CN108531890A - A kind of preparation method of transparent conductive metal oxide film and products thereof and purposes - Google Patents
A kind of preparation method of transparent conductive metal oxide film and products thereof and purposes Download PDFInfo
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- CN108531890A CN108531890A CN201810393733.4A CN201810393733A CN108531890A CN 108531890 A CN108531890 A CN 108531890A CN 201810393733 A CN201810393733 A CN 201810393733A CN 108531890 A CN108531890 A CN 108531890A
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- oxide film
- metal oxide
- transparent conductive
- conductive metal
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 59
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- 238000011065 in-situ storage Methods 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000011261 inert gas Substances 0.000 claims abstract description 20
- 238000004140 cleaning Methods 0.000 claims abstract description 18
- 239000010408 film Substances 0.000 claims description 111
- -1 alkyl compound Chemical class 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 210000002381 plasma Anatomy 0.000 description 48
- 238000000034 method Methods 0.000 description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000151 deposition Methods 0.000 description 14
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- 230000008021 deposition Effects 0.000 description 11
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 10
- 238000000231 atomic layer deposition Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003851 corona treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 3
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 3
- VXZBYIWNGKSFOJ-UHFFFAOYSA-N 2-[4-[5-(2,3-dihydro-1H-inden-2-ylamino)pyrazin-2-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC=1N=CC(=NC=1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 VXZBYIWNGKSFOJ-UHFFFAOYSA-N 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C23C16/44—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 method of coating
- C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
-
- 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
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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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
- C23C16/44—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 method of coating
- C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45536—Use of plasma, radiation or electromagnetic fields
- C23C16/4554—Plasma being used non-continuously in between ALD reactions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
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Abstract
The present invention relates to a kind of preparation methods of transparent conductive metal oxide film and products thereof and purposes, the preparation method to include the following steps：(1) it is passed through the first metal precursor into reaction chamber, cleans, is passed through H2O gases carry out chemisorption, then pass to inert gas auxiliary plasma build-up of luminance, in-situ oxidation, cleaning；(2) step (1) is repeated into N1After secondary, the first metal oxide film is obtained；(3) it is passed through the second metal precursor, cleans, is passed through H2O gases carry out chemisorption, then pass to inert gas auxiliary plasma build-up of luminance, in-situ oxidation, cleaning；(4) step (3) is repeated into N2After secondary, the second metal oxide film is obtained；(5) step (1)~(4) are repeated M times, obtains transparent conductive metal oxide film；Wherein, N1:N2=(14~21):(1~4), M=10~40.Realize the transparent conductive metal oxide film that low-resistivity is prepared under low temperature.
Description
Technical field
The present invention relates to technical field of manufacturing semiconductors more particularly to a kind of preparations of transparent conductive metal oxide film
Method and products thereof and purposes.
Background technology
Oxidic transparent conductive film is important optoelectronic information material, has very high permeability in visible region,
Infrared region has very high reflectivity again.The preparation process and post processing mode of film are special to the structure of transparent conductive film, optics
Property and electrology characteristic have larger impact, in addition, different doped chemicals influences the physically and electrically characteristic of film great, pass through
The doping level of control film can effectively improve film characteristics, these special photoelectric characteristics of oxidic transparent conductive film make
It is used widely in various fields such as solar cell, FPD.It is many that oxidic transparent conductive film method is prepared at present
It is more, include mainly：Magnetron sputtering, pulsed laser deposition, chemical vapor deposition, spray pyrolysis and sol-gel method.But these
There are larger differences for the ratio of preparation method metal oxide when preparing the conductive film of same resistivity, are unable to get quality
Stable Conducting Films with High Performance.
Atomic layer deposition (ALD) technology is sunk as a kind of potential deposition method preparing transparent conductive film compared to traditional
Product method has obvious advantage, including：Extensive deposition accurately controls film thickness by cycle-index, and with good
Uniformity and reproducibility.This novel deposition method can meet new technology research and development demand well, cause in recent years wide
General concern.In addition, be increasingly becoming one of the mainstream technology of the following display development for flexible flat panel display device part, flexible substrate without
Method bears long-time hot environment.Therefore, it is a kind of tool by technique for atomic layer deposition low temperature preparation high-performance nesa coating
Challenging technology.
CN101535524B discloses a kind of method and system carrying out plasma enhanced atomic layer deposition, solves half
Conductor processing is smaller and smaller in line width and conformality, adhesiveness and purity become the more and more important of semiconductor devices obtained by influence
Conditions under and generate various problems, the pollution problem between the material bed boundary of subsequent deposition is reduced, in same system
Middle offer is a kind of to restore compatible configuration with atomic layer deposition and plasma enhancing.But it does not solve efficient cryogenic and prepares gold
Belong to oxidic transparent conductive film.
CN100590819C discloses a kind of plasma enhanced atomic layer deposition method and comprising the film being consequently formed
Second processing material is introduced process chamber, utilizes electromagnetism by semiconductor devices after first introducing the first processing material in process chamber
Power coupling with generate promote first and second processing materials between reduction reaction plasmas, wait for the first processing material and
Reduction reaction between second processing material by the film with solid deposited on substrate after the completion of, third material reacts
Property gas introduce in process chamber and pollutant reaction, it is relatively slow and influence the film of deposition to solve deposition rate to a certain extent
The pollution problem of quality, but be not carried out efficient cryogenic and prepare transparent conductive metal oxide film.
CN1041195523A discloses a kind of plasma enhanced atomic layer deposition and prepares aluminum-doped zinc oxide films preparation
Method.By the way that the combination of n times Zinc oxide-base body thin film ALD deposition cycle and n times Al doping process cycle is carried out M cycle,
Aluminum zinc oxide film is successively formed, wherein Al doping process cycle includes the pretreatment of Al doping process；N=9~29；M=30~
90.Wherein film deposition and doping be all after introducing metal precursor to settling chamber, then directly use oxidized dose it is independent or with
The plasma of inert gas mixing carries out oxide deposition, finally realizes alumina doped into zinc oxide film, inhibition aluminium oxide mass
The generation of cluster and segregation, reduce the resistivity of film, but in its reaction process silicon temperature at 150 DEG C or more, gas
Heating temperature with precursor source pipeline is at 100 DEG C or more.
Therefore, it is necessary to develop a kind of method that high efficient cryogenic prepares low resistivity metal oxide transparent conductive film.
Invention content
In view of problems of the prior art, one of the objects of the present invention is to provide a kind of high efficient cryogenics to prepare low electricity
The method of resistance rate transparent conductive metal oxide film.
In a first aspect, the present invention provides a kind of preparation method of transparent conductive metal oxide film, include the following steps：
(1) it is passed through the first metal precursor into reaction chamber, cleans, is passed through H2O gases carry out chemisorption, then pass to
In-situ oxidation, cleaning occur for inert gas auxiliary plasma build-up of luminance；
(2) step (1) is repeated into N1After secondary, the first metal oxide film is obtained；
(3) it is passed through the second metal precursor, cleans, is passed through H2O gases carry out chemisorption, and it is auxiliary to then pass to inert gas
Plasma glow start is helped, in-situ oxidation, cleaning occurs；
(4) step (3) is repeated into N2After secondary, the second metal oxide film is obtained；
(5) step (1)~(4) are repeated M times, obtains transparent conductive metal oxide film.
Wherein, N1:N2=(14~21):(1~4), such as 14:4、14:1、15:1、16:1、17:2、18:3、19:4、20:
1 or 21:1 etc.；M=10~40, such as 10,12,15,18,20,22,25,28,30,32,35,38 or 40 etc..
The major defect of existing hot ALD method growth transparent conductive metal oxide film is that：If reducing reaction temperature
Degree, metal precursor under cryogenic with H2O can prevent organo-metallic compound from complete when reacting due to steric hindrance
Reaction, and be not easy to remove completely when the organic impurities low temperature of reaction generation.The preparation method of the present invention is made of M cycle, often
Secondary cycle includes two continuous subcycles：Step (1)~(2) be the first metal oxide film deposition cycle, step (3)~
(4) it is the second metal oxide film deposition cycle, the alternating for finally obtaining the first metal oxide and the second metal oxide is folded
Layer structure all includes two kinds of metals different from the doped structure in CN1041195523A, i.e., in each layer.The present invention is each small
Cycle is all made of corona treatment, and water is passed through rear portion and is adsorbed in substrate, and another part is dispersed in chamber, plasma
Two parts water, which can all be excited, in body mechanism generates active group and metal front precursor reactant generation metal oxide, compares
In the method for oxidation of CN1041195523A, invention increases N1Number, plasma processing frequency higher, H2In O hydroxyl from
By disengaging more fully for base, reaction temperature is significantly reduced, while reducing the steric hindrance of hydroxyl and metal precursor, it is real
The transparent conductive metal oxide film that low-resistivity is prepared under low temperature is showed, and overcome that impurity under low temperature is not easy to remove asks
Topic.And the present invention does not use Ar/O directly2Corona treatment is carried out, is different from the prior art by oxygen and carrier inert gas
The method that body is passed through simultaneously, but strictly control reaction gas enters the sequence of cavity, is passed through in advance before plasma glow start
H2O gas plasmas source carry out chemisorption, increase the uniformity of oxide deposition, be unlikely to occur alumina cluster generate with
Segregation.
Preferably, the transparent conductive metal oxide film includes AZO films, GZO films, IZO films or ito thin film
In any one.
Preferably, step (1) first metal precursor and step (2) second metal precursor be each independently
For halide, alkyl compound, alkoxide compound, alkylamino compound, cyclopentadienyl compounds, beta-diketone compound,
In amidino compounds and guanidine compound any one or at least two combination；The wherein restrictive combination of typical solo flight
For：The combination of halide and alkyl compound, the combination of alkoxide compound and alkylamino compound, cyclopentadienyl group chemical combination
The combination of object, beta-diketone compound and amidino compounds, the combination of halide, alkyl compound and guanidine compound.
Preferably, each raw material is electron level purity.
Preferably, the duration for metal precursor being passed through in step (1) and step (3) is each independently 0.01~0.05s,
Such as 0.01s, 0.02s, 0.03s, 0.04s or 0.05s etc., guarantee obtain further decreasing water impurity while uniform film
It is flat.
Preferably, after being passed through metal precursor in step (1) and step (3), residual gas is and then carried out each independently
Body detaches.Detach the precursor source that do not adsorb completely and the byproduct gas of reaction generation.
Preferably, the time detached is not more than 20s, for example, time for detaching be 1s, 2s, 3s, 4s, 5s, 8s, 10s,
12s, 15s, 18s or 20s etc..
It is passed through H described in step (1) and step (3)2The duration of O gases is each independently 0.01~0.05s, such as
0.01s, 0.02s, 0.03s, 0.04s or 0.05s etc..
Preferably, it is passed through H described in step (1) and step (3)2After O gases, residual gas is and then carried out each independently
Body detaches.
Preferably, the time detached is not more than 20s, for example, time for detaching be 1s, 2s, 3s, 4s, 5s, 8s, 10s,
12s, 15s, 18s or 20s etc..
Preferably, the gas H that step (1) is passed through2The molar ratio of O and the first metal precursor is (2~4):1, such as 2:
1、2.2:1、2.5:1、2.8:1、3:1、3.2:1、3.5:1、3.8:1 or 4:1 etc..
Preferably, the gas H that step (3) is passed through2The molar ratio of O and the second metal precursor is (3~6):1, such as 3:
1、3.2:1、3.5:1、3.8:1、4:1、4.2:1、4.5:1、4.8:1、5:1、5.2:1、5.5:1、5.8:1 or 6:1 etc..
Preferably, inert gas described in step (1) and step (3) is each independently selected from nitrogen, helium, neon, argon
In gas, Krypton or xenon any one or at least two combination, wherein it is typical but non-limiting to be combined as nitrogen and helium
The combination of gas, the combination of neon, argon gas and Krypton, the combination of nitrogen and xenon, preferably nitrogen and/or argon gas.
Preferably, inert gas described in step (1) and step (3) be passed through flow be each independently 30~
250sccm, for example, 30sccm, 50sccm, 80sccm, 100sccm, 120sccm, 150sccm, 180sccm, 200sccm,
220sccm or 250sccm etc..
Preferably, the duration of plasma glow start described in step (1) and step (3) is each independently 5~30s, example
Such as 5s, 6s, 8s, 10s, 12s, 15s, 18s, 20s, 22s, 25s, 28s or 30s；Power is each independently 100~300W,
Such as 100W, 120W, 150W, 180W, 200W, 220W, 250W, 280W or 300W etc..By optimize plasma glow start when
Long and power is to optimize H2The reactivity of O, to ensure to react substrate or film not by while plasma etching into one
Step improves the electric conductivity of film.()
Preferably, when in-situ oxidation described in step (1) and step (3), the pressure in the reaction chamber is each independently
For 0.09~0.35Torr, for example, 0.09Torr, 0.10Torr, 0.12Torr, 0.15Torr, 0.18Torr, 0.20Torr,
0.22Torr, 0.25Torr, 0.28Torr, 0.30Torr, 0.32Torr or 0.35Torr etc.；Temperature is 60~90 DEG C, such as
60 DEG C, 62 DEG C, 65 DEG C, 68 DEG C, 70 DEG C, 72 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 85 DEG C or 90 DEG C etc..
Preferably, N2=1~4, such as 1,2,3 or 4 etc..
Preferably, M=20~22, such as 21,21 or 22 etc..
Second aspect, the present invention provide a kind of transparent conductive metal oxide film, including the first metal oxide film and
The layer structure that second metal oxide film is alternately stacked, the transparent conductive metal oxide film is by as described in relation to the first aspect
The preparation method of transparent conductive metal oxide film be prepared.
The third aspect, the present invention provides the purposes of the transparent conductive metal oxide film as described in second aspect, described
Transparent conductive metal oxide film is used as the anode of OLED display, film too can energy battery electrode or touch screen electrode.
Compared with prior art, the present invention at least has the advantages that：
1. the present invention improves plasma processing frequency, H2In O hydroxyl radical free radical disengage more fully, significantly reduce
Reaction temperature realizes the transparent conductive metal oxide film that low-resistivity is prepared under low temperature；
2. the present invention does not use Ar/O directly2Corona treatment is carried out, but strictly control reaction gas enters cavity
Sequence, be passed through H in advance before plasma glow start2O gas plasmas source carries out chemisorption, increases the uniform of oxide deposition
Degree is unlikely to that alumina cluster generation and segregation occurs.
Description of the drawings
Fig. 1 is the flow diagram of 1 preparation method of the embodiment of the present invention.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.But following reality
The simple example that example is only the present invention is applied, the scope of the present invention, protection model of the invention are not represented or limit
It encloses and is subject to claims.
Embodiment 1
A kind of preparation method of transparent conductive metal oxide film, as shown in Figure 1, steps are as follows：
(1) diethyl zinc (DEZ) is passed through into reaction chamber, it is 0.02s to be passed through the time, and it is 35s to detach the time, is cleaned, and is led to
Enter H2O gases carry out chemisorption, and it is 0.015s to be passed through the time, and it is 0s to detach the time, then passes to Ar gas auxiliary plasmas
Build-up of luminance, plasma power 300W, duration 16s detach time 12s, and wherein main pipeline Ar flows are 35sccm；Temperature
60 DEG C, in-situ oxidation occurs under conditions of reaction cavity pressure 0.10torr, clean；
(2) after being repeated 14 times step (1), ZnO film is obtained；
(3) it is passed through trimethyl aluminium (TMA), it is 0.02s to be passed through the time, and it is 35s to detach the time, and cleaning is passed through H2O gases into
Row chemisorption, it is 0.015s to be passed through the time, and it is 0s to detach the time, then passes to inert gas auxiliary plasma build-up of luminance, etc.
Ion power is 300W, duration 16s, detaches time 12s, and wherein main pipeline Ar flows are 35sccm, temperature 60 C, anti-
It answers and in-situ oxidation occurs under conditions of chamber pressure 0.10torr, clean；
(4) after being repeated 4 times step (3), Al is obtained2O3Film；
(5) step (1)~(4) are repeated 18 times, obtain transparent conductive metal oxide film.
Embodiment 2
A kind of preparation method of transparent conductive metal oxide film, steps are as follows：
(1) diethyl zinc (DEZ) is passed through into reaction chamber, it is 0.02s to be passed through the time, and it is 25s to detach the time, is cleaned, and is led to
Enter H2O gases carry out chemisorption, and it is 0.015s to be passed through the time, and it is 10s to detach the time, then passes to Ar gas auxiliary plasmas
Build-up of luminance, plasma power 300W, duration 16s detach time 12s, and wherein main pipeline Ar flows are 35sccm；Temperature
70 DEG C, in-situ oxidation occurs under conditions of reaction cavity pressure 0.10torr, clean；
(2) after being repeated 18 times step (1), ZnO film is obtained；
(3) it is passed through trimethyl aluminium (TMA), it is 0.02s to be passed through the time, and it is 25s to detach the time, and cleaning is passed through H2O gases into
Row chemisorption, it is 0.015s to be passed through the time, and it is 10s to detach the time, then passes to inert gas auxiliary plasma build-up of luminance, etc.
Ion power is 300W, duration 16s, detaches time 12s, and wherein main pipeline Ar flows are 35sccm, temperature 70 C, anti-
It answers and in-situ oxidation occurs under conditions of chamber pressure 0.10torr, clean；
(4) after being repeated 1 times step (3), Al is obtained2O3Film；
(5) step (1)~(4) are repeated 20 times, obtain transparent conductive metal oxide film.
Embodiment 3
A kind of preparation method of transparent conductive metal oxide film, steps are as follows：
(1) diethyl zinc (DEZ) is passed through into reaction chamber, it is 0.02s to be passed through the time, and it is 30s to detach the time, is cleaned, and is led to
Enter H2O gases carry out chemisorption, and it is 0.03s to be passed through the time, and it is 0s to detach the time, then pass to Ar gas auxiliary plasmas and rise
Brightness, plasma power 300W, duration 16s detach time 12s, and wherein main pipeline Ar flows are 35sccm；Temperature 70
DEG C, in-situ oxidation occurs under conditions of reaction cavity pressure 0.10torr, clean；
(2) after being repeated 19 times step (1), ZnO film is obtained；
(3) it is passed through trimethyl aluminium (TMA), it is 0.02s to be passed through the time, and it is 35s to detach the time, and cleaning is passed through H2O gases into
Row chemisorption, be passed through the time be 0.03s, detach the time be 0s, then pass to inert gas auxiliary plasma build-up of luminance, wait from
Sub- power is 300W, duration 16s, detaches time 12s, and wherein main pipeline Ar flows are 35sccm, temperature 70 C, reaction
In-situ oxidation occurs under conditions of chamber pressure 0.10torr, cleans；
(4) after being repeated 1 times step (3), Al is obtained2O3Film；
(5) step (1)~(4) are repeated 22 times, obtains transparent conductive metal oxide film.
Embodiment 4
A kind of preparation method of transparent conductive metal oxide film, steps are as follows：
(1) diethyl zinc (DEZ) is passed through into reaction chamber, it is 0.02s to be passed through the time, and it is 30s to detach the time, is cleaned, and is led to
Enter H2O gases carry out chemisorption, and it is 0.015s to be passed through the time, and it is 0s to detach the time, then passes to Ar gas auxiliary plasmas
Build-up of luminance, plasma power 300W, duration 16s detach time 12s, and wherein main pipeline Ar flows are 35sccm；Temperature
80 DEG C, in-situ oxidation occurs under conditions of reaction cavity pressure 0.15torr, clean；
(2) after being repeated 19 times step (1), ZnO film is obtained；
(3) it is passed through trimethyl aluminium (TMA), it is 0.02s to be passed through the time, and it is 35s to detach the time, and cleaning is passed through H2O gases into
Row chemisorption, it is 0.015s to be passed through the time, and it is 0s to detach the time, then passes to inert gas auxiliary plasma build-up of luminance, etc.
Ion power is 300W, duration 16s, detaches time 12s, and wherein main pipeline Ar flows are 35sccm, 80 DEG C of temperature, anti-
It answers and in-situ oxidation occurs under conditions of chamber pressure 0.15torr, clean；
(4) after being repeated 1 times step (3), Al is obtained2O3Film；
(5) step (1)~(4) are repeated 20 times, obtain transparent conductive metal oxide film.
Embodiment 5
A kind of preparation method of transparent conductive metal oxide film, steps are as follows：
(1) diethyl zinc (DEZ) is passed through into reaction chamber, it is 0.02s to be passed through the time, and it is 30s to detach the time, is cleaned, and is led to
Enter H2O gases carry out chemisorption, and it is 0.02s to be passed through the time, and it is 0s to detach the time, then pass to Ar gas auxiliary plasmas and rise
Brightness, plasma power 300W, duration 16s detach time 12s, and wherein main pipeline Ar flows are 35sccm；Temperature 85
DEG C, in-situ oxidation occurs under conditions of reaction cavity pressure 0.25torr, clean；
(2) after being repeated 18 times step (1), ZnO film is obtained；
(3) it is passed through trimethyl aluminium (TMA), it is 0.02s to be passed through the time, and it is 35s to detach the time, and cleaning is passed through H2O gases into
Row chemisorption, be passed through the time be 0.02s, detach the time be 0s, then pass to inert gas auxiliary plasma build-up of luminance, wait from
Sub- power is 300W, duration 16s, detaches time 12s, and wherein main pipeline Ar flows are 35sccm, 85 DEG C of temperature, reaction
In-situ oxidation occurs under conditions of chamber pressure 0.25torr, cleans；
(4) after being repeated 1 times step (3), Al is obtained2O3Film；
(5) step (1)~(4) are repeated 22 times, obtains transparent conductive metal oxide film.
Embodiment 6
A kind of preparation method of GZO transparent conductive films, steps are as follows：
(1) diethyl zinc (DEZ) is passed through into reaction chamber, it is 0.02s to be passed through the time, and it is 30s to detach the time, is cleaned, and is led to
Enter H2O gases carry out chemisorption, and it is 0.02s to be passed through the time, and it is 0s to detach the time, then pass to Ar gas auxiliary plasmas and rise
Brightness, plasma power 300W, duration 16s detach time 12s, and wherein main pipeline Ar flows are 35sccm；Temperature 90
DEG C, in-situ oxidation occurs under conditions of reaction cavity pressure 0.25torr, clean；
(2) after being repeated 20 times step (1), ZnO film is obtained；
(3) it is passed through trimethyl gallium (TMGa), it is 0.03s to be passed through the time, and it is 35s to detach the time, and cleaning is passed through H2O gases
Chemisorption is carried out, it is 0.02s to be passed through the time, and it is 0s to detach the time, then passes to inert gas auxiliary plasma build-up of luminance, etc.
Ion power is 300W, duration 16s, detaches time 12s, and wherein main pipeline Ar flows are 35sccm, 90 DEG C of temperature, anti-
It answers and in-situ oxidation occurs under conditions of chamber pressure 0.25torr, clean；
(4) after being repeated 1 times step (3), Ga is obtained2O3Film；
(5) step (1)~(4) are repeated 22 times, obtains GZO transparent conductive films.
Embodiment 7
A kind of preparation method of IZO transparent conductive films, steps are as follows：
(1) diethyl zinc (DEZ) is passed through into reaction chamber, it is 0.02s to be passed through the time, and it is 35s to detach the time, is cleaned, and is led to
Enter H2O gases carry out chemisorption, and it is 0.03s to be passed through the time, and it is 0s to detach the time, then pass to Ar gas auxiliary plasmas and rise
Brightness, plasma power 300W, duration 16s detach time 12s, and wherein main pipeline Ar flows are 35sccm；Temperature 70
DEG C, in-situ oxidation occurs under conditions of reaction cavity pressure 0.25torr, clean；
(2) after being repeated 20 times step (1), ZnO film is obtained；
(3) it is passed through trimethyl indium (TMIn), it is 0.03s to be passed through the time, and it is 40s to detach the time, and cleaning is passed through H2O gases
Chemisorption is carried out, it is 0.03s to be passed through the time, and it is 0s to detach the time, then passes to inert gas auxiliary plasma build-up of luminance, etc.
Ion power is 300W, duration 16s, detaches time 12s, and wherein main pipeline Ar flows are 35sccm, temperature 70 C, anti-
It answers and in-situ oxidation occurs under conditions of chamber pressure 0.25torr, clean；
(4) after being repeated 1 times step (3), In is obtained2O3Film；
(5) step (1)~(4) are repeated 22 times, obtains IZO transparent conductive films.
Embodiment 8
A kind of preparation method of transparent conductive film, steps are as follows：
(1) stannous methide (DMSn) is passed through into reaction chamber, it is 0.03s to be passed through the time, and it is 40s to detach the time, is cleaned, and is led to
Enter H2O gases carry out chemisorption, and it is 0.02s to be passed through the time, and it is 0s to detach the time, then pass to Ar gas auxiliary plasmas and rise
Brightness, plasma power 300W, duration 16s detach time 12s, and wherein main pipeline Ar flows are 35sccm；Temperature 80
DEG C, in-situ oxidation occurs under conditions of reaction cavity pressure 0.25torr, clean；
(2) after being repeated 20 times step (1), SnO films are obtained；
(3) it is passed through trimethyl indium (TMIn), it is 0.05s to be passed through the time, and it is 35s to detach the time, and cleaning is passed through H2O gases
Chemisorption is carried out, it is 0.02s to be passed through the time, and it is 0s to detach the time, then passes to inert gas auxiliary plasma build-up of luminance, etc.
Ion power is 300W, duration 16s, detaches time 12s, and wherein main pipeline Ar flows are 35sccm, 80 DEG C of temperature, anti-
It answers and in-situ oxidation occurs under conditions of chamber pressure 0.25torr, clean；
(4) after being repeated 2 times step (3), In is obtained2O3Film；
(5) step (1)~(4) are repeated 22 times, obtains transparent conductive film.
Embodiment 9
With differing only in for embodiment 8：The number of repetition of step (1)~(4) is 40 times.
Embodiment 10
With differing only in for embodiment 8：The number of repetition of step (1)~(4) is 10 times.
Comparative example 8-1
With differing only in for embodiment 8：The number of repetition of step (1) is 6 times.
Comparative example 8-2
With differing only in for embodiment 8：The number of repetition of step (1) is 45 times.
Comparative example 8-3
With differing only in for embodiment 8：Step (1) is changed to：It is passed through DMSn into reaction chamber, cleans, is passed through H2O/Ar,
In-situ oxidation, cleaning occur for plasma glow start；Other technological parameters are same as Example 8.
Comparative example 8-4
With differing only in for embodiment 8：Step (3) is changed to：It is passed through TMIn into reaction chamber, cleans, is passed through H2O/Ar,
In-situ oxidation, cleaning occur for plasma glow start；Other technological parameters are same as Example 8.
Comparative example 8-5
With differing only in for embodiment 8：Step (1) is changed to：It is passed through DMSn into reaction chamber, cleans, is passed through H2O/Ar,
In-situ oxidation, cleaning occur for plasma glow start；
Step (3) is changed to simultaneously：It is passed through TMIn into reaction chamber, cleans, is passed through H2O/Ar, plasma glow start occur
In-situ oxidation, cleaning；Other technological parameters are same as Example 8.
Electrically conducting transparent film resistance and thickness test：
It is tested using four-point probe, probe spacing 1mm, the test electric current of automatic measurement is 10 μ A, is measured
The square resistance of each embodiment and the provided film product of comparative example, thickness are tested using step instrument, are calculated resistivity, are recorded in
Table 1.
Table 1
| Sample | Square resistance Ω/ | Thickness nm | Resistivity Ω cm | Preparation temperature DEG C |
| Embodiment 1 | 370 | 30 | 1.1*10-3 | 60 |
| Embodiment 2 | 800 | 32 | 2.6*10-3 | 70 |
| Embodiment 3 | 350 | 34 | 1.2*10-3 | 70 |
| Embodiment 4 | 800 | 31 | 2.4*10-3 | 80 |
| Embodiment 5 | 1200 | 33 | 3.9*10-3 | 85 |
| Embodiment 6 | 700 | 32 | 2.3*10-3 | 90 |
| Embodiment 7 | 500 | 33 | 1.6*10-3 | 70 |
| Embodiment 8 | 420 | 41 | 1.7*10-3 | 80 |
| Embodiment 9 | 320 | 70 | 2.2*10-3 | 80 |
| Embodiment 10 | 1300 | 20 | 2.6*10-3 | 80 |
| Comparative example 8-1 | 5500 | 25 | 1.4*10-2 | 80 |
| Comparative example 8-2 | 2200 | 55 | 1.2*10-2 | 80 |
| Comparative example 8-3 | 7000 | 45 | 3.2*10-2 | 80 |
| Comparative example 8-4 | 7500 | 42 | 3.2*10-2 | 80 |
| Comparative example 8-5 | 9500 | 50 | 4.8*10-2 | 80 |
As shown in table 1, comparative examples 8~10 and comparative example 8-1, comparative example 8-2 result it is found that the present invention by setting
Set N1:N2In (14~21):In (1~4) range, plasma processing frequency, H are improved2Hydroxyl radical free radical disengages more in O
Fully, reaction temperature is significantly reduced, the transparent conductive metal oxide film for preparing low-resistivity under low temperature is realized.This
Outside, suitable N herein1:N2Under the premise of ratio, setting M is matched in 20~22 ranges, has advanced optimized metal oxidation
The electric conductivity of object transparent conductive film.
The result of comparative examples 8 and comparative example 8-3, comparative example 8-4 and comparative example 8-5 it is found that the present invention rational
N1:N2Under the premise of ratio, the present invention does not use Ar/H directly2O carries out corona treatment, is different from the prior art by oxygen
The method being passed through simultaneously with carrier inert gas, but strictly control reaction gas enters the sequence of cavity, is risen in plasma
H is passed through before brightness in advance2O gas plasmas source carries out chemisorption, from the electric conductivity of gained conductive film it is found that the oxygen of the present invention
Compound depositing homogeneous and impurity content is very low.Therefore, the excellent properties of conductive film are that cycle-index and raw material are added in the present invention
The synthesis result that sequence is worked in coordination.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
1. a kind of preparation method of transparent conductive metal oxide film, which is characterized in that include the following steps：
(1) it is passed through the first metal precursor into reaction chamber, cleans, is passed through H2O gases carry out chemisorption, then pass to inertia
In-situ oxidation, cleaning occur for gas auxiliary plasma build-up of luminance；
(2) step (1) is repeated into N1After secondary, the first metal oxide film is obtained；
(3) it is passed through the second metal precursor, cleans, is passed through H2O gases carry out chemisorption, then pass to inert gas auxiliary etc.
In-situ oxidation, cleaning occur for gas ions build-up of luminance；
(4) step (3) is repeated into N2After secondary, the second metal oxide film is obtained；
(5) step (1)~(4) are repeated M times, obtains transparent conductive metal oxide film；
Wherein, N1:N2=(14~21):(1~4), M=10~40.
2. the preparation method of transparent conductive metal oxide film as described in claim 1, which is characterized in that the metal oxygen
Compound transparent conductive film includes any one in AZO films, GZO films, IZO films or ito thin film.
3. the preparation method of transparent conductive metal oxide film as claimed in claim 1 or 2, which is characterized in that step (1)
First metal precursor and step (2) second metal precursor are each independently halide, alkyl compound, alkane
Oxo-compound, alkylamino compound, cyclopentadienyl compounds, beta-diketone compound, amidino compounds and guanidine compound
In any one or at least two combination；
Preferably, each raw material is electron level purity.
4. such as the preparation method of claims 1 to 3 any one of them transparent conductive metal oxide film, which is characterized in that
The duration that metal precursor is passed through in step (1) and step (3) is each independently 0.01~0.05s；
Preferably, after being passed through metal precursor in step (1) and step (3), residual gas is and then carried out each independently
It detaches；
Preferably, the time detached is not more than 20s.
5. such as the preparation method of Claims 1 to 4 any one of them transparent conductive metal oxide film, which is characterized in that
It is passed through H described in step (1) and step (3)2The duration of O gases is each independently 0.01~0.05s；
Preferably, it is passed through H described in step (1) and step (3)2After O gases, residual gas is and then carried out each independently
It detaches；
Preferably, the time detached is not more than 20s；
Preferably, the gas H that step (1) is passed through2The molar ratio of O and the first metal precursor is (2~4):1；
Preferably, the gas H that step (3) is passed through2The molar ratio of O and the second metal precursor is (3~6):1.
6. such as the preparation method of Claims 1 to 5 any one of them transparent conductive metal oxide film, which is characterized in that
Inert gas is each independently selected from nitrogen, helium, neon, argon gas, Krypton or xenon described in step (1) and step (3)
Any one or at least two combination, preferably nitrogen and/or argon gas；
Preferably, the flow that is passed through of inert gas described in step (1) and step (3) is each independently 30~250sccm；
Preferably, the duration of plasma glow start described in step (1) and step (3) is each independently 5~30s, and power is each
From independently being 100~300W.
7. such as the preparation method of claim 1~6 any one of them transparent conductive metal oxide film, which is characterized in that
Described in step (1) and step (3) when in-situ oxidation, the pressure in the reaction chamber is each independently 0.09~
0.35Torr, temperature are 60~90 DEG C.
8. such as the preparation method of claim 1~7 any one of them transparent conductive metal oxide film, which is characterized in that N2
=1~4；
Preferably, M=20~22.
9. a kind of transparent conductive metal oxide film, which is characterized in that including the first metal oxide film and the second metal oxygen
The layer structure that compound film is alternately stacked, the transparent conductive metal oxide film is by as described in any one of claim 1~8
The preparation method of transparent conductive metal oxide film be prepared.
10. the purposes of transparent conductive metal oxide film as claimed in claim 9, which is characterized in that the metal oxidation
Object transparent conductive film is used as the anode of OLED display, film too can energy battery electrode or touch screen electrode.
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| CN103119695A (en) * | 2010-09-23 | 2013-05-22 | 诺发系统公司 | Plasma-activated deposition of conformal films |
| CN102994975A (en) * | 2011-09-15 | 2013-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of aluminum-doped zinc oxide transparent conductive oxide film |
| CN104746039A (en) * | 2013-12-31 | 2015-07-01 | 嘉兴科民电子设备技术有限公司 | Preparation method of aluminium-doping zinc oxide thin film |
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