisting of P and As. In yet another specific embodiment, E' is N.
The binary group 15 element compound of the general formula (II) is preferably selected from the group consisting of fBuP(NH2)2, fBuAs(NH2)2 and (C6H5)P(NH2)2. These group 15 element sources are suitable for the reproducible representation and/or deposition of nitrogenous, homogeneous, ultrapure 13/15 semiconductors of the defined combination. It is particularly advantageous that 13/15 semiconductors and/or 13/15 semiconductor layers obtained with
the use of the binary group 15 element compounds according to the invention that - compared to the 13/15 semiconductors and/or 13/15 semiconductor levels produced according to the previous production methods - have a drastically reduced level of carbon content since the use of carbonic nitrogen sources is waived. Carbon contaminations possibly contained in the 13/15 semiconductors and/or 13/15 semiconductor layers that are produced usually originate from the group 13 element source or sources that are usually organically substituted.
In another embodiment of the use according to the invention, the educt is a binary group 15 element compound of the general formula (I I) and
- R5 and R7 are selected independently from one another from the group consisting of an alkyl radical (C1 - C10) and an aryl group, and
- R6 = H.
Specifically, R5 and R7 are the same or different and are selected from the group consisting of C1 to C6 alkyl radical and C1 to C8 aryl radical. In particular, R5 and R7 are the same or different and are selected from the groups consisting of C1 to C4 alkyl radical and C1 to C6 aryl radical. More specifically, R5 and R7 are the same or different and are selected from the group consisting of methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (n u), isobutyl (/'Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (tBu or 2-methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
The alkyl or aryl groups can be substituted, particularly fluorinated or perfluorinated and in this case, R5 and R7 are, in particular, trifluormethyl (CF3) or pentafluorophenyl (C6F5). In a specific embodiment, R5 and R7 are different. In another specific embodiment, R5 and R7 may be selected from Me, Et, nBu, tBu, trifluormethyl or phenyl.
In another specific embodiment, E is selected from the group consisting of P, As and Sb and more specifically, may be P. In yet another specific embodiment, E' is selected from the group consisting of N, P and As and more specifically is As.
The alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated. The binary group 15 element compound of the general formula (I I) is preferably selected from the group consisting of nBuP(AsHMe)2 and (C6Hs)P(AsHMe)2. Both single source precursors are suitable for the reproducible production of homogeneous, defined and ultrapure 13/15 semiconductors and/or layers.
In another embodiment of the use according to the invention, the educt is a binary group 15 element compound of the general formula (I I) and
- R5 = H, and
- R6 and R7 are selected from the group consisting of an alkyl radical (C1 - C10) and an aryl group,
Specifically, R6 and R7 are selected from the group consisting of C1 to C6 alkyl radical and C1 to C8 aryl radical. In particular, R6 and R7 are selected from the group consisting of C1 to C4 alkyl radical and C1 to C6 aryl radical. More specifically, R6 and R7 are selected from the group consisting of methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/'Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (tBu or 2-methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl. The alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated. In this case, R6 and R7 may be selected from the group consisting of trifluormethyl (CF3) or pentafluorphenyl (C6F5). In a specific embodiment, R6 and R7 are the same. In specific embodiments, R6 and R7 are may be selected from Me, tBu or phenyl.
In another specific embodiment, E is selected from the group consisting of P and As. In yet another specific embodiment, E' is N.
The binary group 15 element compound of the general formula (II) is preferably selected from the group consisting of HP(AsfBu2)2, HN(SbfBu2)2, HP(N(fBu)2)2, HAs(N(fBu)2)2 and
HP(N(C6H5)2)2. These group 15 element sources are suitable for the reproducible
representation and/or deposition of nitrogenous, homogeneous, ultrapure 13/15
semiconductors of the defined combination. It is particularly advantageous that 13/15 semiconductors and/or 13/15 semiconductor layers obtained with the use of the binary group 15 element compounds according to the invention that - compared to the 13/15
semiconductors and/or 13/15 semiconductor levels produced according to the previous production methods - have a drastically reduced level of carbon content since the use of carbonic nitrogen sources is waived. Carbon contaminations possibly contained in the 13/15 semiconductors and/or 13/15 semiconductor layers that are produced usually originate from the group 13 element source or sources that are usually organically substituted.
Another embodiment of the use according to the invention provides that the educt is a binary group 15 element compound with the general formula (II), and R5, R6 and R7 are independently selected from the group consisting of an alkyl radical (C1 - C10) and an aryl group.
The alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated. The binary group 15 element compound of the general formula (II) is preferably selected from the group consisting of fBuAs(NMe2)2, m-F3CC6H As(NMe2)2 and tBuAs(PMe2)2. All of these compounds are suitable for the reproducible generation and/or deposition of a plurality of homogeneous multinary 13/15 semiconductors of defined combination.
The use of the group 15 element compounds as educt in a vapor deposition process as described above does also encompass a method for vapor deposition, wherein a compound of formula (I) or formula (II) is employed as an educt.
In this way, a 13/15 semiconductor layer can be produced by this method for vapor deposition, using at least one binary group 15 element compound as the educt in a vapor deposition process according to one of the embodiments specified above.
Specifically, the method for vapor deposition, wherein a compound of formula (I) or formula (II) is employed as an educt, which is encompassed by the use of the group 15 element compounds of formula (I) or formula (II) as educt in a vapor deposition process as described above may comprise the steps of
Providing at least one group 15 element compound of formula (I) or formula (II) described above;
Exposing the group 15 element compound of formula (I) or formula (II) to conditions suitable for deposition of a 13/15 semiconductor layer; and
- Deposition of a 13/15 semiconductor layer.
More specifically, the method for vapor deposition, wherein a compound of formula (I) or formula (II) is employed as an educt, which is encompassed by the use of the group 15 element compounds of formula (I) or formula (II) as educt in a vapor deposition process as described above may comprise the steps of
Providing at least one group 15 element compound of formula (I) or formula (II) described above;
Providing at least one group 13 element compound;
Exposing both the group 15 element compound or compounds of formula (I) or formula (II) and the group 13 compound or compounds to conditions suitable for deposition of a
13/15 semiconductor layer; and
Deposition of a 13/15 semiconductor layer.
In the method, the group 15 element compounds of formula (I) or formula (II) can be all compounds described generically or specifically in various embodiments above and are, generally speaking, compounds according to the general formula
R1R2E-E'R3R4 (I), wherein
- R1, R2, R3 and R4 are selected independently from one another from the group
consisting of H, an alkyl radical (C1 - C10) and an aryl group, and
- E and E' are selected independently from one another from the group consisting of P, As, Sb and Bi,
wherein E≠ E', or according to the general formula
wherein
- R5, R6, and R7 are selected independently from one another from the group consisting of H, an alkyl radical (C1 - C10) and an aryl group,
- E is selected from the group consisting of N, P, As, Sb and Bi, and
- E' is selected from the group consisting of P, As, Sb and Bi,
wherein E≠ E.
Hydrazine (H2N-NH2) and its derivatives are not the subject matter of the invention.
Specifically, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C6 alkyl radical and C1 to C8 aryl radical. In particular, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C4 alkyl radical and C1 to C6 aryl radical. More specifically, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/'Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (t u or 2- methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
The alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated. In this case, R1, R2, R3, R4, R5, R6 and R7 may be, in particular, trifluormethyl (CF3) or
pentafluorphenyl (C6F5). In a specific embodiment, E and E' are different and one of E or E' is N. In another specific embodiment of a compound of formula (I), R1 and R2 are hydrogen (H), if R3 and R4 are different from hydrogen, or R3 and R4 are hydrogen, if R1 and R2 are different from hydrogen.
The invention does not concern the use of hydrazine (H2N-NH2) and its derivatives, especially 1.1 dimethyl hydrazine and tertiary butyl hydrazine as the educt in a vapor deposition process. These compounds are regarded as hydrazine derivatives that can be produced, starting with hydrazine by substituting one or several hydrogen atoms. This includes both acyclic and cyclic compounds, e.g. saturated tripartite compounds. Consequently, in a compound of formula (I), if E or E' is nitrogen (N), then E and E' are different from each other.
The group 15 element compounds used according to the invention represent single source precursors (SSP) with regard to the elements of group 15. This means that the single source precursors provided according to the invention each have more than one group 15 element, wherein these are two different group 15 elements. The group 15 elements included in the precursor may be selected or combined according to the characteristics, especially the opto-electronic characteristics that the 13/15 semiconductor that is to be produced and/or deposited on a substrate should have.
In the method for vapor deposition, wherein a compound of formula (I) or formula (II) is employed as an educt, the group 15 element compound of formula (I) or formula (II) may be employed as single compound, as a mixture with each other or with other group 15 compounds which are not subject of this patent application, such as PH3, Ashb, fBuPhb, fBuAshb and Me2NNH2.
Suitable group 13 compounds are, for example, trimethyl indium (Me3ln) trimethyl gallium (MesGa), tri-tertbutyl gallium (fBu3Ga) or triethyl gallium (EbGa).
Exposing both the group 15 element compound or compounds of formula (I) or formula (I I) and the group 13 compound or compounds to conditions suitable for deposition of a 13/15 semiconductor layer is generally known in the art as repeatable vapor deposition processes, like a chemical vapor deposition process, such as methods known as metal-organic chemical vapor deposition (MOCVD) or metal-organic vapor phase epitaxy (MOVPE), which usually yield in deposition of layers that are characterized by being homogeneous, defined and ultrapure.
A binary group 15 element compound fBu2As-NH2 (DTBAA = Di-tertbutylaminoarsan) may, for example, be used as a source or nitrogen and arsenic for the synthesis of Ga(Asi-xNx) layers (0 < X < 1), with a potential gallium source being e.g. trimethylgallium (MesGa), tri-tertbutylgallium (fBu3Ga) or tri-ethylgallium (EtsGa), and the deposition may occur on GaAs as the substrate. This makes it possible to waive the use of an organically substituted nitrogen compound such as 1.1 dimethyl hydrazine as the nitrogen source, which drastically reduces carbon contaminations - compared to the 13/15 semiconductors and/or 13/15 semiconductor layers produced with the known production methods. Any carbon contaminations possibly contained in the 13/15 semiconductors and/or 13/15 semiconductor layers that are produced usually derive from the group 13 element source or sources that are normally organically substituted. In as much as the only source of arsenic is the binary group 15 element compound fBu2As-NH2, the relationship of the group 15 elements that should be contained in the 13/15 semiconductor and/or the 13/15 semiconductor layer to be produced - in this case nitrogen and arsenic - is mainly preset by the composition of the single source precursor fBu2As-NH2. The group 15
element / group 15 element relation, e.g. the relation As/N in the 13/15 semiconductor and/or the 13/15 semiconductor layer may, however, be influenced by a variation of the process parameters, e.g. the partial pressure of the binary group 15 element sources in the reactor or the process temperature. In addition to the group 15 element compound fBu2As-NH2, one or several other group 15 element compounds according to the invention or already known may be used, e.g. the known non-binary group 15 element compound fBuAshb as an additional source of arsenic or the known non-binary group 15 element compound fBuPhb as a source of phosphorus. The use of fBu2As-NH2 as binary group 15 element compounds with the addition of one or several group 15 element compounds allows the production of
Ga(Asi-xNx) layers (0 < x < 1) which have a lower nitrogen content compared to the exclusive use of fBu2As-NH2 as the source of nitrogen and arsenic. This can be attributed to the fact that the nitrogen atoms have to compete with the group 15 element atoms from the additional group 15 element source, e.g. from a source of arsenic or phosphorus. On the whole, the combination and thus the opto-electronic characteristics of the 13/15 semiconductor and/or the 13/15 semiconductor layer may be varied and/or fine-tuned to a large degree.
This purpose is furthermore met by a 13/15 semiconductor layer that is producible in a vapor deposition process using at least one binary group 15 element compound as the educt in a vapor deposition process according to one of the embodiment examples described above.
This refers to a 13/15 semiconductor layer that is producible in a vapor deposition process using at least one binary group 15 element compound as the educt,
wherein at least one binary group 15 element compound has the general formula
R1R2E-E'R3R4 (I), wherein
- R1, R2, R3 and R4 are selected independently from one another from the group
consisting of H, an alkyl radical (C1 - C10) and an aryl group, and
- E and E' are selected independently from one another from the group consisting of N, P, As, Sb and Bi,
wherein E = E' or E≠ E', and/or wherein at least one binary group 15 element compound has the general formula
R5E(E'R6R7)2 (II),
wherein
- R5, R6 and R7 are selected independently from one another from the group
consisting of H, an alkyl radical (C1 - C10) and an aryl group, and
- E and E' are selected independently from one another from the group consisting of N, P, As, Sb and Bi,
wherein E = E' or E≠ E', Specifically, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C6 alkyl radical and C1 to C8 aryl radical. In particular, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C4 alkyl radical and C1 to C6 aryl radical. More specifically, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/'Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (t u or 2- methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
The alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated. In this case, R1, R2, R3, R4, R5, R6 and R7 may be, in particular, trifluormethyl (CF3) or
pentafluorphenyl (C6F5).
The invention does not concern the use of hydrazine (H2N-NH2) and its derivatives, especially 1.1 dimethyl hydrazine and tertiary butyl hydrazine as the educt in a vapor deposition process. These compounds are regarded as hydrazine derivatives that can be produced, starting with hydrazine by substituting one or several hydrogen atoms. This includes both acyclic and cyclic compounds, e.g. saturated tripartite compounds.
The 13/15 semiconductor layer according to the invention, produced in a repeatable vapor deposition process, preferably in a chemical vapor deposition, especially in a metal-organic chemical vapor deposition (MOCVD) or a metal-organic vapor phase epitaxy (MOVPE) is characterized by being homogeneous, defined and ultrapure.
In preparation for the production of the 13/15 semiconductor layer according to the invention, one may choose from a plurality of binary group 15 element compounds of the general formulas (I) and (II) according to the invention. The composition of the single source precursor mainly determines, especially by means of the respective selection of the binary group 15 elements, the relationship of the group 15 elements to be contained in the 13/15 semiconductor layer.
The single source precursors provided according to the invention may also be used with one or several other group 15 element sources according to the invention or already known. This may be particularly advantageous in the case of nitrogenous binary group 15 element compounds of the formula (I) or (II). A controllable addition of one or several other group 15 element sources according to the invention or already known may influence and fine tune the nitrogen content of the 13/15 semiconductor to be produced and/or deposited deriving from the nitrogenous binary group 15 element compound. It is in particular possible to produce or deposit 13/15
semiconductors that do not feature the group 15 elements contained in the binary nitrogenous group 15 element compound at the same ratio that is mainly preset by the composition of the single source precursor. Inasmuch as the only source of arsenic is, for example, the binary group 15 element compound fBu2As-NH2, the relationship of the group 15 elements that should be contained in the 13/15 semiconductor and/or the 13/15 semiconductor layer to be produced and/or deposited - in this case nitrogen and arsenic - is mainly prescribed by the composition of the single source precursor fBu2As-NH2. The group 15 element / group 15 element relation, e.g. the relation As/N in the 13/15 semiconductor to be produced and/or the 13/15 semiconductor layer to be deposited may, however, be influenced by a variation of the process parameters, e.g. the partial pressure of the binary group 15 element sources in the reactor or the process temperature. In addition to the group 15 element compound fBu2As-NH2, one or several other group 15 element compounds according to the invention or already known may be used, e.g. the known non-binary group 15 element compound fBuAshb as an additional source of arsenic or the known non-binary group 15 element compound fBuPhb as a source of phosphorus. If fBu2As-NH2 is used as the binary group 15 element compound with the addition of one or several group 15 element compounds, it is possible to create Ga(Asi-xNx) layers (0 < x < 1), which - compared with the exclusive use of fBu2As-NH2 as the source of nitrogen and arsenic - have a lower nitrogen content. This can be attributed to the fact that the nitrogen atoms have to compete with the group 15 element atoms from the additional group 15 element source, e.g. from a source of arsenic or phosphorus. Accordingly it is possible to vary and/or fine tune the opto-electronic characteristics of the 13/15 semiconductors to be produced and/or deposited to an even larger extent. This allows the production of 13/15 semiconductor compounds and/or layers with defined, settable opto-electronic characteristics 5. Furthermore, the use of binary group 15 element sources as provided according to the invention allows the representation of multinary 13/15 semiconductor layers at relatively low process temperatures, which contributes to an improvement of the energy efficiency and thus in general to process optimization. In addition, the process is particularly easy and safe in execution, as well as atom- and energy-efficient and therefore, on the whole, cost-efficient.
The purpose is further met by the binary group 15 element compounds according to the general formula
R1R2E-E'R3R4 (I), wherein
- R1, R2, R3 and R4 are selected independently from one another from the group consisting of H, an alkyl radical (C1 - C10) and an aryl group, and
- E and E' are selected independently from one another from the group consisting of P, As, Sb and Bi,
wherein E≠ E, or according to the general formula
R5E(E'R6R7)2 (II), wherein
- R5, R6, and R7 are selected independently from one another from the group consisting of H, an alkyl radical (C1 - C10) and an aryl group,
- E is selected from the group consisting of N, P, As, Sb and Bi, and
- E' is selected from the group consisting of P, As, Sb and Bi,
wherein E≠ E'.
Hydrazine (H2N-NH2) and its derivatives are not the subject matter of the invention.
Specifically, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C6 alkyl radical and C1 to C8 aryl radical. In particular, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), C1 to C4 alkyl radical and C1 to C6 aryl radical. More specifically, R1, R2, R3, R4, R5, R6 and R7 are the same or different and are selected from the group consisting of hydrogen (H), methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (/Pr), cyclopropyl, butyl (nBu), isobutyl (/'Bu or 2-methylpropyl), sec-butyl (secBu), tert.-butyl (t u or 2- methylpropyl), cyclopropyl, phenyl (C6H5) or ortho- meta- and para-toluyl.
The alkyl and/or aryl groups may be substituted, e.g. partly fluorinated or perfluorinated. In this case, R1, R2, R3, R4, R5, R6 and R7 may be, in particular, trifluormethyl (CF3) or
pentafluorphenyl (C6F5).
The group 15 element compounds used according to the invention represent single source precursors (SSP) with regard to the elements of group 15. This means that the single source precursors provided according to the invention each have more than one group 15 element, wherein these are two different group 15 elements. The group 15 elements included in the precursor may be selected or combined according to the characteristics, especially the opto-electronic characteristics that the 13/15 semiconductor that is to be produced and/or deposited on a substrate should have.
The group 15 element sources such as PH3, Ashb, fBuPhb, fBuAshb and Μβ2ΝΝΗ2 used until now for chemical vapor deposition processes, each have only one group 15 element, which means that depending on the desired combination of the 13/15 semiconductor to be produced and/or deposited, several group 15 element sources have to be provided and mixed with one another. In contrast, the group 15 element sources of formula (I) and/or (II) used according to the invention advantageously include two group 15 elements that differ from one another. Accordingly, the advantage is the option of producing multinary 13/15 semiconductor connections and/or layers starting from the single source precursors according to the invention, without the necessity of creating a separate precursor connection for each group 15 element contained in the 13/15 semiconductor to be produced.
Consequently, it is not necessary to consider various disintegration temperatures, vapor pressures and the respective varying diffusion ratios of several group 15 element sources and/or precursors in the context of planning and conducting the vapor deposition process. This makes the process particularly easy to execute in the production and/or deposition of 13/15 semiconductors.
Furthermore, the use of the binary group 15 element compounds according to the invention reduces the number of resulting by-products which consequently have to be desorbed by the 13/15 semiconductor produced and/or the respective layer, which leads to an increase in the atom efficiency and the simplification of the process.
The compounds according to the invention have lower disintegration temperatures than the group 15 element sources such as PH3, ASH3, fBuPhb, fBuAshb previously used in chemical vapor deposition processes. Furthermore, the group 15 element precursors according to the invention are not toxic compared to phosphine (PH3) and arsine (ASH3). With the use of the group 15 element precursors according to the invention, the vapor deposition process may be conducted at relatively low process temperatures in a comparably energy- and thus cost- efficient way, as well as in a safe, healthy and environmentally-friendly manner. The selection may be effected from a plurality of single source precursors according to the invention, wherein the relationship of the group 15 elements that should be included in the 13/15 semiconductor to be produced is already preset substantially indicated by the
combination of the single source precursor. This allows the production of 13/15 semiconductor
compounds and/or layers with defined, presettable opto-electronic characteristics. For example, the representation of ternary 13/15 semiconductor compounds and/or layers using the group 15 element compounds according to the invention, e.g. Ga(ExE'i-x) (E≠ E'; 0 < x < 1), is possible in a simple, atom-efficient and cost-efficient manner. The same is true for the production of quaternary 13/15 semiconductor compounds and/or layers, e.g. Ganlni-nExE'i-x (E≠ E'; 0 < x < 1) and Ga(Asi-(x+y)NxPy) (0 < x < 1 and 0 < y < 1).
In a particularly preferred embodiment of the binary group 15 element compounds of the general formula (I) and/or (II) according to the invention, these compounds are nitrogenous single source precursors such as fBu2As-NH2 or HN(SbfBu2)2 that have no nitrogen-bound carbon. These binary group 15 element sources have all the advantageous characteristics of single source precursors, such as, for example, high vapor pressure, low toxicity, simple producibility, easy handling and the existence of a good leaving group without, however, containing a nitrogen-bound carbon atom. It is possible to renounce the addition of an organically substituted nitrogen compound such as 1.1 dimethyl hydrazine as the nitrogen source. Consequently, such compounds are particularly suitable for the representation of ultrapure nitrogenous 13/15 semiconductors and/or layers. It is particularly advantageous that 13/15 semiconductors and/or 13/15 semiconductor layers are obtained with the use of the compounds according to the invention that - compared to the 13/15 semiconductors and/or 13/15 semiconductor levels produced according to the previous production methods - have a drastically reduced level of carbon content since the use of carbonic nitrogen sources is waived. Should carbon contaminations possibly be contained in the 13/15
semiconductors and/or 13/15 semiconductor layers that are produced, they usually derive from the group 13 element source or sources that are usually organically substituted. The single source precursors provided according to the invention may also be used with one or several other group 15 element sources according to the invention or already known. This may be particularly advantageous in the case of nitrogenous binary group 15 element compounds of the formula (I) or (II). The controllable addition of one or several other group 15 element sources may influence and fine tune the nitrogen content of the 13/15 semiconductor to be produced and/or deposited deriving from the nitrogenous binary group 15 element compound. It is in particular possible to produce or deposit 13/15 semiconductors that do not feature the group 15 elements contained in the binary nitrogenous group 15 element compound at the same ratio that is mainly preset by the composition of the single source precursor. Accordingly it is possible to vary and/or fine tune the opto-electronic characteristics of the 13/15 semiconductors to be produced and/or deposited to an even larger extent.
On the whole, it is possible to realize a reproducible production and/or deposition of multinary, homogeneous and ultrapure 13/15 semiconductors of a defined combination at relatively low
process temperatures starting from the binary group 15 element compounds according to the invention. The group 15 element precursors according to the invention allow the simple, secure, comparably atom-efficient and relatively energy-efficient production of a 13/15 semiconductor and/or a respective layer.
Other characteristics, details and advantages of the invention follow from the exact wording of the claims as well as from the following description of the embodiment examples based on the illustrations. They show: Fig. 1 High-resolution X-ray diffraction profiles of Ga(Asi-xNx)/GaAs multiple quantum well structures produced using DTBAA (red graph) and/or using DTBAA and TBAs (black graph) and
Fig. 2 Photoluminescence spectra of Ga(Asi-xNx)/GaAs multiple quantum well structures produced using DTBAA (red graph) and/or using DTBAA and TBAs (black graph).
Synthesis of group 15 element compounds to be used according to the invention
Example 1 : Preparation of fBu2As-PH2
45 ml of a solution of [LiAI(PH2)4] (0.091 M) in DME (4.1 mmol) are presented at -60 °C together with 30 ml THF, and subsequently 2.5 ml fBu2AsCI (12.3 mmol) in 15 ml DME added drop by drop. Once this is heated to room temperature, 100 ml pentane at 0°C are added, and the sediment generated is filtered off. The solvent is removed, and the residue dissolved in pentane and once again filtered. Once the solvent has been removed under vacuum, the product is condensed at room temperature into a template cooled to -196°C. The result is fBu2As-PH2 as a clear, colorless liquid with a yield of 50%.
1H-NMR (300 MHz, C6D6): δ =1 , 17 (d, 4JP,H = 0.4 Hz, 18H, CH3), 2.01 (d, 1JP,H = 181.9 Hz, 2H,
13C{1H}-NMR (75 MHz, C6D6): δ = 30.5 (d, 3JP,C = 4.5 Hz, CH3), 32.4 (s, CqUatemary) ppm.
31P-NMR (121 MHz, C6D6): δ = -204.6 (t, 1JP,H = 181.9 Hz, PH2) ppm.
Example 2: Preparation of fBu2As-NH2 (documented in: O. J. Scherer, W. Janssen, J. Organomet Chem. 1969, 16, P69-P70.)
A continuous N H3 stream of gas is introduced into a solution of fBu2AsCI (4.0 g) in 50 ml diethyl ether for two hours at 20°C. The NH4CI sediment that occurs is subsequently removed by filtration. The solvent is then distilled from the filtrate and the residue is then subjected to precision distillation in a vacuum. The resulting compound is fBu2As-NH2 at a pressure of 0.002 kPa (0.02 mbar) and a temperature of 40°C with a yield of 60%.
1H-NMR (300 MHz, C6D6): δ = 0.53 (s, br, 2H, NH2), 1.06 (s, 18H, CH3) ppm.
13C{1H}-NMR (75 MHz, C6D6): δ = 28.3 (s, CH3), 34.4 (s, CqUatemary) ppm.
Example 3: Preparation of fBu2Sb-PH2
9.2 ml of a solution of [LiAI(PH2)4] in DME (1.62 mmol, 0.176 M in DME) is presented at -78 °C and 1.0 ml fBu2SbCI (4.31 mmol) is added drop by drop. The milkyyellow solution is heated to room temperature after 20 minutes and stirred for another 30 minutes. The solvent is removed at a reduced pressure, and the brown residue extracted with n-pentane (20 ml) and then filtered. Once the solvent is removed at a reduced pressure, the compound fBu2Sb-PH2 is produced as an orange colored oil, which quickly disintegrates at room temperature, generating fBuPH2, PH3, (fBuSb) and (fBu2Sb)2PH, which therefore has to be stored at -80°C.
1H-NMR (300 MHz, C6D6): δ = 1.25 (s, 18H, CH3), 1.63 (d, 1JP,H = 175 Hz, 2H, PH2) ppm.
13C{1H}-NMR (75 MHz, C6D6): δ = 28.0 (d, 2JP,C= 4 Hz, C(CH3)3), 31.9 (d, 3JP,C = 3 Hz, CH3) ppm. 31P-NMR (121 MHz, C6D6): δ = -244.3 (t, 1JP,H= 175 Hz, PH2) ppm.
Example 4: Preparation of fBu2Sb-NH2
0.26 g LiNH2 (11.4 mmol) is suspended in 30 ml diethyl ether. Then, 2.81 g (10.4 mmol) fBu2SbCI is dissolved and added drop by drop to 20 ml diethyl ether at -20°C. Once heated to room temperature, the solvent is removed under a high vacuum, and the residue received in 30 ml /7-pentane. Once the solid is separated by centrifugation, the solvent is removed under a high vacuum. 1.91 g fBu2Sb-NH2 remains (yield 73%) as a colorless liquid.
1H-NMR: (300 MHz, C6D6): δ = 0.19 (s,br, NH2, 2H); 1.15 (s, 18H, CH3) ppm.
13C{1H}-NMR: (75 MHz, C6D6): δ = 29.0 (s, SbC(CH3)3); 29.5 (s, SbC(CH3)3) ppm.
15N{1H}-NMR: (51 MHz, C6D6): δ = -11.0 (s) ppm.
Example 5: Preparation of fBu2Sb-NHfBu
4.45 g fBu2SbCI (16.4 mmol) is suspended in 50 ml n-pentane. The solution is cooled to 0°C and 1.30 g tBuNHLi (16.4 mmol) added. The solution is heated to room temperature, stirred for two hours and then the resulting solid is separated by centrifugation. The solvent is then removed under a high vacuum and the resulting raw product is distilled under a high vacuum (0.0001 kPa (0.001 mbar)). The resulting compound is fBu2Sb-NHfBu (2.56 g, 51% yield) at 36°C as a colorless liquid. 1H-NMR: (300 MHz, C6D6): δ= 1.09 (bs, NH, 1 H); 1.21 (s, Sb(C(CH3)3)2, 18H); 1.23 (s,
NC(CH3)3, 9H) ppm.
13C{1 H}-NMR: (75 MHz, C6D6): δ = 29.97 (s, SbC(CH3)3); 31.53 (s, SbC(CH3)3); 35.10 (s,
NC(CH3)3); 50.94 (s, NC(CH3)3) ppm.
15N{1H}-NMR: (51 MHz, C6D6): δ = 53.47 (s) ppm.
Example 6: Preparation of fBu2Sb-PHfBu
1.55 g fBu2SbCI (5.71 mmol) is suspended in 50 ml n-pentane. 0.55 g fBuPHLi (5.71 mmol) are added at -20°C, which creates a yellow solution that is stirred overnight. The solids are separated by centrifugation, and the solvent removed under a high vacuum. The result is 1.62 g of the compound fBu2Sb-PHfBu (yield 87%) as a yellow oil.
1H-NMR: (300 MHz, C6D6): δ = 1.32 (s, Sb(C(CH3)3)2, 18H); 1.41 (s, PC(CH3)3, 9H); 3.17 (d, 1JPH = 178 Hz, PH, 1 H) ppm.
13C{1H}-NMR: (125 MHz, C6D6): δ = 29.42 (d, 2JCp = 2.37 Hz, Sb(C(CH3)3)2); 32,42
(d, 2Jcp = 4.60 Hz, PC(CH3)3); 34.03 (d, 1 JCp = 12.03 Hz, PC(CH3)3); 35.00 (s, Sb(C(CH3)3)2) ppm. 31P{1H}-NMR: (101 MHz, C6D6): δ = -59.62 (s, PH) ppm.
31P-NMR: (101 MHz, C6D6): δ = -59.62 (d, 1JPH = 178 Hz, PH) ppm.
Example 7: Preparation of fBu2Sb-NH/'Pr
6.20 g fBu2SbCI (22.84 mmol) is dissolved in 40 ml n-pentane, with the former being added drop by drop to a suspension of 1.49 g /'PrNHLi (22.84 mmol) in 50 ml n-pentane at -20°C. After stirring overnight, the solid is separated by centrifugation and the solvent removed under a high vacuum. The subsequent distillation at 2 mm Hg at 68°C results in 3.78 g (yield 56%) of the compound fBu2Sb-NH/'Pr as a colorless liquid.
1H-NMR: (300 MHz, C6D6): 8 = 0.85 (bs, NH, 1 H); 1 , 15 (d, 3JHH = 6.28 Hz, NCH(CH3)2, 6H);
1.21 (s, Sb(C(CH3)3)2, 18H); 3.26 (oct, 3JHH = 6.28 Hz, NCH(CH3)2, 1 H) ppm.
13C{1H}-NMR: (75 MHz, C6D6): δ = 28.57 (s, NCH(CH3)2); 29.91 (s, Sb(C(CH3)3)2); 32.05 (s, Sb(C(CH3)3)2); 49.66 (s, NCH(CH3)2) ppm.
15N-NMR: (51 MHz, C6D6): δ = 39.41 (s, NH) ppm.
Example 8: Preparation of HP(AsfBu2)2
2.20 g fBu2AsCI (9.8 mmol) in approx. 10 ml THF are added drop by drop to a suspension of 1.72 g [Li(dme)PH2] (9.8 mmol) in approx. 150 ml THF at -60°C over a period of 15 minutes. The suspension is stirred overnight. The solvent is removed from the clear orange solution, and the residue is accepted in 100 ml n-pentane and filtered. The volume of the solution is then reduced to 10 ml. The compound HP(AstBu2)2 crystallizes from this solution in the form of yellow needles with a yield of 75% (1.50 g).
1H-NMR (300 MHz, C6D6): δ = 1.31 (s, 18H, CH3), 1.35 (d, 4JP,H = 0.6 Hz, 18H, CH3), 2.72 (d, 1JP,H = 169.5 Hz, 1 H, PH) ppm.
13C{1 H}-NMR (75 MHz, C6D6): δ = 31.2 (d, 3JP,H= 1.0 Hz, CH3), 31.4 (d, 3JP,H = 6.5 Hz, CH3),
34.5 (s, Cquaternary), 36.0 (S, Cquaternary) ΡΡΠΊ
31P-NMR (121 MHz, C6D6): δ = -150.3 (d, 1JP,H = 169.6 Hz, PH) ppm. Example 9: Preparation of HN(SbfBu2)2
1 ml (1.41 g, 5.19 mmol) fBu2SbCI is presented in 100 ml Et20 at O C and then NH3 gas is introduced. This results in spontaneous clouding. After 1.5 hours the reaction comes to an end and the white solid is filtered off. The solvent is removed under a high vacuum, leaving a colorless oil that solidifies into colorless, plate-shaped crystals after some time.
1H-NMR (300 MHz, C6D6): δ = 1 ,30 (s, 36H, C(CH3)3) ppm.
13C{1H}-NMR (75 MHz, C6D6): δ = 29.1 (s, C(CH3)3), 38.7 (s, C(CH3)3) ppm.
Example 10: Preparation of fBu2P-PHfBu
3.79 g (0.022 mol) of fBu2PCI were dissolved in 75 mL of pentane and cooled to -40 °C. 2.50 g (0.026 mol) fBuPHLi were added, resulting in yellow coloration of the reaction mixture. A clear liquid was obtained by filtration and removal of the solvent in vacuum. Distillation in vacuum (10-3 mbar, 100°C) resulted in 2.60 g (52%) fBu2P-P(H)fBu.
31P{1H}-NMR (C6D6): δ = -52.3 (d, 1JPP =232.2 Hz, P(H)fBu), 24.7(d, 1JPP =232,2 Hz, fBu2P). IR v (cm"1) = 2989.33 (w), 2936.72 (s), 2891.75 (s), 2858.39 (s), 2707.05 (w), 2307.53 (m, P-H), 1469.31 (s), 1458.99 (s) 1386.10 (m), 1360.88 (s), 1260.28 (w), 1172.56 (s), 1025.56 (m), 1014.16 (m), 932.42 (w), 862.72 (w), 809.16 (s), 760.77 (w), 690.99 (w), 584.61 (w), 566.72 (w), 497.30 (w), 461.05 (w), 410.82 (w).
Example 11 : Preparation of fBu2P-NH2 (documented in: O. J. Scherer, G. Schieder, Chem. Ber. 1968, 101 , 4184-4198).
28.44 g (0.158 mol, 1.00 eq) of tBu2PCI were suspended in 10 mL diethyl ether and ammonia was condensed into the slurry at -50°C. Ammonium chloride precipitated and formed a white, flaky precipitate. The precipitate was removed by filtration and the raw product was distilled at a pressure of 6,66 mbar and an oil bath temperature of 60°C. 22.8 g (93%) of a colourless, liquid have been obtained.
1H-NMR (300 MHz, C6D6): δ = 1.04 (d, J=11.1 Hz, 18 H, CH3).
13C-NMR 75 MHz, C6D6): δ = 28.1 (d, J=15.3 Hz, CH3), 32.9 (d, J=21.5 Hz, Cquatema-v).
31P{1H}-NMR (C6D6): δ = 62.72 (s, fBu2P-NH2).
31P-NMR (C6D6): δ = 62.72 (s, fBu2P-NH2).
IR v (cm"1) = 3457.64 (w, N-H), 3307.77 (w, N-H), 2937.67 (m), 2893.19 (m), 2860.45
(m), 1559.70 (m), 1470.63 (s), 1384.73 (m). 1361.39 (s), 1260.52 (vw), 1189.44 (br, m), 1 176.09 (br, m), 1017.29 (m), 956.99 (br, w), 930.69 (w), 806.78 (vs), 602.42 (s), 568.16 (w), 466.37 (m), 442.38 (m). Deposition of Ga(Asi-xNx) on GaAs using as a nitrogen source.
fBu2As-NH2 (DTBAA = Di-tertbutyl amino arsane), which is intended according to the invention as an educt in a vapor deposition process, has been successfully used as a nitrogen source for the synthesis of gallium arsenide nitride layers (Ga(Asi-xNx)) (0 < x < 1) in a MOVPE
process, namely for the precipitation of the 13/15 semiconductor Ga(Asi-xNx) (0 < X < 1) on gallium arsenide (GaAs) as the substrate.
A commercial system from the manufacturer AIXTRON AG was used for the precipitation (system type: AIX 200 GFR). The precipitation took place with a hydrogen carrier gas flow at a reactor pressure of 5 kPa (50 mbar). Tri-ethyl gallium (EtsGa) was introduced into the reactor as the gallium source at a pressure of 0.815 X 10"3 kPa (8.15 x 10"3 mbar. The arsenic source used was either the arsenic compound tBuAshb (TBAs = tert-butylarsine) (at a pressure of 0.815 X 10"3 kPa (8.15 X 10"3 mbar) in addition to DTBAA, or no additional arsenic source was used. Precipitation of the Ga(Asi-xNx) layers (0 < x < 1) occurred at a process temperature of 525°C.
In a first experiment, the representation of Ga(Asi-xNx) (0 < x < 1) occurred starting from tri- ethyl gallium (EtsGa) as the group 13 element source and the single source precursor DTBAA, to be used according to the invention, that served as a source of both nitrogen and arsenic.
In a second experiment, fBuAshb (TBAs = tert-butylarsine) was used as an arsenic source in addition to DTBAA.
The characterization of the Ga(Asi-xNx) layers(0 < x < 1) was firstly obtained by X-ray diffraction (XRD), and secondly by photoluminescence spectroscopy. A commercially available diffractometer by
Panalytical (Panalytical XPert Pro) was used in the X-ray diffraction, ω -2Θ measurements were conducted in a high-resolution Eulerian cradle. X-rays were made around the (004) GaAs peak. The recording of the photoluminescence spectra was conducted with the 514 nm line of a cw-Ar ion laser (Coherent Inc) used for excitation. Room temperature
photoluminescence was detected with a 1 m grating monochromator (THR 1000, Jobin-Yvon) and a cooled Ge detector using standard lock-in technology.
The results of the X-ray diffraction experiments as well as the analyses by photoluminescence spectroscopy are graphically depicted in Fig. 1 and Fig. 2 respectively.
Fig. 1 shows high-resolution X-ray diffraction profiles of Ga(Asi-xNx)/GaAs multiple quantum well structures with 0 < x < 1. The red color indicates the high-resolution X-ray diffraction profile of the Ga(Asi-xNx)/GaAs multiple quantum well structure that was generated by the exclusive use of the binary group 15 element compound DTBAA as provided according to the invention as the arsenic and nitrogen source. The black color indicates the high-resolution X- ray diffraction profile of the Ga(Asi-xNx)/GaAs multiple quantum well structure that was generated by using DTBAA with TBAs additions.
While the first experiment resulted in a nitrogen content of 1.3% (see Fig. 1 and 2, red graphs respectively) when only DTBAA was used as a group 15 element precursor, the second experiment saw the inclusion of only 0.3% nitrogen. The nitrogen contents given were determined by dynamic simulations of the X-ray diffraction profiles.
By variation of the process parameters such as, for example, process pressure and temperature, it is possible to also generate higher levels of nitrogen content when only DTBAA is used as the group 15 element precursor.
The values determined from the high-resolution X-ray diffraction profiles (see Fig. 1) for the respective nitrogen content of the two Ga(Asi-xNx)/GaAs multiple quantum well structures analyzed in two independent experiments (see above: first and second experiment) are confirmed by the results from photoluminescence spectroscopy (see Fig. 2), with 0 < x < 1.
Fig. 2 shows photoluminescence spectra of the Ga(Asi-xNx)/GaAs multiple quantum well structures from the first and second experiments. The red color indicates the
photoluminescence spectrum of the Ga(Asi-xNx)/GaAs multiple quantum well structure that was generated by the exclusive use of the binary group 15 element compounds DTBM as provided according to the invention as the arsenic and nitrogen source. The black color indicates in comparison the high-resolution photoluminescence spectrum of the Ga(Asi-xNx)/GaAs multiple quantum well structure that was generated by using DTBAA with TBA additions.
The two peaks in the red and black graphs of Fig. 2 that are both at low energy values can be attributed to the nitrogenous quantum well (red graph: approx. 1.225 eV; black graph: approx. 1.375 eV). The peak at approx. 1.425 eV derives from the GaAs substrate used. The inclusion of nitrogen into the GaAs structure and thus the generation of Ga(Asi-xNx) (0 < x < 1) can be clearly recognized in the case of both experiments by the additional, red-shifted emission - compared to pure GaAs. The exclusive use of DTBAA as the group 15 element precursor (first experiment) allows the observation of a higher nitrogen inclusion (1.3% N) than when DTBAA is used together with TBAs (second experiment, 0.3% N). In Fig. 2, this can be seen in the fact that the red shift in the case of the red graph is greater than in the black graph compared to the pure substrate GaAs.
The use of the binary group 15 element compound DTBAA and the group 13 element precursor EtsGa according to the invention in a vapor deposition process, in this case
MOVPE, therefore leads to the desired deposition of the 13/15 semiconductor Ga(Asi-xNx), with 0 < X < 1. The result with regard to the nitrogen inclusion is better than when a mixture of the two group 15 element precursors DTBM and TBAs is used. This is due to the fact that
when a mixture of DTBM and TBAs is used, the nitrogen atoms have to compete with the arsenic atoms resulting from the additional arsenic source TBAs, which leads to the result of an overall lower nitrogen content in the desired 13/15 semiconductor Ga(Asi-xNx) (0 < x < 1). The use according to the invention of the binary group 15 element compound DTBAA in a vapor deposition process, here MOVPE, leads to the representation of a ternary, nitrogenous 13/15 semiconductor. The relation of the group 15 elements that should be included in the 13/15 semiconductor to be produced - in this case nitrogen and arsenic - is mainly determined by the composition of the single source precursor. The nitrogen content of the 13/15 semiconductor Ga(Asi-xNx) (0 < X < 1) may be influenced and fine tuned by the specific and controlled addition of one or several other group 15 element sources, either according to the invention or already known - as for example in this case the additional, non-binary arsenic source TBAs. This allows the production of 13/15 semiconductors which - compared to the exclusive use of fB^As-Nhb as the source of nitrogen and arsenic - have a lower nitrogen content. This may be attributed to the fact that the nitrogen atoms have to compete with the arsenic atoms from the additional arsenic source. The As/N ratio in the 13/15 semiconductor Ga(Asi-xNx) (0 < x < 1) to be produced may therefore, for example, be influenced by the variation of the partial pressures of the binary group 15 element source DTBAA and TBAs in the reactor. As an alternative or supplement, for example, the process temperature may be modified. On the whole, the combination and, subsequently, the opto-electronic characteristics of the 13/15 semiconductor and/or the 13/15 semiconductor layers may be varied and/or fine-tuned to a large degree.
The use of an organically substituted nitrogen compound such as 1.1 di-methylhydrazine as the nitrogen source may be waived completely, which drastically reduces nitrogen contaminations - compared to the 13/15 semiconductors and/or 13/15 semiconductor layers produced with the known production methods. Should carbon contaminations possibly be contained in the 13/15 semiconductors and/or 13/15 semiconductor layers that are produced, they usually derive from the group 13 element source or sources that are usually organically substituted. On the whole, the use of the binary group 15 element compound DTBAA according to the invention - without the addition of an organically substituted nitrogen compound as the nitrogen source - allows the production of a defined, ultrapure Ga(Asi-xNx) layer (0 < x < 1) with selectable opto-electronic characteristics.
The invention is not limited to one of the embodiments described above, but may be modified in many ways.
Any characteristics and advantages resulting from the claims, the description and the illustrations, including constructive details, spatial arrangement and process steps may be relevant to the invention either separately or in any different combination.
Claims
Claims
Use of at least one binary group 15 element compound as the educt in a vapor deposition process,
wherein at least one binary group 15 element compound has the general formula
R1R2E-E'R3R4 (I), wherein
- R1, R2, R3 and R4 are selected independently from one another from the group consisting of H, an alkyl radical (C1 - C10) and an aryl group, and
- E and E' are selected independently from one another from the group consisting of N, P, As, Sb and Bi,
wherein E = E' or E≠ E', and
wherein hydrazine and its derivatives are excluded from the usage indicated, and/or
wherein at least one binary group 15 element compound has the general formula
R5E(E'R6R7)2 (II),
wherein
- R5, R6 and R7 are selected independently from one another from the group consisting of H, an alkyl radical (C1 - C10) and an aryl group, and
- E and E' are selected independently from one another from the group consisting of N, P, As, Sb and Bi,
wherein E = E' or E≠ E',
Use according to claim 1 , characterized in that the educt is a binary group 15 element compound of the general formula (I) and
- R1 and R2 are selected independently from one another from the group consisting of an alkyl radical (C1 - C10) and an aryl group, and
- R3 = R4 = H.
Use according to claim 2, characterized in that the binary group 15 element compound of the general formula (I) is selected from the group consisting of fBu2P-NH2, (CF3)2P-NH2, Ph2P-NH2, fBu2P-AsH2, fBu2As-NH2, fBu2As-PH2, Ph2As-PH2, fBu2Sb-NH2 and fBu2Sb-PH2.
Use according to claim 1 , characterized in that the educt is a binary group 15 element compound of the general formula (I) and
- R1, R2 and R4 are selected independently from one another from the group
consisting of an alkyl radical (C1 - C10) and an aryl group, and
- R3 = H.
Use according to claim 4, characterized in that the binary group 15 element 15 compound of the general formula (I) is selected from the group consisting of fBu2As- PHMe, fBu2Sb-NHtBu, fBu2Sb-PHtBu and fBu2Sb-NH/Pr.
Use according to claim 1 , characterized in that the educt is a binary group 15 element compound wherein the general formula (I), and R1, R2, R3 and R4 are independently selected from each other from the group consisting of an alkyl radical (C1 - C10) and an aryl group.
Use according to claim 6, characterized in that the binary group 15 element compound of the general formula (I) is selected from the group consisting of Me2As-AsMe2, fBu2Sb- NMe2, /Pr2Sb-PMe2, Et2Sb-NMe2, Et2Sb-P(C6H5)2, fBu2Bi-PfBu2 and fBu2Bi-AsfBu2.
Use according to claim 1 , characterized in that the educt is a binary group 15 element compound of the general formula (II) and
R5 = H.
Use according to claim 8, characterized in that the binary group 15 element compound of the general formula (II) is selected from the group consisting of
HP(AsfBu2)2 and HN(SbfBu2)2.
Use according to claim 1 , characterized in that the educt is a binary group 15 element compound of the general formula (II) and
- R5 is selected from the group consisting of an alkyl radical (C1 - C10) and an group, and
Use according to claim 10, characterized in that the binary group 15 element compound of the general formula (ii) is selected from the group consisting of fBuP(NH2)2, fBuAs(NH2)2 and (C6H5)P(NH2)2.
12. Use according to claim 1 , characterized in that the educt is a binary group 15 element compound of the general formula (II) and
- R5 and R7 are selected independently from one another from the group consisting of an alkyl radical (C1 - C10) and an aryl group, and
- R6 = H.
13. Use according to claim 12, characterized in that the binary group 15 element
compound of the general formula (II) is selected from the group consisting of nBuP(AsHMe)2 and (C6H5)P(AsHMe)2.
14. Use according to claim 1 , characterized in that the educt is a binary group 15 element compound of the general formula (II) and
R5, R6, and R7 are selected independently from one another from the group consisting of an alkyl radical (C1 - C10) and an aryl group,
15. Use according to claim 14, characterized in that the binary group 15 element
compound of the general formula (II) is selected from the group consisting of fBuAs(NMe2)2, m-F3CC6H As(NMe2)2 and fBuAs(PMe2)2.
16. 13/15 Semiconductor layer producible in a vapor deposition process using at least one binary group 15 element compound as the educt in a vapor deposition process according to one of claims 1 to 15.
17. Binary group 15 element compounds according to the general formula
R1R2E-E'R3R4 (I) wherein
- R1, R2, R3 and R4 are selected independently from one another from the group consisting of H, an alkyl radical (C1 - C10) and an aryl group, and
- E and E' are selected independently from one another from the group consisting of P, As, Sb and Bi,
wherein E≠ E, or according to the general formula
R5E(E'R6R7)2 (II),
R5, R6 and R7 are selected independently from one another from the group consisting of H, an alkyl radical (C1 - C10) AND AN aryl group,
E are selected from the group consisting of N, P, As, Sb and Bi, and E' are selected from the group consisting of P, As, Sb and Bi,
wherein E≠ E,
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201580051595.6A CN107075672B (en) | 2014-09-26 | 2015-09-25 | 15 group element compound of purposes, 13/15 semiconductor layer and binary of at least one 15 group element compound of binary |
| US15/511,911 US10269562B2 (en) | 2014-09-26 | 2015-09-25 | Use of at least one binary group 15 element compound, a 13/15 semiconductor layer and binary group 15 element compounds |
| EP15781035.9A EP3198053B1 (en) | 2014-09-26 | 2015-09-25 | Use of at least one binary group 15 element compound, a 13/15 semiconductor layer and binary group 15 element compounds. |
| JP2017535963A JP6695883B2 (en) | 2014-09-26 | 2015-09-25 | Use of at least one group 15 element binary compound, group III-V semiconductor layer, and group 15 element binary compound |
| KR1020237033905A KR20230142844A (en) | 2014-09-26 | 2015-09-25 | Use of at least one binary group 15 element compound, a 13/15 semiconductor layer and binary group 15 element compounds |
| RU2017114394A RU2705365C2 (en) | 2014-09-26 | 2015-09-25 | Using at least one binary compound of group element 15, 13/15 of semiconductor layer and binary compounds of element of group 15 |
| KR1020177010647A KR20170070062A (en) | 2014-09-26 | 2015-09-25 | Use of at least one binary group 15 element compound, a 13/15 semiconductor layer and binary group 15 element compounds |
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| DE102014014036.9 | 2014-09-26 | ||
| DE102014014036.9A DE102014014036A1 (en) | 2014-09-26 | 2014-09-26 | Use of at least one binary group 15 element compound, a 13/15 semiconductor layer and binary group 15 element compounds |
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| US (1) | US10269562B2 (en) |
| EP (1) | EP3198053B1 (en) |
| JP (1) | JP6695883B2 (en) |
| KR (2) | KR20230142844A (en) |
| CN (1) | CN107075672B (en) |
| DE (1) | DE102014014036A1 (en) |
| RU (1) | RU2705365C2 (en) |
| TW (1) | TWI679208B (en) |
| WO (1) | WO2016046394A1 (en) |
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| FR2190830A1 (en) * | 1972-07-06 | 1974-02-01 | Inst Francais Du Petrole | Asymmetric bidentate coordinating cmpds - for prepn of hydrogenation catalysts giving optically active products |
| US20140220733A1 (en) * | 2006-11-02 | 2014-08-07 | Advanced Technology Materials, Inc. | Antimony and germanium complexes useful for cvd/ald of metal thin films |
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| US4999223A (en) * | 1990-02-22 | 1991-03-12 | Cvd Incorporated | Chemical vapor deposition and chemicals with diarsines and polyarsines |
| US5124278A (en) * | 1990-09-21 | 1992-06-23 | Air Products And Chemicals, Inc. | Amino replacements for arsine, antimony and phosphine |
| JPH05121340A (en) * | 1991-03-29 | 1993-05-18 | Toshiba Corp | Vapor phase growth method of chemical compound semiconductor film |
| US6060119A (en) * | 1997-02-10 | 2000-05-09 | The United States Of America As Represented By The Secretary Of The Navy | Compound tertiarybutylbis-(dimethylamino)phosphine and a process for preparing the compound tertiarybutylbis-(dimethylamino)phosphine |
| US5902639A (en) * | 1997-03-31 | 1999-05-11 | Advanced Technology Materials, Inc | Method of forming bismuth-containing films by using bismuth amide compounds |
| JP2000082673A (en) * | 1998-09-04 | 2000-03-21 | Telecommunication Advancement Organization Of Japan | Thin-film formation method and device |
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2014
- 2014-09-26 DE DE102014014036.9A patent/DE102014014036A1/en not_active Withdrawn
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2015
- 2015-09-25 EP EP15781035.9A patent/EP3198053B1/en active Active
- 2015-09-25 US US15/511,911 patent/US10269562B2/en active Active
- 2015-09-25 CN CN201580051595.6A patent/CN107075672B/en active Active
- 2015-09-25 KR KR1020237033905A patent/KR20230142844A/en active Application Filing
- 2015-09-25 RU RU2017114394A patent/RU2705365C2/en active
- 2015-09-25 JP JP2017535963A patent/JP6695883B2/en active Active
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| FR2190830A1 (en) * | 1972-07-06 | 1974-02-01 | Inst Francais Du Petrole | Asymmetric bidentate coordinating cmpds - for prepn of hydrogenation catalysts giving optically active products |
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| EP3198053A1 (en) | 2017-08-02 |
| US10269562B2 (en) | 2019-04-23 |
| US20170243740A1 (en) | 2017-08-24 |
| TW201619172A (en) | 2016-06-01 |
| RU2705365C2 (en) | 2019-11-07 |
| CN107075672B (en) | 2019-10-18 |
| JP2017537478A (en) | 2017-12-14 |
| JP6695883B2 (en) | 2020-05-20 |
| DE102014014036A1 (en) | 2016-03-31 |
| RU2017114394A (en) | 2018-10-26 |
| RU2017114394A3 (en) | 2019-01-30 |
| TWI679208B (en) | 2019-12-11 |
| KR20230142844A (en) | 2023-10-11 |
| KR20170070062A (en) | 2017-06-21 |
| EP3198053B1 (en) | 2021-07-28 |
| CN107075672A (en) | 2017-08-18 |
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