DD294976A5 - METHOD FOR PRODUCING DUENNER OXYDE LAYERS THROUGH THE PLASMA IMPLEMENTATION OF METAL ORGANIC COMPOUNDS - Google Patents
METHOD FOR PRODUCING DUENNER OXYDE LAYERS THROUGH THE PLASMA IMPLEMENTATION OF METAL ORGANIC COMPOUNDS Download PDFInfo
- Publication number
- DD294976A5 DD294976A5 DD34136990A DD34136990A DD294976A5 DD 294976 A5 DD294976 A5 DD 294976A5 DD 34136990 A DD34136990 A DD 34136990A DD 34136990 A DD34136990 A DD 34136990A DD 294976 A5 DD294976 A5 DD 294976A5
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- German Democratic Republic
- Prior art keywords
- metal compounds
- compounds
- layers
- metal
- plasma
- Prior art date
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- 150000002902 organometallic compounds Chemical class 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 31
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000006073 displacement reaction Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 239000001272 nitrous oxide Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 210000002381 plasma Anatomy 0.000 description 16
- 238000000151 deposition Methods 0.000 description 15
- 230000008021 deposition Effects 0.000 description 15
- 239000007858 starting material Substances 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- ZRLCXMPFXYVHGS-UHFFFAOYSA-N tetramethylgermane Chemical compound C[Ge](C)(C)C ZRLCXMPFXYVHGS-UHFFFAOYSA-N 0.000 description 8
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- -1 cyclooctadienyl Chemical group 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000002887 superconductor Substances 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 101150071927 AANAT gene Proteins 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 150000004697 chelate complex Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 238000001182 laser chemical vapour deposition Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- 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
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
-
- 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
- C23C16/40—Oxides
-
- 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
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
-
- 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
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur Herstellung duenner Oxidschichten durch die Plasmaumsetzung metallorganischer Verbindungen, dadurch gekennzeichnet, dasz fluechtige Metallverbindungen oder Mischungen aus Metallverbindungen verwendet werden. Das erfindungsgemaesze Verfahren vermeidet nicht nur die Nachteile der bekannten Verfahren, sondern es schafft darueber hinaus voellig neue technische Perspektiven.{Verfahren; Herstellung duenner Oxidschichten; Plasmaumsetzung metallorganischer Verbindungen; fluechtige Metallverbindungen}The invention relates to a process for the preparation of thin oxide layers by the plasma displacement of organometallic compounds, characterized in that volatile metal compounds or mixtures of metal compounds are used. The process according to the invention not only avoids the disadvantages of the known processes, but also creates completely new technical perspectives. Production of thin oxide layers; Plasma decomposition of organometallic compounds; volatile metal compounds}
Description
Anwendungsgebiet dor ErfindungField of application of the invention
Die Erfindung betrifft ein Verfahren zur Herstellung dünner Oxydschichten durch die Plasmaumsetzung metallorganischer Verbindungen.The invention relates to a method for producing thin oxide layers by the plasma displacement of organometallic compounds.
Charakteristik des bekannten Standes der TechnikCharacteristic of the known state of the art
Die Herstellung von Oxydschichten oder -filmen ist an sich bekannt.The preparation of oxide layers or films is known per se.
So kann man Oxydschichten durch Sputtern erzeugen. Aber Oxyde sputtern relativ schlecht. Oft weisen die Produkte Sauerstoffdefizite auf und müssen nachoxydiert werden.So you can produce oxide layers by sputtering. But oxides sputter relatively badly. Often, the products have oxygen deficiencies and need to be post-oxygenated.
Weiterhin kann man Oxydschichten durch reaktives Sputtern erzeugen. Dies vermeidet die Notwendigkeit der Nachoxydation.Furthermore, one can produce oxide layers by reactive sputtering. This avoids the need for postoxidation.
Oft sind die Abscheideraten gering. Ferner ist der apparative Aufwand (sehr gutes Vakuum erforderlich) beträchtlich. Bei allen Sputtorverfahren tritt Schattenbildung auf, das heißt dreidimensionale Objekte werden nicht gleichmäßig beschichtet.Often the deposition rates are low. Furthermore, the expenditure on equipment (very good vacuum required) is considerable. Shadow formation occurs in all sputtering processes, ie three-dimensional objects are not uniformly coated.
Es ist auch möglich, Oxydschichten in Einzelfällen durch galvanische Verfahren oder auf Metallen durch Oxydation bei höheren Temperaturen zu erzeugen.It is also possible to produce oxide layers in individual cases by galvanic processes or on metals by oxidation at higher temperatures.
Schließlich können Oxydschichten durch thermisches- oder Laser-CVD-Verfahren abgeschieden werden.Finally, oxide layers can be deposited by thermal or laser CVD method.
Ziel der ErfindungObject of the invention
Das erfindungsgemäße Verfahren vermeidet nicht nur die Nachteile der bekannten Verfahren, sondern es schafft darüber hinaus völlig neue technische Perspektiven.The method according to the invention not only avoids the disadvantages of the known methods, but also creates completely new technical perspectives.
Darlegung dos Wesens der ErfindungExplanation of the essence of the invention
Aufgabe der vorliegenden Erfindung Ist die Zurverfügungstellung eines Verfahrens, welches in technisch einfacher Weise für eine Vielzahl von Beschichtungen anwendbar ist, welches Metall für Beschichtungen zugänglich macht, von denen es keine flüchtigen Hydride oder Halogenide gibt und das hierdurch eine erhöhte Anwendungsbreite besitzt und welches die Herstellung von Oxydschichten erlaubt, die ganz oder weitgehend frei von Verunreinigungen sind.Object of the present invention is the provision of a method which is applicable in a simple manner for a variety of coatings, which makes metal accessible for coatings, of which there are no volatile hydrides or halides and thereby has an increased application and which the production allowed by oxide layers that are wholly or largely free of impurities.
Diese Aufgabe wird erfindungsgemäß durch ein Verfahren zur Herstellung dünner Oxydschichten durch die Plasmaumsetzung metallorganischer Verbindungen gelöst, welches sich dadurch auszeichnet, daß flüchtige Metallverbindungen oder Mischungen aus Metallverbindungen verwendet werden.This object is achieved by a method for producing thin oxide layers by the plasma decomposition of organometallic compounds, which is characterized in that volatile metal compounds or mixtures of metal compounds are used.
Weitere Ausgestaltungen der Erfindung zeichnen sich dadurch aus,Further embodiments of the invention are characterized by
- daß Metallverbindungen verwendet werden, die außer den Metallatomen auch Kohlenstoff enthalten;- That metal compounds are used which contain carbon in addition to the metal atoms;
- daß Metallverbindungen verwendet werden, bei denen die Metallatome entweder direkt oder über n-Bindungen oder über Heteroatome wie Sauerstoff, Stickstoff, Schwefel oder Phosphor mit dem Kohlenstoff verbunden sind;- That metal compounds are used in which the metal atoms are connected either directly or via n-bonds or heteroatoms such as oxygen, nitrogen, sulfur or phosphorus with the carbon;
- daß die Metallverbindungen zusammen mit einem Oxydationsmittel als Reaktivgas verwendet werden;- That the metal compounds are used together with an oxidizing agent as a reactive gas;
- daß als Oxydationsmittel Sauerstoff, Kohlendioxyd, Distickstoffoxyd oder deren Mischungen verwendet werden;- That are used as the oxidant oxygen, carbon dioxide, nitrous oxide or mixtures thereof;
- daß das Reaktivgas in Mischung mit einem Verdünnungsmittel wie Helium, Argon oder Stickstoff verwendet wird, Das erfindungsgemäße Verfahren ist durch folgende Verfahrensschritte gekennzeichnet:- That the reactive gas is used in admixture with a diluent such as helium, argon or nitrogen, The inventive method is characterized by the following process steps:
- Zufügüng der Metallverbindungen über Dosierventile dem Reaktor- Zufügüng the metal compounds via metering the reactor
- Beheizung des Verdampfungsgefäßes für die Metallverbindungen und der Zuleitungen zum Reaktor- Heating the evaporation vessel for the metal compounds and the supply lines to the reactor
- Umsetzung bei vermindertem Druck, wobei die Verbindungen dem Plasma einer elektrischen Entladung ausgesetzt werden. Eine weitere bevorzugte Ausführungsform der Erfindung besteht darin, daß für die Umsetzung eine Glimmentladung verwendet wird. Diese Glimmentladung wird in Parallelplattenreaktoren, Barrelreaktoren oder anderen Anlagen erzeugt. Die Glimmentladung kann mit Gleichspannung oder nieder- oder hochfrequenter Wechselspannung betrieben werden. Wiederum eine weitere bevorzugte Ausführungsform der Erfindung ist dadurch gekennzeichnet, daß an die Elektroden der Parallelreaktoren eine Zusatzspannung angelegt wird. Die Elektroden, auf denen die zu beschichtenden Substrate liegen sowie andere Substratträger werden thermostatisiert.- Reaction at reduced pressure, wherein the compounds are exposed to the plasma of an electrical discharge. Another preferred embodiment of the invention is that a glow discharge is used for the reaction. This glow discharge is generated in parallel plate reactors, barrel reactors or other equipment. The glow discharge can be operated with DC voltage or low or high frequency AC voltage. Yet another preferred embodiment of the invention is characterized in that an additional voltage is applied to the electrodes of the parallel reactors. The electrodes on which the substrates to be coated and other substrate carriers are thermostated.
Das Verfahren ist einfach und für eine Vielzahl von Beschichtungen anwendbar. Je nach gewünschtem Oxyd muß eine geeignete metallhaltige Verbindung eingesetzt werden. Die experimentellen Parameter unterscheiden sich für die meisten Probleme nur wenig voneinander.The process is simple and applicable to a variety of coatings. Depending on the desired oxide, a suitable metal-containing compound must be used. The experimental parameters differ little from each other for most problems.
Durch die Verwendung von metallhaltigen Ausgangsverbindungen werden auch Metalle für die Beschichtungen zugänglich, von denen es keine flüchtigen Hydride oder Halogenide gibt. Dadurch wird die Anwendungsbreite wesentlich vergrößert.The use of metal-containing starting compounds also makes metals accessible to the coatings, of which there are no volatile hydrides or halides. As a result, the scope of application is significantly increased.
Durch den Zusatz von Oxydationsmitteln werden Verunreinigungen aus den Filmen ganz oder weitgehend entfernt.The addition of oxidants impurities from the films are completely or largely removed.
Durch die Verwendung von elektrischen Entladungen (Plasmen) kenn die Zersetzungstemperatur gegenüber dem thermischen CVD erheblich herabgesetzt werden. Erfahrungen auszahlreichen Systemen zeigen, daß Plasmaverfahren schon bei um 5000C tieferen Temperaturen als die thermischen Verfahren zur Beschichtung eingesetzt werden. Dadurch können die Verfahren auch bei temperaturempfindlichen Materialien wie organischen Polymeren eingesetzt werden.By using electrical discharges (plasmas), the decomposition temperature can be significantly reduced compared to thermal CVD. Experiences auszahlreichen systems show that plasma processes are already used at 0 to 500 C lower temperature than the thermal method for coating. As a result, the methods can also be used in temperature-sensitive materials such as organic polymers.
Durch die Verwendung von Plasmen treten keine Probleme mit der Schattenbildung auf. Es können dreidimensionale Objekte und auch Hohlräume (Löcher) beschichtet werden.The use of plasmas does not cause any problems with shadowing. Three-dimensional objects as well as cavities (holes) can be coated.
Durch die Verwendung von Plasmen ist die wachsende Schicht einem ständigen Bombardement von Ionen, Elektronen und Photonen ausgesetzt. Diese bewirken die Entfernung von Verunreinigungen und erhöhen die Oberflächenbeweglichkeit der auftreffenden Teilchen.Through the use of plasmas, the growing layer is exposed to a constant bombardment of ions, electrons and photons. These cause the removal of impurities and increase the surface mobility of the impinging particles.
Durch die Verwendung von Plasmen werden die zu beschichtenden Substrate von Verunreinigungen und anhaftonder Feuchtigkeit gereinigt. Dadurch werden wesentlich bessere Haftfestigkeiten erzielt als bei anderen Verfahren.By using plasmas, the substrates to be coated are cleaned of impurities and adhesive moisture. As a result, much better adhesive strengths are achieved than with other methods.
Durch die Verwendung von Zusatzpotentialen an den Elektroden kann das Ionenbombardement der wachsenden Schicht gesteuert werden.By using additional potentials at the electrodes, the ion bombardment of the growing layer can be controlled.
Durch die Temperierung der Elektrode, die die Substrate trägt oder der Substrathalter kann die Abscheidegeschwindigkeit und das Ausmaß der zulässigen Verunreinigungen gesteuert werden.By controlling the temperature of the electrode carrying the substrates or the substrate holder, the rate of deposition and the extent of permissible contaminants can be controlled.
Zur Durchführung des erfindungsgemäßen Verfahrens kommen als Ausgangsmaterialien alle flüchtigen metallhaltigen beziehungsweise metallorganischen Verbindungen in Frage, vor allem solche, die bei Raumtemperatur einen Dampfdruck von > 1 Pa besitzen sowie all diejenigen Verbindungen, die man ohne Zersetzung auf Temperaturen bringen kann, bei denen diese Drücke erreicht werden, und ferner diejenigen, die solche Temperaturbehandlung zumindest ohne übermäßige Zersetzung überstehen.Suitable starting materials for carrying out the process according to the invention are all volatile metal-containing or organometallic compounds, especially those which have a vapor pressure of> 1 Pa at room temperature and all those compounds which can be brought to temperatures without decomposition at which these pressures are reached and, furthermore, those which survive such thermal treatment at least without excessive decomposition.
Folgende Ausgangsverbindungen sind zu nennen:The following starting compounds can be mentioned:
Substanzen können eingesetzt werden, bei denen direkte Metall-Kohlenstoff-Bindungen wie zum Beispiel bei den Metallalkylen Sn(CH3I4, SN(C2Hg)4 oder Sn(C3H7J4SOWIe solchen mit gemischten Alkylen SnR'R"R'"R"", wie GeR4, PbR4, ZnR2, CdR2, InR31AsR3 oder BiR3.Substances can be used in which direct metal-carbon bonds, such as, for example, with the metal alkyls Sn (CH 3 I 4 , SN (C 2 Hg) 4 or Sn (C 3 H 7 J 4 SO with those with mixed alkylene SnR'R "R '" R "" such as GeR 4 , PbR 4 , ZnR 2 , CdR 2 , InR 31 AsR 3 or BiR 3 .
- Gebundene Komplexe wib Verbindungen mit Allyl-, Cyclopentadienyl-, Alkylcyclopentadienyl-, Cyclooctadienyl- oder Aromatenkomplexe wie zum Beispiel Pd(C3He)2, Pd(C5H6I2, (C6H5)Pd(C3Ha), Pd(RnC6H6^)2 oder (C6H6)Pd(RnC6^) oder entsprechende Verbindungen andrerer Metalle zum Beispiel des Eisens, Cobalts oder Nickels wie Fe(C6H6I2, Co(C5H5I2, Ni(C6H5)2 oder solche mit anderen Liganden wie FelRnCeHe-nfo.Bound complexes are compounds with allyl, cyclopentadienyl, alkylcyclopentadienyl, cyclooctadienyl or aromatic complexes, for example Pd (C 3 H e ) 2 , Pd (C 5 H 6 I 2 , (C 6 H 5 ) Pd (C 3 Ha), Pd (RnC 6 H 6 ^) 2 or (C 6 H 6 ) Pd (R n C 6 ^) or corresponding compounds of other metals, for example of iron, cobalt or nickel, such as Fe (C 6 H 6 I 2 , Co (C 5 H 5 I 2 , Ni (C 6 H 5 ) 2 or those with other ligands such as FelRnCeHe-nfo.
Metallcarbonyle wie Cr(CO)6, Mo(CO),, W(CO)6, Mn2(CO)10, Re,(CO))0, Fe(CO)8, Ru(CO)6, Os2(CO)8, Co2(CO)8, Rh2(CO)8, Ir2(CO)8, Ni(CO)4, und deren Derivate wie die Metall-carbonyl-nitrosyle (M(NO)x(CO)y Metall-carbonyl-hydride MHx(CO)7 Metall-carbonyl-halide MHalx(C0)y zum Beispiel Co(CO)3(NO), FE(CO)2(NO)2 und mehrkernige CarbonyleMetal carbonyls such as Cr (CO) 6 , Mo (CO), W (CO) 6 , Mn 2 (CO) 10 , Re, (CO) ) O, Fe (CO) 8 , Ru (CO) 6 , Os 2 ( CO) 8 , Co 2 (CO) 8 , Rh 2 (CO) 8 , Ir 2 (CO) 8 , Ni (CO) 4 , and their derivatives such as the metal carbonyl nitrosyls (M (NO) x (CO) y metal carbonyl hydrides MH x (CO) 7 metal carbonyl halides MHal x (CO) y for example Co (CO) 3 (NO), FE (CO) 2 (NO) 2 and polynuclear carbonyls
Diketonatokomplexe wie die Acetylacetonate und deren durch Substitution durch Fluor oder Alkylgruppen gewonnenen Abkömmlinge. Typische Chelatbildner sind 2,4-Pentandion („acac"), 1,1,1-Trifluor-2,4-pentandion(„tfa"), 1,1,1,5,5,5-Hexafluor-2,4-pentandion(„hfa") 2,26,6-Tetramethyl-heptandion („thd") wie zum Beispiel Al(acac)3, Cr(acac)3, Zr(thd)2> Mg(thd)2, Cu(tfa)2, Metallalkoxyde M(OR)x wie zum Beispiel Ti(OC2Hs)41Ti(OC3H7I41Ti(OC4H1O)4USW.Diketonato complexes such as the acetylacetonates and their derivatives obtained by substitution by fluorine or alkyl groups. Typical chelating agents are 2,4-pentanedione ("acac"), 1,1,1-trifluoro-2,4-pentanedione ("tfa"), 1,1,1,5,5,5-hexafluoro-2,4 penta-dione ("hfa") 2,26,6-tetramethylheptanedione ("thd") such as Al (acac) 3 , Cr (acac) 3 , Zr (thd) 2> Mg (thd) 2 , Cu ( tfa) 2 , metal alkoxides M (OR) x such as Ti (OC 2 Hs) 41 Ti (OC 3 H 7 I 41 Ti (OC 4 H 1 O) 4 USW.
Entsprechende Verbindungen mitgemischten AlkoxygruppenM(OR)x.n(OR')n sowie die entsprechenden Silizium-oder Hafniumoder Zirkoniumverbindungen. Derivate organischer Säuren wie AI(CH3COO)3 Corresponding compounds with mixed alkoxy groups M (OR) x . n (OR ') n and the corresponding silicon or hafnium or zirconium compounds. Derivatives of organic acids such as Al (CH 3 COO) 3
Verbindungen mit verschiedenen Typen von Liganden wie zum Beispiel die oben erwähnten Nitrosyl-Carbonyl oder Halogenid-Carbonyl-Verbindungen.Compounds with various types of ligands such as the above-mentioned nitrosyl-carbonyl or halide-carbonyl compounds.
Kombinationen von Carbonylgruppen mit n-Systemen zum Beispiel (CsH6)Ti(CO)3 und entsprechende Zirkonium, Hafnium oder Siliziumverbindungen Kombinationen von n-Systemen mit Amingruppen wie zum Beispiel (RCsH4)Ti(NR2)3.Combinations of carbonyl groups with n-systems for example (CsH 6 ) Ti (CO) 3 and corresponding zirconium, hafnium or silicon compounds Combinations of n-systems with amine groups such as (RCsH 4 ) Ti (NR 2 ) 3 .
Kombinationen von Alkylgruppen und Alkoxygruppen zum Beispiel RnTi(OR)4.,, und entsprechende Zirkonium, Hafnium oder Siliziumverbindungen.Combinations of alkyl groups and alkoxy groups, for example R n Ti (OR) 4. ,, and corresponding zirconium, hafnium or silicon compounds.
Kombinationen von Alkylgruppen und Chelat-Liganden zum Beispiel (CH3)2Au(acac) Kombinationen von Alkylgruppen und n-Systemen zum Beispiel (C '3I3Pt(C6H6) sowie Kombinationen mit Nitril-, Isonitril-, Phosphin, Thioäther oder Thiol-Gruppen usw.Combinations of alkyl groups and chelate ligands for example (CH 3 ) 2 Au (acac) combinations of alkyl groups and n-systems for example (C '3I 3 Pt (C 6 H 6 ) and combinations with nitrile, isonitrile, phosphine, Thioethers or thiol groups, etc.
Erfindungsgemäß lassen sich insbesondere folgende Oxydschichten herstellen:In particular, the following oxide layers can be produced according to the invention:
SnO2, GeO2, Oxyde der Seltenen Erden, CuO, TiO2, MnOx, Cr2O3, ZnO, PtO2, AI2O3, BaO, SrO, ZrO2, Nb2O3, WO3, In2O3, NiO, Fe2O3, MoO3, AgO, CoO, HfO2, TaO2, PbO, Bi2O3 und Sb2O3.SnO 2 , GeO 2 , rare earth oxides, CuO, TiO 2 , MnO x , Cr 2 O 3 , ZnO, PtO 2 , Al 2 O 3 , BaO, SrO, ZrO 2 , Nb 2 O 3 , WO 3 , In 2 O 3 , NiO, Fe 2 O 3 , MoO 3 , AgO, CoO, HfO 2 , TaO 2 , PbO, Bi 2 O 3 and Sb 2 O 3 .
Für die erfindungsgemäß hergestellten Oxydschichten finden sich vielseitige Anwendungen, von denen beispielsweise die folgenden zu nennen sind:For the oxide layers produced according to the invention, there are versatile applications, of which the following can be mentioned, for example:
mechanische Schutzschichten Hartschichten Kratzschutzschichten Diffusionsbarrieren Korrosionsschutzschichten Dekorationsschichten optische Filter Antireflexbelege leitende und halbleitende Schichten dielektrische Schichten antistatische Belege für organische Polymere antistatische Belege in der Mikroelektronik Masken in der Mikroelektronik transparente Elektroden für Solarzellen heizbare Schichten zum Beispie! für Autofenster haftvermittelnde Schichten Basismaterialien für Supraleiter HTC-Supraleitermechanical protective coatings hard coatings scratch protection coatings diffusion barriers anticorrosive coatings decorative coatings optical filters antireflective coatings conductive and semiconducting layers dielectric layers antistatic proofs for organic polymers antistatic evidence in microelectronics masks in microelectronics transparent electrodes for solar cells heatable layers! Coating layers for car windows Base materials for superconductors HT C superconductor
Im Vordergrund stehen die mechanischen Eigenschaften, Härte, Elastizität, optischen Eigenschaften, Transparenz, Farbe, Brechungsindex, elektrischen Eigenschaften: Isolatoren, Halbleiter und Leiter. Die folgenden Beispiele dienen zur Erläuterung der Erfindung.In the foreground are the mechanical properties, hardness, elasticity, optical properties, transparency, color, refractive index, electrical properties: insulators, semiconductors and conductors. The following examples serve to illustrate the invention.
SnOjt-FilmeSnOjt movies
Als Ausgangsmaterial dient Tetramethylzinn (TMT).The starting material is tetramethyltin (TMT).
Apparatur: Parallelplattenreaktor, Aluminiumelektroden 13cm 0,3cm Abstand Frequenz: 13,56MHz Art der Substrate: Glas Vorbehandlung: 30min Argonplasma Temperatur des Verdampfungsgefäßes: 25°C Gasart: O2/Ar (2:1 bis 3:1) Gasdurchsatz: 45sccm Druck: 50-133PaApparatus: Parallel plate reactor, aluminum electrodes 13cm 0.3cm spacing Frequency: 13.56MHz Type of substrates: glass Pretreatment: 30min Argon plasma Evaporator temperature: 25 ° C Gas type: O 2 / Ar (2: 1 to 3: 1) Gas flow rate: 45sccm Pressure : 50-133Pa
Leistungsdichte W/cm2 Elektrodenfläche: 1,5 Temperatur der Substrat tragenden Elektrode: 90°C Abscheldungsrate: bei 50-80Pa 50 A/min Filmeigenschaften: Farblose, transparente Filme, bei 50-80Pa Kohlenstoffgehalt unter Nachweisgrenze, bei Gesamtdruck 133Pa Abscheiderate 650A/min, 2-3% C Maximale Leitfähigkeit = 1,1 χ 103 ~' wird erreicht bei 50W Gesamtdruck 47 Pa, Verhältnis p(Oj)/p(TMT) = 2:1.Power density W / cm 2 Electrode area: 1.5 Substrate carrying electrode temperature: 90 ° C Rate of rejection: 50-80Pa 50 A / min Film properties: colorless, transparent films, at 50-80Pa carbon content below detection limit, at total pressure 133Pa, deposition rate 650A / min, 2-3% C Maximum conductivity = 1.1 χ 10 3 ~ 'is achieved at 50W total pressure 47 Pa, ratio p (Oj) / p (TMT) = 2: 1.
GeQ2-FilmeGeQ 2 movies
Als Ausgangsmaterial dient Tetramethylgermanium (TMG) Apparatur: ParallelplaUenreaktor, Aluminiumelektrode!! 13cm 0,3cm Abstand Frequenz: 13,56MHz Art der Substrate: Glas Vorbehandlung: 30min Argonplasma Temperatur des Verdampfungsgefäßes: -500C Gasart: O?/Ar (2:1 bis 3:1) Gasdurchsatz: 35sccm Druck: zum Beispiel 10Pa O2,5Pa Ar and 2,7 Pa TMG, Leistung: 70W Temperatur der Substrat tragenden Elektrode: 120°C Abscheidungsrate: SO A/min Filmeigenschaften:The starting material is tetramethylgermanium (TMG) Apparatus: parallel plate reactor, aluminum electrode !! 13cm 0,3cm distance Frequency: 13,56MHz Kind of substrates: glass Pretreatment: 30min Argon plasma Temperature of the evaporation vessel: -50 0 C Gas type: O ? / Ar (2: 1 to 3: 1) Gas flow rate: 35sccm Pressure: for example 10Pa O 2 , 5Pa Ar and 2.7 Pa TMG, Power: 70W Substrate carrying electrode temperature: 120 ° C Deposition rate: SO A / min Film properties :
Farblose, transparente Filme, Eigenschaften und Zusammensetzung weitgehend unabhängig von den Abscheidungsparametern.Colorless, transparent films, properties and composition largely independent of the deposition parameters.
Ge-Gehalt 70 + 4% (GeO2 = 69,4% Ge) Dichte 3,5-4,5g/cm3 Ge content 70 + 4% (GeO 2 = 69.4% Ge) Density 3.5-4.5 g / cm 3
Gemischte GeO2-SnO2 Filme Als Ausgangsmaterial dient Tetramethylgermanium (TMG) und Tetramethylzinn (TMT).Mixed GeO 2 -SnO 2 Films The starting material is tetramethylgermanium (TMG) and tetramethyltin (TMT).
Apparatur: ParallelplaUenreaktor, Aluminiumelektroden 13 cm 0,3 cm Abstand Frequenz: 13,56MHz Art der Substrate: Glas Vorbehandlung: 30min Argonplasma Temperatur des Verdampfungsgefäßes: 250C beziehungsweise -5O0C TMT und TMG werden vor dem Eintritt in die Reaktionskammer gemischt Gasart: Ar/O2 (1:3) Gasdurchsatz: 40sccm Druck: Gesamtdruck 30Pa, Partialdruck der organomet. Verbindungen 5Pa Leistung: 8OW Temperatur der Substrat tragenden Elektrode:Apparatus: parallel plate reactor, aluminum electrodes 13 cm 0.3 cm distance Frequency: 13.56MHz Type of substrates: glass Pretreatment: 30min Argon plasma Evaporator temperature: 25 0 C or -5O 0 C TMT and TMG are mixed before entering the reaction chamber : Ar / O 2 (1: 3) Gas flow rate: 40sccm Pressure: total pressure 30Pa, partial pressure of organomet. Compounds 5Pa Performance: 8OW Temperature of Substrate Carrying Electrode:
Abscheidungsrate: 50-100 A/min Filmeigenschaften:Deposition rate: 50-100 A / min.
Die Filmzusammensetzung hängt ab vom Mischungsverhältnis TMG/TMTThe film composition depends on the mixing ratio TMG / TMT
P(TMT)Pa p(TMG)Pa Snat.-% Geat.-% Cat.-% Oat.-%P (TMT) Pa p (TMG) Pa Snat% Geat% Cat% Oat%
Filme aus Zirkondioxid Ausgangsmaterial: Zirkoniumhexaf luoroacetylacetonat Apparatur: ParallelplaUenreaktor, Aluminiumelektroden = 30cm Abstand 3cm Frequenz: 30,5MHz Art der Substrate: Glas, Quarz Vorbehandlung: 10min Argonplasma Temperatur des Verdampfungsgefäßes: 6O0C Gasart: Sauerstoff Gasdurchsatz: SOsccm Druck: 23PaZirconium dioxide films Starting material: zirconium hexafluoroacetylacetonate Apparatus: parallel plate reactor, aluminum electrodes = 30cm 3cm spacing Frequency: 30.5MHz Substrate type: glass, quartz Pretreatment: 10min Argon plasma Evaporating vessel temperature: 6O 0 C Gas type: oxygen Gas flow rate: SOsccm Pressure: 23Pa
Leistung: 5OW Temperatur der Substrat tragenden Elektrode: 15O0C Abscheidungsrate: 12,5nm/min Filmeigenschaften: Durchsichtige farblose, nichtleitende, amorphe, sehr harte und kraufeste Filme Filmanalyse 69,3% Zr, 0,4% C (ZrO2 74%)Performance: 5OW Substrate Electrode Temperature: 15O 0 C Deposition Rate: 12.5nm / min Film Properties: Clear Colorless, Nonconductive, Amorphous, Very Hard and Resistant Films Film Analysis 69.3% Zr, 0.4% C (ZrO 2 74% )
Abscheidung von ZrOj-Fllmen Ausgangsmaterial Dicyclopentadlenyl-dlmethyl-Zlrkonium Cp2ZrMe2 Apparatur: Parallelplattenreaktor, Alumlniumelektroden 16cm 0,3,5cm Abstand Frequenz: 13,56MHz Art der Substrate: Glas, Quarz, Polycarbonat Vorbehandlung: 30min Argonplasma 100W Temperatur des Verdampfungsgefäßes:Separation of ZrOj liquids Starting material Dicyclopentadlenyl-dlmethyl-Zlrkonium Cp 2 ZrMe 2 Apparatus: Parallel plate reactor, aluminum electrodes 16cm 0,3,5cm distance Frequency: 13,56MHz Kind of substrates: glass, quartz, polycarbonate Pretreatment: 30min Argon plasma 100W Temperature of evaporating vessel:
Gasarti'Sauerstoff Gasdurchsatz: lOOsccm Druck: 22Pa Leistung: 100W Temperatur der Substrat tragenden Elektrode: 3000C Abscheidungsrate: 0,3-0,Bg/cm2 min Filmeigenschaften: Klare transparente, sehr harte Filme. Analyse 72,3 + 4% Zr (theor. für ZrO2 74,0%).Gasarti'Sauerstoff gas flow rate: lOOsccm pressure: 22Pa Power: 100W temperature of the substrate-supporting electrode 300 0 C deposition rate: 0.3 to 0, Bg / cm 2 min Film Characteristics: Clear transparent, very hard films. Analysis 72.3 + 4% Zr (theor. For ZrO 2 74.0%).
Abscheidung von AI2Oa-FiImCn Ausgangsmaterial Trimethylaluminium Apparatur: Parallelplattenreaktor, Aluminiumelektroden 11 cm 0,2,5cm Abstand Frequenz: 13,66MHz Art der Substrate: Glas, AI2O3 Vorbehandlung: 15min Argonplasma Temperatur des Verdampfungsgefäßes: O0C Gasart: Argon/Wasserstoff Gasdurchsatz: 20sccm Druck: 200mtorr (40% Argon, 40% H2,10% Alkylverbindung) Leistung: 60 Watt Temperatur der Substrat tragenden Elektrode: 15O0C Abscheidungsrate: 40-60A Filmeigenschaften: farblose, transparente Filme Die geringen Mengen an adsorbiertem Wasser aus der Apparatur oder aus Lecks sind ausreichend für die Oxydbildung.Deposition of Al 2 Oa-FiImCn starting material trimethylaluminium apparatus: parallel plate reactor, aluminum electrodes 11 cm 0,2,5cm distance frequency: 13,66MHz kind of substrates: glass, Al 2 O 3 pretreatment: 15min argon plasma temperature of evaporation vessel: O 0 C gas type: Argon / Hydrogen Gas flow rate: 20sccm Pressure: 200mtorr (40% argon, 40% H 2 , 10% alkyl compound) Power: 60 Watt Temperature of substrate supporting electrode: 15O 0 C Deposition rate: 40-60A Film properties: colorless, transparent films The small amounts of adsorbed water from the apparatus or leaks are sufficient for oxide formation.
Erzeugung von Cr2Os-FiImBn Ausgangsmaterial Chromhexacarbonyl Cr(CO)6 Apparatur: Parallelplattenreaktor, Aluminiumelektroden 13 cm 0,3 cm Absta nd Frequenz: 13,56MHz Art der Substrate: Glas, Quarz, Stahl Vorbehandlung: keine Temperatur des Verdampfungsgefäßes: 50°C Gasart: Argon/Sauerstoff zu gleichen Teilen Gasdurchsatz: 25sccm Druck: 20Pa Leistung: 100 Watt Temperatur der Substrat tragenden Elektrode: 1000C Abscheidungsrate: 23 A/min Filmeigenschaften:Generation of Cr 2 Os-FiImBn Starting material Chromium hexacarbonyl Cr (CO) 6 Apparatus: Parallel plate reactor, aluminum electrodes 13 cm 0.3 cm spacing Frequency: 13.56MHz Substrate type: glass, quartz, steel Pretreatment: none Evaporating vessel temperature: 50 ° C Gases: argon / oxygen in equal gas flow rate: 25sccm pressure: 20Pa power: 100 W temperature of the substrate-supporting electrode 100 0 C deposition rate: 23 A / min film properties:
Film transparent, schwach grün, 67% Cr (Cr2O3 theor. 68,4% Cr)Film transparent, pale green, 67% Cr (Cr 2 O 3 theor. 68.4% Cr)
Erzeugung von armorphen Mnx0y-Filmen Ausgangsverbindung: Dimangandecacarbonyl Mn2(CO)10 Apparatur: Parallelplattenreaktor, Aluminiumelektroden 13cm 0,3cm Abstand Frequenz: 13,56MHz Art der Substrate:Generation of Armor Mn x 0 y Films Starting Compound: Dimangandecacarbonyl Mn 2 (CO) 10 Apparatus: Parallel Plate Reactor, Aluminum Electrodes 13cm 0.3cm Spacing Frequency: 13.56MHz Substrate Type:
Vorbehandlung:pretreatment:
Temperatur des Verdampfungsgefäßes: 600C Gasart: Argon beziehungsweise Sauerstoff Gasdurchsatz: 3Üsccm Druck: 25Pa Leistung: 100 Watt Temperatur der Substrat tragenden Elektrode: 100°C Abscheidungsrate: 2,5-3,5A/sec Filmeigenschaften:Temperature of the evaporation vessel: 60 0 C Type of gas: argon and oxygen, gas flow rate: 3Üsccm pressure: 25Pa power: 100 W Temperature of the substrate carrying electrode: 100 ° C Deposition Rate: 2,5-3,5A / sec film properties:
Mit Trägergas Argon bräunliche transparente Filme mit 71 % Mn (Mn2O3 69,6%, Mn3O4 72,0%).With carrier gas argon brownish transparent films with 71% Mn (Mn 2 O 3 69.6%, Mn 3 O 4 72.0%).
Mit Trägergas Sauerstoff (35sccm, 28Pa) dunkelbraune Filme, derun Metallgehalt 65% beträgt, laut ESCA-Untersuchungen liegt ein Gemisch aus MnO2 und Mn2O3 vor.With carrier gas oxygen (35sccm, 28Pa) dark brown films, which has a metal content of 65%, according to ESCA studies, there is a mixture of MnO 2 and Mn 2 O 3 .
Druck: 26PaPressure: 26Pa
85,1 % Er, Kohlenstoff unter Nachweisgrenze,85.1% Er, carbon below detection limit,
10cm 0,4cm Absta nd10cm 0.4cm spacing
Druck: 93PaPressure: 93Pa
Leistung: 100WPower: 100W
Claims (14)
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| Application Number | Priority Date | Filing Date | Title |
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| DE19893918932 DE3918932A1 (en) | 1989-06-08 | 1989-06-08 | METHOD FOR PRODUCING THIN OXIDE LAYERS BY PLASMA IMPLEMENTATION OF METAL ORGANIC COMPOUNDS |
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| EP (1) | EP0460254A1 (en) |
| JP (1) | JPH03111574A (en) |
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| US5395642A (en) * | 1992-10-21 | 1995-03-07 | Solvay Deutschland Gmbh | Process for depositing layers having high specific electrical conductivity |
| JPH06248455A (en) * | 1993-02-25 | 1994-09-06 | Japan Energy Corp | Method for manufacturing ZrO2 film |
| GB9421335D0 (en) * | 1994-10-22 | 1994-12-07 | Epichem Ltd | Chemical vapour deposition |
| KR0164984B1 (en) * | 1995-12-04 | 1999-01-15 | 강박광 | Method of forming aluminum oxide film from dialkyl aluminum alkylate by chemical vapor deposition |
| WO1998016667A1 (en) * | 1996-10-16 | 1998-04-23 | The President And Fellows Of Harvard College | Chemical vapor deposition of aluminum oxide |
| JP2002105641A (en) | 2000-10-03 | 2002-04-10 | Murakami Corp | Composite material and manufacturing method |
| JP4221526B2 (en) * | 2003-03-26 | 2009-02-12 | キヤノンアネルバ株式会社 | Film forming method for forming metal oxide on substrate surface |
| US7160578B2 (en) | 2004-03-10 | 2007-01-09 | Pilkington North America | Method for depositing aluminum oxide coatings on flat glass |
| GB2432363B (en) | 2005-11-16 | 2010-06-23 | Epichem Ltd | Hafnocene and zirconocene precursors, and use thereof in atomic layer deposition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4140814A (en) * | 1977-12-01 | 1979-02-20 | Texas Instruments Incorporated | Plasma deposition of transparent conductive layers |
| US4675089A (en) * | 1985-11-25 | 1987-06-23 | At&T Technologies, Inc. | Low temperature deposition method for high quality aluminum oxide films |
| US4975324A (en) * | 1986-10-21 | 1990-12-04 | Matsushita Electric Industrial Co., Ltd. | Perpendicular magnetic film of spinel type iron oxide compound and its manufacturing process |
| JPH0829943B2 (en) * | 1988-05-13 | 1996-03-27 | 沖電気工業株式会社 | Method of forming superconductor thin film |
-
1989
- 1989-06-08 DE DE19893918932 patent/DE3918932A1/en not_active Withdrawn
-
1990
- 1990-06-06 DD DD34136990A patent/DD294976A5/en not_active IP Right Cessation
- 1990-06-06 EP EP90110659A patent/EP0460254A1/en not_active Withdrawn
- 1990-06-07 CA CA 2018464 patent/CA2018464A1/en not_active Abandoned
- 1990-06-08 JP JP14885890A patent/JPH03111574A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CA2018464A1 (en) | 1990-12-08 |
| EP0460254A1 (en) | 1991-12-11 |
| DE3918932A1 (en) | 1990-12-13 |
| JPH03111574A (en) | 1991-05-13 |
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| EP | Request for examination under paragraph 12(1) filed | ||
| WP12 | As result of examination under paragraph 12 erstrg. patent revoked | ||
| WP12 | As result of examination under paragraph 12 erstrg. patent revoked |