CN108531890B - Preparation method of metal oxide transparent conductive film, product and application thereof - Google Patents
Preparation method of metal oxide transparent conductive film, product and application thereof Download PDFInfo
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 68
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000004140 cleaning Methods 0.000 claims abstract description 52
- 239000007789 gas Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 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 27
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000001179 sorption measurement Methods 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000011261 inert gas Substances 0.000 claims abstract description 22
- 239000010408 film Substances 0.000 claims description 116
- 238000000034 method Methods 0.000 claims description 50
- -1 alkyl compound Chemical class 0.000 claims description 19
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-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
- 239000002994 raw material Substances 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
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 20
- 230000008569 process Effects 0.000 description 16
- 238000000151 deposition Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 14
- 238000000605 extraction Methods 0.000 description 13
- 230000008021 deposition Effects 0.000 description 12
- 238000005086 pumping Methods 0.000 description 11
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 10
- 238000000231 atomic layer deposition Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012495 reaction gas 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
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000356 contaminant 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
- 230000007547 defect Effects 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
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000005204 segregation Methods 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- 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
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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
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- 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
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- 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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- 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
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- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C23C16/45536—Use of plasma, radiation or electromagnetic fields
- C23C16/4554—Plasma being used non-continuously in between ALD reactions
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Abstract
The invention relates to a preparation method of a metal oxide transparent conductive film, a product and application thereof, wherein the preparation method comprises the following steps: (1) introducing a first metal precursor into the reaction chamber, cleaning, and introducing H2Carrying out chemical adsorption on O gas, then introducing inert gas to assist plasma to glow, carrying out in-situ oxidation, and cleaning; (2) repeating the step (1) by N1Then, obtaining a first metal oxide film; (3) introducing a second metal precursor, cleaning, introducing H2Carrying out chemical adsorption on O gas, then introducing inert gas to assist plasma to glow, carrying out in-situ oxidation, and cleaning; (4) repeating the step (3) by N2Then, obtaining a second metal oxide film; (5) repeating the steps (1) - (4) for M times to obtain the metal oxide transparent conductive film; wherein N is1:N2(14-21) and (1-4), and M is 10-40. The preparation of the metal oxide transparent conductive film with low resistivity at low temperature is realized.
Description
Technical Field
The invention relates to the technical field of semiconductor manufacturing, in particular to a preparation method of a metal oxide transparent conductive film, a product and application thereof.
Background
The oxide transparent conductive film is an important optoelectronic information material, and has high transmittance in a visible light region and high reflectivity in an infrared region. The preparation process and the post-treatment mode of the film have great influence on the structure, optical property and electrical property of the transparent conductive film, in addition, different doping elements have great influence on the physical and electrical properties of the film, the film property can be effectively improved by controlling the doping level of the film, and the special photoelectric properties of the oxide transparent conductive film can be widely applied to a plurality of fields such as solar cells, flat panel displays and the like. At present, a plurality of methods for preparing the oxide transparent conductive film mainly comprise the following steps: magnetron sputtering, pulsed laser deposition, chemical vapor deposition, spray pyrolysis, and sol-gel processes. However, these methods have a large difference in the ratio of metal oxides when preparing conductive films of the same resistivity, and thus a high-performance conductive film having stable quality cannot be obtained.
Atomic Layer Deposition (ALD) technology, as a potential deposition method for preparing transparent conductive films, has significant advantages over conventional deposition methods, including: large-area deposition, accurate control of the film thickness through the cycle number, and good uniformity and reproducibility. This new deposition method is well suited to meet the new technological development needs and has attracted considerable attention in recent years. In addition, a flexible flat panel display device is becoming one of mainstream technologies of future display development, and a flexible substrate cannot withstand a high-temperature environment for a long time. Therefore, the low temperature preparation of high performance transparent conductive films by atomic layer deposition techniques is a challenging technique.
CN101535524B discloses a method and system for performing plasma enhanced atomic layer deposition, which solves various problems of semiconductor processing caused by smaller and smaller line width and the condition that conformality, adhesiveness and purity become more and more important factors affecting the obtained semiconductor device, reduces the problem of contamination between the interfaces of material layers of subsequent deposition, and provides a configuration compatible with atomic layer deposition and plasma enhanced reduction in the same system. But it does not solve the problem of preparing the metal oxide transparent conductive film at low temperature and high efficiency.
CN100590819C discloses a plasma enhanced atomic layer deposition method and a semiconductor device including a film formed thereby, wherein a first processing material is introduced into a process chamber, a second processing material is introduced into the process chamber, electromagnetic power coupling is utilized to generate plasma for promoting a reduction reaction between the first and second processing materials, and after the reduction reaction between the first and second processing materials is completed to deposit the film on a substrate in a solid state, a third material, i.e. a reactive gas, is introduced into the process chamber to react with contaminants, thereby solving the problems of slow deposition rate and contamination affecting the quality of the deposited film to a certain extent, but not realizing the low-temperature and high-efficiency preparation of a metal oxide transparent conductive film.
CN1041195523A discloses a method for preparing an aluminum-doped zinc oxide film by plasma-enhanced atomic layer deposition. Performing M times of circulation on the combination of N times of ALD deposition circulation of the zinc oxide substrate film and N times of Al doping process circulation to form the aluminum zinc oxide film layer by layer, wherein the Al doping process circulation comprises Al doping process pretreatment; n is 9-29; and M is 30-90. The film deposition and doping are carried out by introducing metal precursor into deposition chamber, oxidizing deposition with oxidant or plasma mixed with inert gas, doping aluminum oxide into zinc oxide layer, inhibiting generation and segregation of aluminum oxide cluster, and reducing film resistivity, wherein the substrate heating temperature is above 150 deg.C, and the gas and precursor source pipeline heating temperature is above 100 deg.C.
Therefore, it is required to develop a method for preparing a low-resistivity metal oxide transparent conductive film with high efficiency and low temperature.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a method for efficiently preparing a low-resistivity metal oxide transparent conductive film at a low temperature.
In a first aspect, the present invention provides a method for preparing a metal oxide transparent conductive film, comprising the steps of:
(1) introducing a first metal precursor into the reaction chamber, cleaning, and introducing H2Carrying out chemical adsorption on O gas, then introducing inert gas to assist plasma to glow, carrying out in-situ oxidation, and cleaning;
(2) repeating the step (1) by N1Then, obtaining a first metal oxide film;
(3) introducing a second metal precursor, cleaning, introducing H2Carrying out chemical adsorption on O gas, then introducing inert gas to assist plasma to glow, carrying out in-situ oxidation, and cleaning;
(4) repeating the step (3) by N2Then, obtaining a second metal oxide film;
(5) repeating the steps (1) - (4) for M times to obtain the metal oxide transparent conductive film.
Wherein N is1:N2(1-4) for example, 14:4, 14:1, 15:1, 16:1, 17:2, 18:3, 19:4, 20:1, 21:1, etc.; for example, M is 10to 40, such as 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, or 40.
The existing thermal ALD method for growing the metal oxide transparent conductive film has the following serious defects: if the reaction temperature is lowered, the metal precursor reacts with H under low temperature conditions2In the O reaction, the organometallic compound cannot be completely reacted due to steric hindrance, and organic impurities formed by the reaction are not easily removed at low temperatures. The preparation method of the invention consists of M cycles, each cycle comprising two consecutive sub-cycles: steps (1) to (2) are deposition cycles of the first metal oxide film, and steps (3) to (4) are deposition cycles of the second metal oxide film, and finally an alternating stacked structure of the first metal oxide and the second metal oxide is obtained, which is different from the doped structure in CN1041195523A, that is, each layer contains two metals. In the invention, each small cycle is treated by adopting plasma, one part of water is adsorbed on the substrate after being introduced, the other part of water is dispersed in the chamber, and two parts of water can be excited to generate active groups in the plasma action process and react with metal precursors to generate metal oxides, compared with the oxidation method of CN1041195523A, the method increases N in the invention1Higher frequency of plasma treatment, H2The release of hydroxyl free radicals in O is more sufficient, the reaction temperature is greatly reduced, the steric hindrance of hydroxyl and a metal precursor is reduced, the preparation of the metal oxide transparent conductive film with low resistivity at low temperature is realized, and the problem that impurities are not easy to remove at low temperature is solved. And the invention does not directly use Ar/O2Plasma treatment is carried out, which is different from the method of introducing oxygen and carrier inert gas simultaneously in the prior art, but strictly controls the sequence of reaction gas entering a cavity, and H is introduced in advance before plasma glow is started2The O gas plasma source is used for chemical adsorption, so that the uniformity of oxidation deposition is improved, and alumina clusters are prevented from being generated and segregated.
Preferably, the metal oxide transparent conductive film includes any one of an AZO film, a GZO film, an IZO film, or an ITO film.
Preferably, the first metal precursor in step (1) and the second metal precursor in step (2) are each independently any one of or a combination of at least two of a halide, an alkyl compound, an alkoxy compound, an alkylamino compound, a cyclopentadienyl compound, an β -dione compound, an amidino compound and a guanidino compound, wherein typical single-flight limiting combinations are a combination of a halide and an alkyl compound, a combination of an alkoxy compound and an alkylamino compound, a combination of a cyclopentadienyl compound, a β -dione compound and an amidino compound, and a combination of a halide, an alkyl compound and a guanidino compound.
Preferably, each feedstock is of electronic grade purity.
Preferably, the time period for introducing the metal precursor in step (1) and step (3) is 0.01 to 0.05s, such as 0.01s, 0.02s, 0.03s, 0.04s, or 0.05s, respectively, so as to ensure that a uniform thin film is obtained and the impurity level is further reduced.
Preferably, the step (1) and the step (3) are each independently followed by a residual gas removal after the metal precursor is introduced. And pumping away the incompletely adsorbed precursor source and the byproduct gas generated by the reaction.
Preferably, the time of the drawing-off is not more than 20s, for example, the time of the drawing-off is 1s, 2s, 3s, 4s, 5s, 8s, 10s, 12s, 15s, 18s or 20s, and the like.
Introducing H in the step (1) and the step (3)2The O gas is independently used for 0.01 to 0.05s, such as 0.01s, 0.02s, 0.03s, 0.04s, or 0.05 s.
Preferably, said passing H in step (1) and step (3)2The residual gas is then removed independently of each other after the O gas.
Preferably, the time of the drawing-off is not more than 20s, for example, the time of the drawing-off is 1s, 2s, 3s, 4s, 5s, 8s, 10s, 12s, 15s, 18s or 20s, and the like.
Preferably, the gas H introduced in step (1)2The molar ratio of O to the first metal precursor is (2-4): 1, for example, 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.
Preferably, the gas H introduced in step (3)2The molar ratio of O to the second metal precursor is (3-6: 1), for example, 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.
Preferably, the inert gas in step (1) and step (3) is independently selected from any one of nitrogen, helium, neon, argon, krypton or xenon or a combination of at least two of the same, wherein a typical but non-limiting combination is a combination of nitrogen and helium, neon, argon and krypton, nitrogen and xenon, preferably nitrogen and/or argon.
Preferably, the flow rate of the inert gas introduced in step (1) and step (3) is 30-250 sccm, such as 30sccm, 50sccm, 80sccm, 100sccm, 120sccm, 150sccm, 180sccm, 200sccm, 220sccm, or 250sccm, respectively.
Preferably, the plasma ignition time in the step (1) and the step (3) is 5-30 s, such as 5s, 6s, 8s, 10s, 12s, 15s, 18s, 20s, 22s, 25s, 28s or 30s, etc. independently; the power is 100-300W, such as 100W, 120W, 150W, 180W, 200W, 220W, 250W, 280W or 300W. By optimizing the duration and power of plasma ignition to optimize H2And O, thereby ensuring that the reaction substrate or the film is not etched by the plasma and simultaneously further improving the conductivity of the film. ()
Preferably, in the in-situ oxidation in step (1) and step (3), the pressure in the reaction chamber is 0.09to 0.35Torr, such as 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, respectively; the temperature is 60 to 90 ℃, for example, 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃, 85 ℃ or 90 ℃.
Preferably, N21-4, for example, 1, 2, 3, or 4.
Preferably, M is 20 ~ 22, such as 21, 21 or 22.
In a second aspect, the present invention provides a metal oxide transparent conductive film comprising a layered structure in which first metal oxide films and second metal oxide films are alternately stacked, the metal oxide transparent conductive film being prepared by the method for preparing a metal oxide transparent conductive film according to the first aspect.
In a third aspect, the present invention provides the use of a metal oxide transparent conductive film according to the second aspect as an anode for an OLED display, a thin film solar cell electrode or a touch screen electrode.
Compared with the prior art, the invention has at least the following beneficial effects:
1. the invention increases the plasma processing frequency, H2The release of hydroxyl free radicals in O is more sufficient, the reaction temperature is greatly reduced, and the preparation of the metal oxide transparent conductive film with low resistivity at low temperature is realized;
2. the invention does not directly use Ar/O2Plasma treatment is carried out, the sequence of the reaction gases entering the cavity is strictly controlled, and H is introduced in advance before plasma glow is started2The O gas plasma source is used for chemical adsorption, so that the uniformity of oxidation deposition is improved, and alumina clusters are prevented from generating and deviating.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
A preparation method of a metal oxide transparent conductive film is shown in figure 1, and comprises the following steps:
(1) introducing diethyl zinc (DEZ) into the reaction chamber for 0.02s and extracting for 35s, cleaning, and introducing H2Performing chemical adsorption on O gas, wherein the introducing time is 0.015s, the extraction time is 0s, then introducing Ar gas to assist plasma to glow, the plasma power is 300W, the duration is 16s, and the extraction time is 12s, wherein the Ar flow of the main pipeline is 35 sccm; the in-situ oxidation and the cleaning are carried out under the conditions that the temperature is 60 ℃ and the pressure of a reaction cavity is 0.10 torr;
(2) repeating the step (1) for 14 times to obtain a ZnO film;
(3) introducing Trimethylaluminum (TMA) for 0.02s and extracting for 35s, cleaning, and introducing H2Performing chemical adsorption on O gas, wherein the introducing time is 0.015s, the extraction time is 0s, then introducing inert gas to assist plasma to glow, the plasma power is 300W, the duration is 16s, and the extraction time is 12s, wherein the in-situ oxidation and cleaning are performed under the conditions that the main pipeline Ar flow is 35sccm, the temperature is 60 ℃ and the pressure of a reaction cavity is 0.10 torr;
(4) repeating the step (3) for 4 times to obtain Al2O3A film;
(5) repeating the steps (1) to (4) 18 times to obtain the metal oxide transparent conductive film.
Example 2
A preparation method of a metal oxide transparent conductive film comprises the following steps:
(1) introducing diethyl zinc (DEZ) into the reaction chamber for 0.02s and 25s, cleaning, and introducing H2Performing chemical adsorption on O gas, wherein the introducing time is 0.015s, the extraction time is 10s, then introducing Ar gas to assist plasma to glow, the plasma power is 300W, the duration is 16s, and the extraction time is 12s, wherein the Ar flow of the main pipeline is 35 sccm; at a temperature of 70 ℃ and a pressure of 0.10torr in the reaction chamberIn-situ oxidation and cleaning are carried out under the condition;
(2) repeating the step (1) for 18 times to obtain a ZnO film;
(3) introducing Trimethylaluminum (TMA) for 0.02s and extracting for 25s, cleaning, and introducing H2Performing chemical adsorption on O gas, wherein the introducing time is 0.015s, the extraction time is 10s, then introducing inert gas to assist plasma to glow, the plasma power is 300W, the duration is 16s, and the extraction time is 12s, wherein the in-situ oxidation and cleaning are performed under the conditions that the main pipeline Ar flow is 35sccm, the temperature is 70 ℃ and the pressure of a reaction cavity is 0.10 torr;
(4) repeating the step (3) for 1 time to obtain Al2O3A film;
(5) repeating the steps (1) - (4) for 20 times to obtain the metal oxide transparent conductive film.
Example 3
A preparation method of a metal oxide transparent conductive film comprises the following steps:
(1) introducing diethyl zinc (DEZ) into the reaction chamber for 0.02s and extracting for 30s, cleaning, and introducing H2Performing chemical adsorption on O gas for 0.03s, pumping off for 0s, then introducing Ar gas to assist plasma to glow, wherein the plasma power is 300W, the duration is 16s, and the pumping off time is 12s, wherein the Ar flow of the main pipeline is 35 sccm; the in-situ oxidation and the cleaning are carried out under the conditions that the temperature is 70 ℃ and the pressure of a reaction cavity is 0.10 torr;
(2) repeating the step (1) for 19 times to obtain a ZnO film;
(3) introducing Trimethylaluminum (TMA) for 0.02s and extracting for 35s, cleaning, and introducing H2Performing chemical adsorption on O gas, wherein the introducing time is 0.03s, the extracting time is 0s, then introducing inert gas to assist plasma to glow, the plasma power is 300W, the duration is 16s, the extracting time is 12s, wherein the in-situ oxidation and cleaning are performed under the conditions that the main pipeline Ar flow is 35sccm, the temperature is 70 ℃ and the pressure of a reaction cavity is 0.10 torr;
(4) repeating the step (3) for 1 time to obtain Al2O3A film;
(5) repeating the steps (1) to (4) for 22 times to obtain the metal oxide transparent conductive film.
Example 4
A preparation method of a metal oxide transparent conductive film comprises the following steps:
(1) introducing diethyl zinc (DEZ) into the reaction chamber for 0.02s and extracting for 30s, cleaning, and introducing H2Performing chemical adsorption on O gas, wherein the introducing time is 0.015s, the extraction time is 0s, then introducing Ar gas to assist plasma to glow, the plasma power is 300W, the duration is 16s, and the extraction time is 12s, wherein the Ar flow of the main pipeline is 35 sccm; the in-situ oxidation and the cleaning are carried out under the conditions that the temperature is 80 ℃ and the pressure of a reaction cavity is 0.15 torr;
(2) repeating the step (1) for 19 times to obtain a ZnO film;
(3) introducing Trimethylaluminum (TMA) for 0.02s and extracting for 35s, cleaning, and introducing H2Performing chemical adsorption on O gas, wherein the introducing time is 0.015s, the extraction time is 0s, then introducing inert gas to assist plasma to glow, the plasma power is 300W, the duration is 16s, and the extraction time is 12s, wherein the in-situ oxidation and cleaning are performed under the conditions that the main pipeline Ar flow is 35sccm, the temperature is 80 ℃ and the pressure of a reaction cavity is 0.15 torr;
(4) repeating the step (3) for 1 time to obtain Al2O3A film;
(5) repeating the steps (1) - (4) for 20 times to obtain the metal oxide transparent conductive film.
Example 5
A preparation method of a metal oxide transparent conductive film comprises the following steps:
(1) introducing diethyl zinc (DEZ) into the reaction chamber for 0.02s and extracting for 30s, cleaning, and introducing H2Performing chemical adsorption on O gas for 0.02s, pumping off for 0s, then introducing Ar gas to assist plasma to glow, wherein the plasma power is 300W, the duration is 16s, and the pumping off time is 12s, wherein the Ar flow of the main pipeline is 35 sccm; in-situ oxidation is carried out at the temperature of 85 ℃ and the pressure of the reaction cavity of 0.25torr, and cleaning is carried out;
(2) repeating the step (1) for 18 times to obtain a ZnO film;
(3) introducing Trimethylaluminum (TMA) for 0.02s and extracting for 35s, cleaning, and introducing H2Performing chemical adsorption on O gas, wherein the introducing time is 0.02s, the extracting time is 0s, then introducing inert gas to assist plasma to glow, the plasma power is 300W, the duration is 16s, the extracting time is 12s, wherein the in-situ oxidation and cleaning are performed under the conditions that the main pipeline Ar flow is 35sccm, the temperature is 85 ℃ and the pressure of a reaction cavity is 0.25 torr;
(4) repeating the step (3) for 1 time to obtain Al2O3A film;
(5) repeating the steps (1) to (4) for 22 times to obtain the metal oxide transparent conductive film.
Example 6
A preparation method of a GZO transparent conductive film comprises the following steps:
(1) introducing diethyl zinc (DEZ) into the reaction chamber for 0.02s and extracting for 30s, cleaning, and introducing H2Performing chemical adsorption on O gas for 0.02s, pumping off for 0s, then introducing Ar gas to assist plasma to glow, wherein the plasma power is 300W, the duration is 16s, and the pumping off time is 12s, wherein the Ar flow of the main pipeline is 35 sccm; the in-situ oxidation and the cleaning are carried out under the conditions that the temperature is 90 ℃ and the pressure of a reaction cavity is 0.25 torr;
(2) repeating the step (1) for 20 times to obtain a ZnO film;
(3) introducing trimethyl gallium (TMGa) for 0.03s and extracting for 35s, cleaning, and introducing H2Performing chemical adsorption on O gas, wherein the introducing time is 0.02s, the extracting time is 0s, then introducing inert gas to assist plasma to glow, the plasma power is 300W, the duration is 16s, the extracting time is 12s, wherein the in-situ oxidation and cleaning are performed under the conditions that the main pipeline Ar flow is 35sccm, the temperature is 90 ℃ and the pressure of a reaction cavity is 0.25 torr;
(4) repeating the step (3) for 1 time to obtain Ga2O3A film;
(5) repeating the steps (1) to (4) for 22 times to obtain the GZO transparent conductive film.
Example 7
A method for preparing an IZO transparent conductive film comprises the following steps:
(1) introducing diethyl zinc (DEZ) into the reaction chamber for 0.02s and extracting for 35s, cleaning, and introducing H2Performing chemical adsorption on O gas for 0.03s, pumping off for 0s, then introducing Ar gas to assist plasma to glow, wherein the plasma power is 300W, the duration is 16s, and the pumping off time is 12s, wherein the Ar flow of the main pipeline is 35 sccm; the in-situ oxidation and the cleaning are carried out under the conditions that the temperature is 70 ℃ and the pressure of a reaction cavity is 0.25 torr;
(2) repeating the step (1) for 20 times to obtain a ZnO film;
(3) introducing trimethyl indium (TMIn) for 0.03s and extracting for 40s, cleaning, and introducing H2Performing chemical adsorption on O gas, wherein the introducing time is 0.03s, the extracting time is 0s, then introducing inert gas to assist plasma to glow, the plasma power is 300W, the duration is 16s, the extracting time is 12s, wherein the in-situ oxidation and cleaning are performed under the conditions that the Ar flow of a main pipeline is 35sccm, the temperature is 70 ℃ and the pressure of a reaction cavity is 0.25 torr;
(4) repeating the step (3) for 1 time to obtain In2O3A film;
(5) repeating the steps (1) to (4) for 22 times to obtain the IZO transparent conductive film.
Example 8
A preparation method of an ITO transparent conductive film comprises the following steps:
(1) introducing dimethyl tin (DMSn) into the reaction chamber for 0.03s and 40s, cleaning, and introducing H2Performing chemical adsorption on O gas for 0.02s, pumping off for 0s, then introducing Ar gas to assist plasma to glow, wherein the plasma power is 300W, the duration is 16s, and the pumping off time is 12s, wherein the Ar flow of the main pipeline is 35 sccm; the in-situ oxidation and the cleaning are carried out under the conditions that the temperature is 80 ℃ and the pressure of a reaction cavity is 0.25 torr;
(2) repeating the step (1) for 20 times to obtain a SnO film;
(3) introducing trimethyl indium (TMIn) is introduced for 0.05s, the extraction time is 35s, cleaning is carried out, and H is introduced2Performing chemical adsorption on O gas, wherein the introducing time is 0.02s, the extracting time is 0s, then introducing inert gas to assist plasma to glow, the plasma power is 300W, the duration is 16s, the extracting time is 12s, wherein the in-situ oxidation and cleaning are performed under the conditions that the main pipeline Ar flow is 35sccm, the temperature is 80 ℃ and the pressure of a reaction cavity is 0.25 torr;
(4) repeating the step (3) for 2 times to obtain In2O3A film;
(5) repeating the steps (1) to (4) for 22 times to obtain the ITO transparent conductive film.
Example 9
The only difference from example 8 is: the number of repetitions of steps (1) to (4) was 40.
Example 10
The only difference from example 8 is: the number of repetitions of steps (1) to (4) was 10.
Comparative example 8-1
The only difference from example 8 is: the number of repetitions of step (1) was 6.
Comparative examples 8to 2
The only difference from example 8 is: the number of repetition of step (1) was 45.
Comparative examples 8to 3
The only difference from example 8 is: the step (1) is changed into the following steps: introducing DMSn into the reaction chamber, cleaning, and introducing H2O/Ar, plasma glow, in-situ oxidation and cleaning; the other process parameters were the same as in example 8.
Comparative examples 8to 4
The only difference from example 8 is: the step (3) is changed into: introducing TMIn into the reaction chamber, cleaning, and introducing H2O/Ar, plasma glow, in-situ oxidation and cleaning; the other process parameters were the same as in example 8.
Comparative examples 8to 5
The only difference from example 8 is: the step (1) is changed into the following steps: introducing DMSn into the reaction chamber, cleaning, and introducing H2O/Ar, plasma glow, in-situ oxidation and cleaning;
meanwhile, the step (3) is changed into the following steps: introducing TMIn into the reaction chamber, cleaning, and introducing H2O/Ar, plasma glow, in-situ oxidation and cleaning; the other process parameters were the same as in example 8.
Testing the resistance and the thickness of the transparent conductive film:
the test was carried out using a four-probe tester with a probe pitch of 1mm and an automatic measurement current of 10 μ a, and the sheet resistance of the film products provided in the examples and comparative examples was measured, the thickness was measured using a step tester, the resistivity was calculated and recorded in table 1.
TABLE 1
| Sample (I) | Square resistance omega/□ | Thickness nm | Resistivity omega cm | The preparation temperature is lower |
| Example 1 | 370 | 30 | 1.1*10-3 | 60 |
| Example 2 | 800 | 32 | 2.6*10-3 | 70 |
| Example 3 | 350 | 34 | 1.2*10-3 | 70 |
| Example 4 | 800 | 31 | 2.4*10-3 | 80 |
| Example 5 | 1200 | 33 | 3.9*10-3 | 85 |
| Example 6 | 700 | 32 | 2.3*10-3 | 90 |
| Example 7 | 500 | 33 | 1.6*10-3 | 70 |
| Example 8 | 420 | 41 | 1.7*10-3 | 80 |
| Example 9 | 320 | 70 | 2.2*10-3 | 80 |
| Example 10 | 1300 | 20 | 2.6*10-3 | 80 |
| Comparative example 8-1 | 5500 | 25 | 1.4*10-2 | 80 |
| Comparative examples 8to 2 | 2200 | 55 | 1.2*10-2 | 80 |
| Comparative examples 8to 3 | 7000 | 45 | 3.2*10-2 | 80 |
| Comparative examples 8to 4 | 7500 | 42 | 3.2*10-2 | 80 |
| Comparative examples 8to 5 | 9500 | 50 | 4.8*10-2 | 80 |
As shown in Table 1, it can be seen from the results of comparative examples 8to 10, comparative examples 8-1 and 8-2 that the present invention is achieved by providing N1:N2In the range of (14 to 21) to (1 to 4), the plasma processing frequency, H, is increased2The release of hydroxyl free radicals in O is more sufficient, the reaction temperature is greatly reduced, and the preparation of the metal oxide transparent conductive film with low resistivity at low temperature is realized. In addition, N is suitable here1:N2On the premise of the ratio, M is set to be in a range of 20-22 to be matched with the transparent conductive film, so that the conductivity of the transparent conductive film of the metal oxide is further optimized.
Comparing the results of example 8 with comparative examples 8-3, 8-4 and 8-5, it can be seen that the invention is at reasonable N1:N2On the premise of the ratio, the invention does not directly use Ar/H2The O is processed by plasma, which is different from the method of introducing oxygen and carrier inert gas simultaneously in the prior art, but strictly controls the sequence of reaction gas entering the cavity, and H is introduced in advance before plasma glow is started2The O gas plasma source performs chemisorption, and it is known from the conductivity of the resulting conductive film that the oxide deposition of the present invention is uniform and the impurity content is very low. Therefore, the excellent properties of the conductive film in the present invention are the combined result of the number of cycles and the order of addition of the raw materials in cooperation with each other.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (20)
1. A preparation method of a metal oxide transparent conductive film is characterized by comprising the following steps:
(1) introducing a first metal precursor into the reaction chamber, cleaning, and introducing H2Carrying out chemical adsorption on O gas, then introducing inert gas to assist plasma to glow, carrying out in-situ oxidation, and cleaning;
(2) repeating the step (1) by N1Then, obtaining a first metal oxide film;
(3) introducing a second metal precursor, cleaning, introducing H2Carrying out chemical adsorption on O gas, then introducing inert gas to assist plasma to glow, carrying out in-situ oxidation, and cleaning;
(4) repeating the step (3) by N2Then, obtaining a second metal oxide film;
(5) repeating the steps (1) - (4) for M times to obtain a metal oxide transparent conductive film;
wherein N is1:N2＝(14～21):(1～4)，M＝10～40。
2. The method of preparing a metal oxide transparent conductive film according to claim 1, wherein the metal oxide transparent conductive film comprises any one of an AZO film, a GZO film, an IZO film or an ITO film.
3. The method for preparing a metal oxide transparent conductive film according to claim 1 or 2, wherein the first metal precursor in step (1) and the second metal precursor in step (3) are each independently any one of a halide, an alkyl compound, an alkoxy compound, an alkylamino compound, a cyclopentadienyl compound, an β -dione compound, an amidino compound and a guanidino compound, or a combination of at least two thereof.
4. The method of claim 3, wherein each raw material has an electronic grade purity.
5. The method for preparing a metal oxide transparent conductive film according to claim 1, wherein the time period for introducing the metal precursor in the step (1) and the metal precursor in the step (3) are each independently 0.01 to 0.05 s.
6. The method for preparing a metal oxide transparent conductive film according to claim 1 or 5, wherein the step (1) and the step (3) are each independently followed by extracting a residual gas after the metal precursor is introduced.
7. The method of claim 6, wherein the time for the pump-off is not greater than 20 seconds.
8. The method for preparing a metal oxide transparent conductive film according to claim 1, wherein the H is introduced in the step (1) and the step (3)2The O gas is independently used for 0.01 to 0.05 s.
9. The method for preparing a metal oxide transparent conductive film according to claim 1 or 8, wherein the H is introduced in the step (1) and the step (3)2The residual gas is then removed independently of each other after the O gas.
10. The method of claim 9, wherein the time for the pump-off is not greater than 20 seconds.
11. The method for preparing a metal oxide transparent conductive film according to claim 1, wherein the gas H introduced in the step (1)2The molar ratio of O to the first metal precursor is (2-4): 1.
12. The method for preparing a metal oxide transparent conductive film according to claim 1 or 11, wherein the gas H introduced in the step (3)2The molar ratio of O to the second metal precursor is (3-6): 1.
13. The method for preparing a metal oxide transparent conductive film according to claim 1, wherein the inert gas in the steps (1) and (3) is independently selected from any one or a combination of at least two of nitrogen, helium, neon, argon, krypton, or xenon.
14. The method for preparing a metal oxide transparent conductive film according to claim 13, wherein the inert gas in step (1) and step (3) is independently selected from nitrogen and/or argon.
15. The method for preparing a metal oxide transparent conductive film according to claim 1, wherein the inert gas is introduced at a flow rate of 30to 250sccm in each of the step (1) and the step (3).
16. The method for preparing a metal oxide transparent conductive film according to claim 1, wherein the plasma ignition time in step (1) and step (3) is 5to 30s and the power is 100 to 300W, respectively.
17. The method according to claim 1, wherein the pressure in the reaction chamber is 0.09to 0.35Torr and the temperature is 60 to 90 ℃ independently from the temperature in the in-situ oxidation in the step (1) and the step (3).
18. The method for preparing a metal oxide transparent conductive film according to claim 1, wherein N is2＝1～4；M＝20～22。
19. A metal oxide transparent conductive film comprising a layered structure in which first metal oxide films and second metal oxide films are alternately stacked, the metal oxide transparent conductive film being produced by the method for producing a metal oxide transparent conductive film according to any one of claims 1 to 18.
20. Use of the metal oxide transparent conductive film according to claim 19 as an anode for OLED displays, thin film solar cell electrodes or touch screen electrodes.
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