CN104078531A - Method for manufacturing ZnO:Li transparent conducting thin film with wide spectral domain light transmission characteristic and directly-growing meteor crater fabric surface - Google Patents
Method for manufacturing ZnO:Li transparent conducting thin film with wide spectral domain light transmission characteristic and directly-growing meteor crater fabric surface Download PDFInfo
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- CN104078531A CN104078531A CN201410299623.3A CN201410299623A CN104078531A CN 104078531 A CN104078531 A CN 104078531A CN 201410299623 A CN201410299623 A CN 201410299623A CN 104078531 A CN104078531 A CN 104078531A
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000005540 biological transmission Effects 0.000 title claims abstract description 13
- 239000010409 thin film Substances 0.000 title abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 239000004744 fabric Substances 0.000 title abstract 3
- 230000003595 spectral effect Effects 0.000 title abstract 2
- 238000004544 sputter deposition Methods 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005530 etching Methods 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 17
- 230000007704 transition Effects 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 6
- 238000002834 transmittance Methods 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000005036 potential barrier Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 238000005137 deposition process Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 28
- 238000005516 engineering process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 241001251949 Xanthium sibiricum Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000002294 plasma sputter deposition Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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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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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/541—Heating or cooling of the substrates
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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
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
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Abstract
The invention relates to a method for manufacturing a ZnO:Li transparent conducting thin film with a wide spectral domain light transmission characteristic and a directly-growing meteor crater fabric surface and a manufactured product of the method. A magnetron sputtering method is adopted, the high-temperature volatile characteristic of Li atoms is utilized, the temperature of a high and low temperature substrate in the sputtering deposition process is controlled to achieve modulation doping, and the problem that the light transmission rate and electrical conductivity of a visible-infrared waveband of a ZnO transparent conducting thin film are restricted mutually is solved. A ZnO:Li thin film layer is hydrogenated, a ZnO:Li-H transitional loose layer grows, a dipole face (1000) appears, oxygen is absorbed, a vacuum level is moved upwards, and the problem that a potential barrier between ZnO:X-H and a battery window layer is too high is solved. The surface of the transitional loose layer is bombarded by etching and sputtering particles through hydrogen plasma, and the meteor crater fabric surface directly grows. The light transmission rate of the ZnO:Li transparent conducting thin film reaches more than 85 percent within the light wavelength range of 480 nm-2300 nm, the specific resistance also reaches 10<4> omega cm, and the thin film can be applied to amorphous silicon laminated solar battery front electrodes.
Description
Technical field
The present invention relates to the front electrode nesa coating manufacturing technology field of solar cell, specifically a kind of preparation method of the ZnO:Li transparent conductive film with wide range territory light transmission characteristic and crater matte direct growth and make product.
Background technology
Transparent conductive film has been widely used in daily photovoltaic---solar cell transparency electrode, liquid crystal display, touch control display, the high printing opacity protective glass of radioresistance line and automobile front windowpane heater circuit etc.; one of critical material of photovoltaic, be China be badly in need of to solve there is one of great basic research problems of general character.
The nesa coating being applied at present on the front electrode of solar cell (as shown in Figure 1) mainly contains two kinds.A kind of is that tin is mixed indium oxide (ITO), and this nesa coating can reach more than 90% visible light transmissivity, and resistivity can be low to moderate 10
-5Ω cm, product is ripe.But the defect of this product maximum is: chemical element indium belongs to rare element on earth, few at occurring in nature storage capacity, price is higher, not environmental protection; Another kind is the SnO that mixes fluorine
2conducting film (SnO
2: F, referred to as FTO), can be as the replacement articles for use of ITO conducting film.But SnO
2when conducting film is used as the front electrode of solar cell, under plasma environment, its electric property is stable not, will affect battery performance.
The disclosed bibliographical information result overwhelming majority is just extended to 900nm wavelength good light transmission rate, although the people such as Yang M have obtained good effect widening aspect infrared light transmitance, but has used phosphide element rare on the earth.Known, in the work of widening aspect the visible-near-infrared high permeability of zno-based film, still shoulder heavy responsibilities at present.Therefore, in research method and thinking, break through the restriction of plasma frequency theory, by ZnO film is carried out to doping vario-property, research improves carrier mobility and reduces theory and the method for ZnO thin film doped charge carrier effective mass, guaranteeing under the prerequisite of film excellent conductive performance, reach and widen infrared light through scope object, this is one of ZnO thin film doped key foundation problem that is applied to the required solution of front electrodes of solar cells.
Can enhanced light scattering effect due to the application of suede structure TCO film, improve and fall into light effect, on improving efficiency and the stability of Si base thin film solar battery, play conclusive impact.J. the people such as H ü pkes report, by optimizing magnetron sputtering technique, the sample of preparing under 4.3 Pa conditions at deposition pressure, by harsh method, obtains crater body structure surface pattern; People's reports such as national section Siberian cocklebur is big, Xue Junming, suitably oxygen flow preparation has petal-shaped film surface appearance, and harsh rear film surface is cratering.The suede structure that this method obtains, there is good light trapping effect, be suitable for front electrodes of solar cells, but large area corrosion ZnO has high risk and causes waste of material when film forms suede structure, this method need to first carry out magnetron sputtering preparation then etching two steps complete, increased the complexity of technique.Solve cratering textured ZnO
-the preparation of TCO intrinsic, and solve ZnO
-high Potential Barrier Problems between TCO and p-SiC:H Window layer is ZnO thin film doped two other key foundation problem that is applied to the required solution of front electrodes of solar cells.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind ofly there is high conductivity, high light transmittance, higher suede degree, intrinsic crater matte, excellently fall into optical property, wide range territory photopermeability, with the preparation method of the low ZnO:Li transparent conductive film of p-type Window layer contact berrier and make product.
Technical scheme of the present invention is: a kind of preparation method with the ZnO:Li transparent conductive film of wide range territory light transmission characteristic and crater matte direct growth, comprises the following steps:
(1) load: selecting mol ratio is the Li of Li:Zn=3.5～5.5:96.5～94.5
2o and ZnO are raw material, pulverize and process by high temperature sintering, make Li
2o:ZnO ceramic target; By the above-mentioned Li making
2o:ZnO ceramic target and substrate interval relatively pack in the vacuum cavity of magnetic-controlled sputtering coating equipment;
(2) growth of ZnO:Li thin layer: first the background gas pressure of vacuum chamber is evacuated to 4.5～8.0 * 10
-4pa, pass into sputter air source A r, its gas flow is 29.4～30sccm, adjust the position of vacuum valve, make the sputtering pressure of vacuum chamber maintain 0.7～1.0Pa, sputtering power 200～300 W, then on temperature is the substrate of 450～550 ℃ and 200～250 ℃, deposit respectively 30～40min and 40～50min, make ZnO:Li thin layer;
(3) growth of ZnO:Li-H transition weaker zone: first keep passing into sputter gas Ar, add another kind of impurity gas H
2, H
2flow 0.6～1.2sccm, makes Ar and H
2total flow remains on 30～31.2sccm, adjusts sputtering pressure and maintains 0.7～1.0Pa; Sputtering power is 300～350W, and then bias voltage 50～100V deposits 10～15min on temperature is the substrate of 100～150 ℃, on ZnO:Li thin layer basis, obtains the ZnO:Li-H transition weaker zone that a layer thickness is 50～100nm;
(4) ZnO:Li crater suede structure is directly grown: first maintenance passes into sputter gas Ar, its flow is reduced to 28.8～29.6sccm, impurity gas H
2, its flow is increased to 0.8～1.2sccm, Ar and H
2total flow remains on 29.6～30.8sccm, adjust sputtering pressure and be reduced to 0.1～0.3Pa, sputtering power 350～400W, underlayer temperature is 0～100 ℃, then by hydrogen plasma, ZnO:Li-H transition weaker zone is bombarded and etching 5～10 min energetically, obtain ZnO:Li crater suede structure.
Described ceramic target and substrate are spaced apart 51～71 mm.
Described Li
2the high temperature sintering temperature of O:ZnO ceramic target is 1220～1310 ℃.
The suede degree of described ZnO:Li crater matte is 25～35%.
The ZnO:Li transparent conductive film that above-mentioned preparation method makes, is characterized in that: described ZnO:Li transparent conductive film has well-crystallized orientation, and resistivity is lower than 1.0 * 10
-4Ω cm, the light transmittance in 480nm～2300nm optical wavelength range reaches more than 85%.
Described ZnO:Li transparent conductive film and battery Window layer have low contact berrier.
The present invention adopts magnetically controlled sputter method, utilizes the volatile characteristic of high temperature of Li atom, and high low temperature underlayer temperature is realized modulation doping when controlling sputtering sedimentation, solve ZnO nesa coating visible-infrared band light transmission rate and conductivity phase restriction problem; By the hydrogenation to ZnO:Li thin layer,, there is (1000) dipole face in growth ZnO:Li-H transition weaker zone, and adsorb oxygen, above moves vacuum level, solves the too high problem of potential barrier between ZnO:X-H and battery Window layer; By hydrogen plasma etching and sputtering particle bombardment transition weaker zone surface, direct growth crater matte.This ZnO:Li transparent conductive film, reaches more than 85% at 480nm-2300nm optical wavelength range light transmission rate, and resistivity is lower than 1.0 * 10
-4Ω cm; Crater matte is directly prepared, its suede degree is 25%-35%, be applied to amorphous silicon laminated front electrodes of solar cells, the p-type Window layer contact berrier of itself and solar cell is low, having widened the absorption region of battery to optical band, is a kind of front electrode material of amorphous silicon solar cell of Performance Ratio conventional transparent electrode excellence.
Accompanying drawing explanation
Accompanying drawing 1 is solar battery structure schematic diagram;
Accompanying drawing 2 is for preparing the ZnO:Li thin-film technique sketch with intrinsic crater suede structure;
Accompanying drawing 3 is the XRD result figure of ZnO:Li film;
Accompanying drawing 4 is the ZnO:Li film transmitance within the scope of 400-2300 nm;
Accompanying drawing 5 is for having the surface topography map of the ZnO:Li film of intrinsic crater suede structure.
Embodiment
Below 1-5 and embodiment carry out saying in detail as follows to the present invention with reference to the accompanying drawings:
Embodiment 1
A preparation method with the ZnO:Li transparent conductive film of wide range territory light transmission characteristic and crater matte direct growth, adopts a magnetic control sputtering system, and directly sputter obtains having the ZnO:Li film of crater suede structure; Simplified preparation technology's flow process, comprised the following steps as shown in Figure 2:
(1) load: selecting mol ratio is the Li of Li:Zn=3.5:96.5
2o and ZnO are raw material, pulverize and process by 1250 ℃ of high temperature sinterings, make Li
2o:ZnO ceramic target; By the above-mentioned Li making
2o:ZnO ceramic target and substrate interval 52mm relatively pack in the vacuum cavity of magnetic-controlled sputtering coating equipment;
(2) growth of ZnO:Li thin layer: first the background gas pressure of vacuum chamber is evacuated to 5.0 * 10
-4pa, pass into sputter air source A r, its gas flow is 30sccm, adjust the position of vacuum valve, make the sputtering pressure of vacuum chamber maintain 1.0Pa, sputtering power 200W, then on temperature is the substrate of 500 ℃ and 200 ℃, deposit respectively 35min and 45min, make ZnO:Li thin layer as (as shown in Figure 4);
(3) growth of ZnO:Li-H transition weaker zone: first keep passing into sputter gas Ar, add another kind of impurity gas H
2, H
2flow 0.8sccm, makes Ar and H
2total flow remains on 30.8sccm, adjusts sputtering pressure and maintains 0.8Pa; Sputtering power is 310W, and then bias voltage 60V deposits 12min on temperature is the substrate of 120 ℃, on ZnO:Li thin layer basis, obtains the ZnO:Li-H transition weaker zone that a layer thickness is 60nm;
(4) ZnO:Li crater suede structure is directly grown: first maintenance passes into sputter gas Ar, its flow is reduced to 29sccm, impurity gas H
2, its flow is increased to 1.0sccm, Ar and H
2total flow remains on 30sccm, adjust sputtering pressure and be reduced to 0.1Pa, sputtering power 350W, underlayer temperature is 20 ℃, then by hydrogen plasma, ZnO:Li-H transition weaker zone is bombarded and etching 5min energetically, obtain suede degree and be 28% ZnO:Li crater suede structure (as shown in Figure 5).
Make ZnO:Li transparent conductive film and have well-crystallized orientation (as shown in Figure 3), resistivity is low to moderate 0.8 * 10
-4Ω cm, the light transmittance in 480nm～2300nm optical wavelength range reaches 88%.
Embodiment 2
A preparation method with the ZnO:Li transparent conductive film of wide range territory light transmission characteristic and crater matte direct growth, adopts a magnetic control sputtering system, and directly sputter obtains having the ZnO:Li film of crater suede structure; Simplified preparation technology's flow process, comprised the following steps as shown in Figure 2:
(1) load: selecting mol ratio is the Li of Li:Zn=4:96
2o and ZnO are raw material, pulverize and process by 1280 ℃ of high temperature sinterings, make Li
2o:ZnO ceramic target; By the above-mentioned Li making
2o:ZnO ceramic target and substrate interval 67mm relatively pack in the vacuum cavity of magnetic-controlled sputtering coating equipment;
(2) growth of ZnO:Li thin layer: first the background gas pressure of vacuum chamber is evacuated to 6.5 * 10
-4pa, passes into sputter air source A r, its gas flow is 29.6sccm, adjusts the position of vacuum valve, make the sputtering pressure of vacuum chamber maintain 0.8Pa, sputtering power 280W then deposits respectively 35min and 45min on temperature is the substrate of 500 ℃ and 230 ℃, makes ZnO:Li thin layer;
(3) growth of ZnO:Li-H transition weaker zone: first keep passing into sputter gas Ar, add another kind of impurity gas H
2, H
2flow 1.0sccm, makes Ar and H
2total flow remains on 30.6sccm, adjusts sputtering pressure and maintains 0.9Pa; Sputtering power is 340W, and then bias voltage 90V deposits 14min on temperature is the substrate of 150 ℃, on ZnO:Li thin layer basis, obtains the ZnO:Li-H transition weaker zone that a layer thickness is 90nm;
(4) ZnO:Li crater suede structure is directly grown: first maintenance passes into sputter gas Ar, its flow is reduced to 29sccm, impurity gas H
2, its flow is increased to 1.2sccm, Ar and H
2total flow remains on 30.2sccm, adjust sputtering pressure and be reduced to 0.2Pa, sputtering power 390W, underlayer temperature is 80 ℃, then by hydrogen plasma, ZnO:Li-H transition weaker zone is bombarded and etching 8min energetically, obtain suede degree and be 33% ZnO:Li crater suede structure.
Make ZnO:Li transparent conductive film and have well-crystallized orientation, resistivity is low to moderate 0.9 * 10
-4Ω cm, the light transmittance in 480nm～2300nm optical wavelength range reaches 90%.
Claims (6)
1. a preparation method with the ZnO:Li transparent conductive film of wide range territory light transmission characteristic and crater matte direct growth, comprises the following steps:
(1) load: selecting mol ratio is the Li of Li:Zn=3.5～5.5:96.5～94.5
2o and ZnO are raw material, pulverize and process by high temperature sintering, make Li
2o:ZnO ceramic target; By the above-mentioned Li making
2o:ZnO ceramic target and substrate interval relatively pack in the vacuum cavity of magnetic-controlled sputtering coating equipment;
(2) growth of ZnO:Li thin layer: first the background gas pressure of vacuum chamber is evacuated to 4.5～8.0 * 10
-4pa, pass into sputter air source A r, its gas flow is 29.4～30sccm, adjust the position of vacuum valve, make the sputtering pressure of vacuum chamber maintain 0.7～1.0Pa, sputtering power 200～300 W, then on temperature is the substrate of 450～550 ℃ and 200～250 ℃, deposit respectively 30～40min and 40～50min, make ZnO:Li thin layer;
(3) growth of ZnO:Li-H transition weaker zone: first keep passing into sputter gas Ar, add another kind of impurity gas H
2, H
2flow 0.6～1.2sccm, makes Ar and H
2total flow remains on 30～31.2sccm, adjusts sputtering pressure and maintains 0.7～1.0Pa; Sputtering power is 300～350W, and then bias voltage 50～100V deposits 10～15min on temperature is the substrate of 100～150 ℃, on ZnO:Li thin layer basis, obtains the ZnO:Li-H transition weaker zone that a layer thickness is 50～100nm;
(4) ZnO:Li crater suede structure is directly grown: first maintenance passes into sputter gas Ar, its flow is reduced to 28.8～29.6sccm, impurity gas H
2, its flow is increased to 0.8～1.2sccm, Ar and H
2total flow remains on 29.6～30.8sccm, adjust sputtering pressure and be reduced to 0.1～0.3Pa, sputtering power 350～400W, underlayer temperature is 0～100 ℃, then by hydrogen plasma, ZnO:Li-H transition weaker zone is bombarded and etching 5～10 min energetically, obtain ZnO:Li crater suede structure.
2. preparation method according to claim 1, is characterized in that: described ceramic target and substrate are spaced apart 51～71 mm.
3. preparation method according to claim 1, is characterized in that: described Li
2the high temperature sintering temperature of O:ZnO ceramic target is 1220～1310 ℃.
4. preparation method according to claim 1, is characterized in that: the suede degree of described ZnO:Li crater matte is 25～35%.
5. the ZnO:Li transparent conductive film making according to the arbitrary described preparation method of claim 1-4, is characterized in that: described ZnO:Li transparent conductive film has well-crystallized orientation, and resistivity is lower than 1.0 * 10
-4Ω cm, the light transmittance in 480nm～2300nm optical wavelength range reaches more than 85%.
6. ZnO:Li transparent conductive film according to claim 5, is characterized in that: described ZnO:Li transparent conductive film and battery Window layer have low contact berrier.
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