CN105140312A - Composite TCO film and preparation method thereof - Google Patents
Composite TCO film and preparation method thereof Download PDFInfo
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- CN105140312A CN105140312A CN201510541318.5A CN201510541318A CN105140312A CN 105140312 A CN105140312 A CN 105140312A CN 201510541318 A CN201510541318 A CN 201510541318A CN 105140312 A CN105140312 A CN 105140312A
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- zio
- transparent conductive
- ito
- oxide film
- conductive oxide
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- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 41
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 150000002471 indium Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 5
- 229950009789 cetomacrogol 1000 Drugs 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229920003091 Methocel™ Polymers 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- KKKAMDZVMJEEHQ-UHFFFAOYSA-N [Sn].[N+](=O)(O)[O-] Chemical compound [Sn].[N+](=O)(O)[O-] KKKAMDZVMJEEHQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- -1 oxygen alkane Chemical class 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229920003064 carboxyethyl cellulose Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
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- 239000010408 film Substances 0.000 description 93
- 239000011521 glass Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 230000003667 anti-reflective effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
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- 230000008901 benefit Effects 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 229910004541 SiN Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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- 238000001451 molecular beam epitaxy Methods 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a composite TCO film and a preparation method thereof. The composite TCO film comprises an ITO layer and a ZIO layer, wherein the ITO layer is arranged on a substrate, the ZIO layer is arranged on the ITO layer, and the surface structure of the ZIO layer is a texture structure. The preparation method comprises: (1) preparing an ITO precursory solution; (2) preparing a film coating substrate, and heating and baking the film coating substrate to obtain a substrate with the ITO layer; and (3) preparing a ZIO hydrothermal solution, placing the substrate with the ITO layer in the ZIO hydrothermal solution to perform hydro-thermal reaction to obtain a TCO film. The composite TCO film has the characteristics of higher transmittance, lower resistivity, proper refractive index and thickness, good surface viscosity and surface light tripping effect, stable physical property, low cost preparation method, simple equipment and zero production pollution.
Description
Technical field
The invention belongs to technical field of photovoltaic power generation, relate to the developmental research of the important component part of HIT solar cell or thin film silicon solar cell, be specifically related to transparent conductive oxide film of a kind of novel composite layered structure and preparation method thereof.
Background technology
Along with the development of photovoltaic power generation technology, especially the industrialization of novel solar battery (as: thin-film solar cells, HIT battery etc.) in recent years, transparent conductive oxide film (TCO), as the indispensable part of novel solar battery, causes great concern.
Transparent conductive oxide film is important a member of semiconductor family, and its fundamental characteristics comprises: larger energy gap (>3.0ev), DC resistivity (N-shaped) reaches 10
-5~ 10
-4Ω cm, the transmitance (>80%) etc. that visible region is higher.Conventional transparent conductive oxide film mainly comprises SnO
2, In
2o
3, ZnO, CdO, Ca
2o
3deng and their bases on doping system.
Sn adulterates In
2o
3(ITO) film has that light transmittance is high, good conductivity, resistance to wear are good, chemical stability is high, substrate adhesion is strong and hardness comparatively advantages of higher.ITO has been widely used in the fields such as flat panel display, micro-wave screening, solar cell.People attempt the resistivity, the raising visible light transmissivity that constantly go to reduce ITO, have correspondingly developed laser molecular beam epitaxy, magnetron sputtering, thermal spraying, vapour deposition, sputtering sedimentation, solwution method etc.Although the excellent performance of ITO, the sale price of ITO is up to 500 yuan/m
2, limit popularization.
Zn in ZnO is rich content, nontoxic, low price in the earth's crust, and unadulterated ZnO is not used widely due to shortcomings such as resistivity are high, unstable.The IIIA race elements such as usual employing B, Al, Ga, In adulterate to improve its conductivity and thermal stability to ZnO.With B
3+, Al
3+, Ga
3+compare, In
3+ionic radius and Zn
2+more close, it is just smaller that such In mixes rear caused distortion of lattice; And In has larger electronegativity, be not as active as Al, Ga, Zn, not easily form oxide, be more conducive to In and be present in lattice with the form of displacement, improve the conductivity of film.Compared with the transparent conductive material ITO of present extensive use, In doping in ZIO is only 0.5-5% (molar percentage), and its production cost can be controlled in acceptable scope.
Before solar cell requires, electrode has high light transmission rate and high conductivity.In prior art, before solar cell, the functionalization of electrode coating is single, as: TiO
2, SnO
2, SiO
2, SiN
x, ITO and MgF
2films etc., can not meet photovoltaic development in science and technology to the diversified requirement of electrode coating performance before solar energy etc.Specific surface treatment and structural design are carried out to transparent conductive film, makes film while electrically conducting transparent, also have the effect of anti-reflection, anti-reflection to a certain degree, thus to a certain degree improving battery efficiency down.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, there is provided a kind of and there is good light transmission rate, lower resistivity, suitable refractive index and thickness, good surface adhesiveness and surperficial light trapping effect, stable physical property and have both the composite transparent conductive oxide film of anti-reflection anti-reflection function, also provide a kind of with low cost, equipment simple, it is pollution-free to produce, can the preparation method of composite transparent conductive oxide film of suitability for industrialized production.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A kind of composite transparent conductive oxide film, comprise ITO layer and ZIO layer, described ITO layer is located on a substrate, and described ZIO layer is located in described ITO layer; The surface texture of described ZIO layer is suede structure.
In above-mentioned composite transparent conductive oxide film, preferably, the refractive index of described composite transparent conductive oxide film is 2.1 ~ 2.5, and thickness is 60nm ~ 80nm, light transmission rate > 90%, resistivity < 4 × 10
-4Ω cm.
As a total technical conceive, the present invention also provides a kind of preparation method of composite transparent conductive oxide film, comprises the following steps:
Comprise the following steps:
(1) by water-soluble to indium salt, pink salt, thickener, levelling agent and dispersant, after dispersion, ITO precursor solution is obtained;
(2) described ITO precursor solution is coated on a substrate by lift plated film, then dry, repeat described coating and dry run, until rete reaches desired thickness, obtain film substrate; Described film base plate heating is warming up to 250 DEG C ~ 350 DEG C, after constant temperature is roasted, with stove cooling, obtains the substrate being with ITO layer;
(3) by water-soluble to zinc salt, indium salt, weak base and dispersant, after dispersion, ZIO hydrothermal solution is obtained; The substrate of band ITO layer step (2) obtained is placed in described ZIO hydrothermal solution, at 60 DEG C ~ 95 DEG C, carry out hydro-thermal reaction, then washing, drying, form ZIO layer on the ito layer, obtain ITO/ZIO composite coating, be composite transparent conductive oxide film.
In the preparation method of above-mentioned composite transparent conductive oxide film, preferably, in described step (1) (in ITO precursor solution), by mass parts, indium salt is 20.7 ~ 44.0 parts, and pink salt is 2.3 ~ 4.9 parts, thickener is 0.1 ~ 2.0 part, levelling agent is 0.1 ~ 2.0 part, and dispersant is 0.1 ~ 4.4 part, and water is 46.8 ~ 75.3 parts.
In the preparation method of above-mentioned composite transparent conductive oxide film, preferably, in described step (3) (in ZIO hydrothermal solution), by mass parts, described zinc salt is 0.35 ~ 9.32 part, and described indium salt is 0.05 ~ 1 part, and described weak base is 0.35 ~ 3.26 part, described dispersant is 0.1 ~ 1 part, and described water is 85.42 ~ 99.15 parts.
In the preparation method of above-mentioned composite transparent conductive oxide film, preferably, in described step (2), the process conditions of described lift plated film are: lift temperature is 20 DEG C ~ 35 DEG C, decrease speed is 6mm/min ~ 10mm/min, pull rate is 0.6mm/min ~ 3mm/min, is 5min ~ 8min during the stop of described substrate in ITO precursor solution; The temperature of described drying is 100 DEG C ~ 200 DEG C, and the time of described drying is 2min ~ 15min, and the atmosphere of described drying is air atmosphere; Described coating and dry number of repetition are 5 times ~ 10 times.
In the preparation method of above-mentioned composite transparent conductive oxide film, preferably, in described step (2), described heat temperature raising carries out in air atmosphere, heating rate is 45 DEG C/min ~ 55 DEG C/min, and described constant temperature roasted time is 0.5 hour ~ 2 hours; In described step (3), the time of described hydro-thermal reaction is 5h ~ 42h, and the temperature of described drying is 100 ~ 200 DEG C, and the time of described drying is 2min ~ 15min.
In the preparation method of above-mentioned composite transparent conductive oxide film, preferably, in described step (1) (in ITO precursor solution), described indium salt is inidum chloride and/or indium nitrate; Described pink salt is stannic chloride and/or nitric acid tin; Described thickener is one or more in methylcellulose, carboxymethyl cellulose, carboxyethyl cellulose and carboxylic propyl methocel; Described levelling agent is one or more in polyether silicones oxygen alkane levelling agent, Sodium Polyacrylate and polyacrylamide; Described dispersant is one or more in polyvinylpyrrolidone, cetane trimethyl ammonium bromide, calgon, sodium polyphosphate, cetomacrogol 1000 and silane coupler.
In the preparation method of above-mentioned composite transparent conductive oxide film, preferably, in described step (3) (in ZIO hydrothermal solution), described zinc salt is zinc acetate and/or zinc nitrate; Described indium salt is inidum chloride and/or indium nitrate; Described weak base is one or more in triethylamine, pyridine, urea, cyclohexylamine, aniline, hexamethylenetetramine and ammoniacal liquor; Described dispersant is one or more in polyvinylpyrrolidone, neopelex, calgon, sodium polyphosphate, cetomacrogol 1000 and silane coupler.
In the preparation method of above-mentioned composite transparent conductive oxide film, preferably, in described step (1), the process of described dispersion comprises first mechanical dispersion, then ultrasonic disperse, shear agitation dispersion again, wherein, the operating frequency of described ultrasonic disperse is 20KHz ~ 30KHz, and the time of described ultrasonic disperse is 5min ~ 10min, the rotating speed of described shear agitation dispersion is 500r/min ~ 6000r/min, and the time of described shear agitation dispersion is 2min ~ 20min;
In described step (3), the process of described dispersion comprises first mechanical dispersed with stirring, then ultrasonic disperse, and wherein, the operating frequency of described ultrasonic disperse is 20KHz ~ 30KHz, and the time of described ultrasonic disperse is 5min ~ 30min.
In preparation method of the present invention, described substrate can select glass substrate, silicon chip (as amorphous silicon chip) substrate or thin-film solar cells, and ITO layer is Sn doping In
2o
3, ZIO layer is In doping ZnO.
In preparation method of the present invention, the ITO precursor solution pH value that described step (1) obtains is usually between 7.0 ~ 8.5; The pH value of the ZIO hydrothermal solution that described step (3) obtains is usually between 7.0 ~ 8.5.
In preparation method of the present invention, the composition of the zinc salt selected in the indium salt selected in ITO precursor solution, pink salt, thickener, levelling agent, dispersant and ZIO hydro-thermal reaction solution, indium salt, dispersant, weak base can difference also can be identical, preferably identical.
In preparation method of the present invention, before carrying out hydro-thermal reaction, usually can first clean and drying the substrate of band ITO layer, baking temperature is 100 DEG C ~ 200 DEG C, and drying time is 2min ~ 15min.
Acid solution, aqueous slkali soaking can be used successively before glass substrate film in said method, then use water, ethanol purge successively, finally use alcohol immersion stand-by.
The present invention carries out surface treatment to ZIO film, and film surface can be made to form light trapping structure.Light trapping structure is the suede structure that surface is formed, also known as surface-texturing.Light beam is radiated on suede structure, and reverberation can be radiated on adjacent suede structure, and reduce the reflection of light, the surface of the chemical polishing that this structural rate is smooth has better anti-reflection effect.Be slanted through film with the time and can increase light path, improve efficiency of light absorption, thus improve the operating efficiency of cell piece.
In addition, anti-reflection effect is played in the reflection selecting the transparent membrane of suitable refractive index can reduce light.Take glass as the crystal silicon solar batteries assembly of encapsulating material, choose refractive index n the most obvious (wherein at the antireflective effect of the transparent membrane of about 2.4
glass refraction n
0=1.5, crystal silicon chip refractive index n
sf=3.9).According to reported in literature, the refractive index of the ito thin film prepared under general condition and ZIO film is respectively 1.8-1.9 and 1.9-2.0, closely the best refractive index 2.4 of anti-reflection film.Under certain conditions, by certain process means be expected to prepare refractive index close to 2.4 ITO/ZIO laminated film.Therefore, ITO/ZIO laminated film, except the collection of photogenerated current, is suitable for the anti-reflection film of silicon solar cell equally.
When transparent membrane thickness is in certain specific size, certain anti-reflection effect can also be played.Research shows, reaches the energy peak wavelength X of the solar spectrum on ground
0for 500nm, the optical wavelength scope of crystal silicon battery response is 300 ~ 1100nm.For reaching high battery efficiency, the sunlight that wavelength is 500-700nm should be collected emphatically, usually get 640nm.Due to the interference effect of light, the optical thickness nd=λ of film
0when/4, (wherein n: the refractive index of film, d: the physical thickness of film) wavelength is λ
0the transmitance of light the highest, be namely λ to wavelength
0light have anti-reflection effect.For making solar cell have high battery efficiency, strengthen wavelength X
0(λ
0=500nm) the transmitance of light wave, then the optical thickness dn getting transparent membrane is 160nm.
ITO semiconductive thin film function admirable, technology of preparing are ripe; The cost of ZIO film is lower, carries out surface treatment it can be made to have light trapping structure to ZIO film.ITO, ZIO are made as composite coating by the present invention, can fully carry out having complementary advantages, Synergistic, and carrying out structural design to ITO/ZIO composite coating simultaneously and composite coating can be made to have both the effect of anti-reflection anti-reflection, is electrode material before the ideal of solar cell.
Compared with prior art, the invention has the advantages that:
1, composite transparent conductive oxide film of the present invention takes full advantage of the synergistic function of ITO layer and ZIO layer, ITO layer substrate adhesion is strong, good conductivity, resistance to wear are good, chemical stability is high, and ZIO layer cost is lower, and have the roughness (i.e. suede structure) of microscopic dimensions, ZIO is placed on outermost end, coating can be made to have light trapping structure, and the reflection reducing light reaches anti-reflection effect.
2, composite transparent conductive oxide film Surface Creation of the present invention suede structure, have light trapping effect, be the ideal material of electrode before novel solar battery.The refractive index of this composite transparent conductive oxide film is 2.1-2.5, it is desirable antireflective film material, the thickness of the ITO/ZIO laminated film prepared by the present invention is about 60nm ~ 80nm, and the optical thickness dn of film is very near the optimal thickness (160nm) of solar cell antireflective film.This ITO/ZIO laminated film has good light transmission rate (T>90%), lower resistivity (ρ <4 × 10
-4Ω cm), good surface adhesiveness and stable physical property.
3, composite transparent conductive oxide film of the present invention adopts liquid phase method to produce, and without the need to large-scale instrument and equipment, technique is simple, with low cost, pollution-free, and has a wide range of applications market.
Accompanying drawing explanation
Fig. 1 is the structural representation of composite transparent conductive oxide film in the embodiment of the present invention (i.e. ITO/ZIO composite coating).
Fig. 2 is the transmittance curve figure of the visible ray-ultraviolet light of composite transparent conductive oxide film prepared by the embodiment of the present invention 1,2,3.
Fig. 3 is the scanning electron microscope sem photo of composite transparent conductive oxide film prepared by the embodiment of the present invention 1.
Fig. 4 is the scanning electron microscope sem photo of composite transparent conductive oxide film prepared by the embodiment of the present invention 2.
Fig. 5 is the scanning electron microscope sem photo of composite transparent conductive oxide film prepared by the embodiment of the present invention 3.
Fig. 6 is the principle schematic adopting four probe method to survey semiconductor resistor rate in the embodiment of the present invention.
Marginal data:
1, substrate; 2, ITO layer; 3, ZIO layer; 4, suede structure.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection range not thereby limiting the invention.
The material adopted in following examples and instrument are commercially available.
Embodiment 1:
A kind of composite transparent conductive oxide film of the present invention, as shown in Figure 1, be located on substrate 1, this film comprises ITO layer 2 and ZIO layer 3, and ITO layer 2 is located on substrate 1, and ZIO layer 3 is located in ITO layer 2, and the surface texture of ZIO layer 3 is suede structure.
A preparation method for the composite transparent conductive oxide film of above-mentioned the present embodiment, comprises the following steps:
(1) preparation of ITO precursor solution: 29.05g inidum chloride, 3.23g stannic chloride, 1.98g methylcellulose, 0.63g polyether silicones oxygen alkane levelling agent (FL-3), 2.34g polyvinylpyrrolidone PVP are dissolved in the water of 70mL by mechanical dispersion after, at the ultrasonic lower dispersion 10min of operating frequency 20KHz, again by rotating speed be 6000r/min emulsification pretreatment mixer stir 10min, obtain the ITO precursor solution that pH is 7.3.
(2) preparation of ITO layer:
(2.1) film: under the environment of 25 DEG C, with the lift coating process that decrease speed 8mm/min, pull rate 1.5mm/min, time of staying are in the solution 6min, ITO precursor solution is coated on glass baseplate surface, then in thermostatic drying chamber in air atmosphere in 150 DEG C of freeze-day with constant temperature 5min, above-mentioned coating and dry run 8 times, obtain film substrate repeatedly.
(2.2) heat treatment: by film substrate in air atmosphere, after being heated to 320 DEG C from room temperature with the heating rate of 50 DEG C/min, the roasted 40min of constant temperature, with stove cooling, obtains the substrate being with ITO layer.
(3) preparation of ITO/ZIO composite coating (i.e. composite transparent conductive oxide film)
(3.1) configuration of ZIO hydrothermal solution: 9.32g zinc acetate and 1g inidum chloride are dissolved in 99mL water, add 3.26g hexamethylenetetramine, 1g polyvinylpyrrolidone PVP, after mechanical agitation, be after the ultrasonic disperse machine ultrasonic disperse 5min of 20KHz in operating frequency, obtain the ZIO hydrothermal solution that pH value is 8.4.
(3.2) hydro-thermal reaction: by the substrate clean water of band ITO layer, hydro-thermal glassware is put into after dry 10min at 120 DEG C, and in glassware, add above-mentioned joined ZIO hydrothermal solution, clean after 60 DEG C of hydro-thermal reaction 30h, dry 10min at 120 DEG C, finally on substrate, obtain ITO/ZIO composite coating, i.e. composite transparent conductive oxide film.
Embodiment 2:
A kind of composite transparent conductive oxide film of the present invention, as shown in Figure 1, be located on substrate 1, this film comprises ITO layer 2 and ZIO layer 3, and ITO layer 2 is located on substrate 1, and ZIO layer 3 is located in ITO layer 2, and the surface texture of ZIO layer 3 is suede structure.
A preparation method for the composite transparent conductive oxide film of above-mentioned the present embodiment, comprises the following steps:
(1) preparation of ITO precursor solution: 37.13g indium nitrate, 3.62g nitric acid tin, 1.03g carboxymethyl cellulose, 1.27g Sodium Polyacrylate, 0.68g cetane trimethyl ammonium bromide are dissolved in the water of 60mL by mechanical dispersion after, at the ultrasonic lower dispersion 7min of operating frequency 30KHz, again by rotating speed be 5000r/min emulsification pretreatment mixer stir 8min, obtain the ITO precursor solution that pH value is 7.0.
(2) preparation of ITO layer:
(2.1) film: under the environment of 25 DEG C, with the lift coating process that decrease speed 6mm/min, pull rate 1mm/min, time of staying are in the solution 5min, ITO precursor solution is coated on glass baseplate surface, then in thermostatic drying chamber in air atmosphere in 100 DEG C of freeze-day with constant temperature 15min, above-mentioned coating and dry run 10 times, obtain film substrate repeatedly.
(2.2) heat treatment: by film substrate in air atmosphere, after being heated to 350 DEG C, after insulation 30min, with stove cooling, obtains the substrate being with ITO layer from room temperature with the heating rate of 45 DEG C/min;
(3) preparation of ITO/ZIO composite coating (i.e. composite transparent conductive oxide film)
(3.1) configuration of ZIO hydrothermal solution: 6.35g zinc nitrate and 0.87g inidum chloride are dissolved in 98mL water, add 2.34g hexamethylenetetramine, 0.84g neopelex, after mechanical agitation, be after the ultrasonic disperse machine ultrasonic disperse 6min of 20KHz in operating frequency, obtain the ZIO hydrothermal solution that pH value is 8.2.
(3.2) hydro-thermal reaction: by the substrate clean water of band ITO layer, hydro-thermal glassware is put into after dry 8min at 130 DEG C, and in glassware, add above-mentioned joined ZIO hydrothermal solution, clean after 60 DEG C of hydro-thermal reaction 30h, dry 15min at 100 DEG C, substrate obtains ITO/ZIO composite coating, i.e. composite transparent conductive oxide film.
Embodiment 3:
A kind of composite transparent conductive oxide film of the present invention, as shown in Figure 1, be located on substrate 1, this film comprises ITO layer 2 and ZIO layer 3, and ITO layer 2 is located on substrate 1, and ZIO layer 3 is located in ITO layer 2, and the surface texture of ZIO layer 3 is suede structure.
A preparation method for the composite transparent conductive oxide film of above-mentioned the present embodiment, comprises the following steps:
(1) preparation of ITO precursor solution: 43.2g indium nitrate, 4.64 stannic chlorides, 1.8g carboxylic propyl methocel, 1.8g polyacrylamide, 1.8g cetomacrogol 1000 are dissolved in the water of 70mL by mechanical dispersion after, at the ultrasonic lower dispersion 10min of operating frequency 20KHz, again by rotating speed be 4000r/min emulsification pretreatment mixer stir 20min, obtain the ITO precursor solution that pH value is 7.2.
(2) preparation of ITO layer:
(2.1) film: under the environment of 25 DEG C, with the lift coating process that decrease speed 8mm/min, pull rate 1mm/min, time of staying are in the solution 6min, ITO precursor solution is coated on glass baseplate surface, then in thermostatic drying chamber in air atmosphere in 140 DEG C of freeze-day with constant temperature 5min, above-mentioned coating and dry run 8 times, obtain film substrate repeatedly.
(2.2) heat treatment: by film substrate in air atmosphere, after being heated to 250 DEG C from room temperature with the heating rate of 45 DEG C/min, insulation 60min, with stove cooling, obtains the substrate being with ITO layer;
(3) preparation of ITO/ZIO composite coating (i.e. composite transparent conductive oxide film)
(3.1) configuration of ZIO hydrothermal solution: 7.3g zinc acetate and 0.8g indium nitrate are dissolved in 90mL water, add 2.8g hexamethylenetetramine, 0.8g neopelex, after mechanical agitation, be after the ultrasonic disperse machine ultrasonic disperse 10min of 30KHz in operating frequency, obtain the ZIO hydrothermal solution that pH value is 8.3.
(3.2) hydro-thermal reaction: by the substrate clean water of band ITO layer, hydro-thermal glassware is put into after dry 10min at 120 DEG C, and in glassware, add above-mentioned joined ZIO hydrothermal solution, clean after 60 DEG C of hydro-thermal reaction 34h, dry 12min at 100 DEG C, finally obtain the substrate being with ITO/ZIO composite coating, i.e. composite transparent conductive oxide film.
The performance test of composite transparent conductive oxide film (i.e. ITO/ZIO composite coating) prepared by the various embodiments described above:
Refractive index: Gangdong, the refractive index Tianjin automatic elliptical polarization instrument instrument of ITO/ZIO composite coating measures (incidence angle is 70 °), and result is as shown in table 1.The refractive index of embodiment 1, embodiment 2, embodiment 3 is respectively 2.116,2.140,2.316, and the refractive index of three presses close to the best refractive index 2.4 of antireflective film all very much.
Physical property: the physical property of ITO/ZIO composite coating prepared by the present invention is in table 1; The hardness of coating is according to [GB/T6739.1996] standard, measures with pencil hardness method; Coating adhesion measures employing, and [GB/T9286.19981 (test of paint and varnish paint film lattice drawing) is bioassay standard; According to national standard [GBl733.79 (88)] regulation, 2/3 area of japanning model is put into the distilled water that temperature is about 25 DEG C, product standard official hour to be achieved takes out, and whether visual evaluation has the phenomenons such as foaming, loss of gloss, variable color; As can be seen from Table 1, embodiment 1,2,3 all has good resistance to water and hardness, has higher adhesive force.
The physical property of ITO/ZIO composite coating prepared by table 1 embodiment 1,2,3
| Numbering | Pencil hardness | Adhesive force | Resistance to water | Refractive index |
| Embodiment 1 | 6H | 0 grade | Non-foaming, do not come off | 2.116 |
| Embodiment 2 | 5H | 0 grade | Non-foaming, do not come off | 2.140 |
| Embodiment 3 | 6H | 0 grade | Non-foaming, do not come off | 2.316 |
Thin visible light transmissivity: choosing glass is substrate, and substrate is prepared ITO/ZIO composite coating.The transmittance curve of ITO/ZIO composite coating to visible ray and black light prepared by the present invention is shown in Fig. 2, by measuring its transmitance in UV-2100 type ultraviolet-visible spectrophotometer, be consequently standard gained in the transmitance of blank glass as 100% using the light wave of different wave length.The transmitance of the visible-range (λ=390 ~ 1000nm) of embodiment 1, embodiment 2, embodiment 3 is greater than 90%, namely has good visible light transmissivity.
Light trapping structure: Fig. 3 ~ Fig. 5 is shown in by the scanning electron microscope sem photo of ITO/ZIO composite coating prepared by the present invention, SEM photo is by captured by FEISirion200 type ESEM, Fig. 3,4,5 corresponding embodiment 1, embodiment 2, embodiment 3 respectively; The equal surfacing of three, the defects such as pore-free, slight crack and cavity, there is nano level roughness on three kinds of composite coating surfaces, can increase light path, show light trapping effect.
Electric property: the electrical parameter of ITO/ZIO composite coating prepared by the present invention is in table 2; The conductivity of coating adopts SB2331 DC digital resistance meter to survey its resistance R.Four probe method surveys the principle of semiconductor resistor rate, as shown in Figure 6: by four probes arranged in parallel to be vertically pressed on the surface of tested sample under certain pressure, between 1 and 4 probes, pass to electric current I.Because film thickness d is far smaller than electrode spacing s, being approximately equipotential surface is that (high t, the radius of any equipotential surface is set to r), can make to produce certain voltage V between 2 and 3 probes, measures this voltage, thus draws resistance R on the face of cylinder.Layer resistivity computing formula is:
ρ＝R×π×W×f(a)/ln2(Ω·cm)
Wherein: ρ-resistivity, Ω cm; The resistance that R-measures, Ω; W-film thickness, cm; A=W/S (S=S1=S2=S3, S=3mm in this experiment), dimensionless; F (a)-film thickness correction factor.Correction factor can be found from correction function subordinate list.Then by square resistance R
sh=ρ/d converts and namely obtains the square resistance R of film
sh(sheet resistance).
The resistivity of embodiment 1, embodiment 2, embodiment 3 is respectively 2.39 × 10
-4Ω cm, 3.46 × 10
-4Ω cm, 2.39 × 10
-4Ω cm, three kinds of composite coatings square resistance be respectively 33.2 Ω/, 44.4 Ω/, 34.6 Ω/, as can be seen here, ITO/ZIO composite coating shows excellent electric conductivity.
Film thickness: the thickness of ITO/ZIO composite coating prepared by the present invention is in table 2, contact pin type contourgraph is adopted to check film thickness, first the one end of the substrate being coated with ITO/ZIO composite coating is placed in watery hydrochloric acid a period of time of 0.1mol/L, the laminated film of one end to be soaked removes completely, expose matrix surface, cause the surface of seal coat and the difference in height of matrix surface, carrying out scanning by probe to " difference in height " can measure film thickness.
The composite coating thickness of embodiment 1, embodiment 2, embodiment 3 is respectively 72nm, 78nm, 69nm, experimental result is known, the refractive index of three is respectively 2.116,2.140,2.316, then the optical thickness dn of embodiment 1, embodiment 2, embodiment 3 is respectively 152.4nm, 166.9nm, 159.8nm.The film thickness monitoring of composite coating prepared by the present invention is very accurate, and the best optical thickness 160nm of the optical thickness of the ITO/ZIO composite coating prepared by the present invention closely anti-reflection antireflective film.
The electrical parameter of ITO/ZIO composite coating prepared by table 2 embodiment 1,2,3
| Numbering | Square resistance/(Ω/) | Resistivity/(10 -4Ω·cm) | Thickness/(nm) |
| Embodiment 1 | 33.2 | 2.39 | 72 |
| Embodiment 2 | 44.4 | 3.46 | 78 |
| Embodiment 3 | 34.6 | 2.39 | 69 |
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is also not only confined to above-described embodiment.All technical schemes belonged under thinking of the present invention all belong to protection scope of the present invention.It is noted that for those skilled in the art, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a composite transparent conductive oxide film, comprise ITO layer (2) and ZIO layer (3), it is characterized in that, described ITO layer (2) is located on a substrate (1), and described ZIO layer (3) is located in described ITO layer (2); The surface texture of described ZIO layer (3) is suede structure.
2. composite transparent conductive oxide film according to claim 1, it is characterized in that, the refractive index of described composite transparent conductive oxide film is 2.1 ~ 2.5, and thickness is 60nm ~ 80nm, light transmission rate > 90%, resistivity < 4 × 10
-4Ω cm.
3. a preparation method for composite transparent conductive oxide film, comprises the following steps:
(1) by water-soluble to indium salt, pink salt, thickener, levelling agent and dispersant, after dispersion, ITO precursor solution is obtained;
(2) described ITO precursor solution is coated on a substrate by lift plated film, then dry, repeat described coating and dry run, until rete reaches desired thickness, obtain film substrate; Described film base plate heating is warming up to 250 DEG C ~ 350 DEG C, after constant temperature is roasted, with stove cooling, obtains the substrate being with ITO layer;
(3) by water-soluble to zinc salt, indium salt, weak base and dispersant, after dispersion, ZIO hydrothermal solution is obtained; The substrate of band ITO layer step (2) obtained is placed in described ZIO hydrothermal solution, at 60 DEG C ~ 95 DEG C, carry out hydro-thermal reaction, then washing, drying, form ZIO layer on the ito layer, obtain ITO/ZIO composite coating, be composite transparent conductive oxide film.
4. the preparation method of composite transparent conductive oxide film according to claim 3, it is characterized in that, in described step (1), by mass parts, indium salt is 20.7 ~ 44.0 parts, and pink salt is 2.3 ~ 4.9 parts, thickener is 0.1 ~ 2.0 part, levelling agent is 0.1 ~ 2.0 part, and dispersant is 0.1 ~ 4.4 part, and water is 46.8 ~ 75.3 parts.
5. the preparation method of composite transparent conductive oxide film according to claim 3, it is characterized in that, in described step (3), by mass parts, described zinc salt is 0.35 ~ 9.32 part, and described indium salt is 0.05 ~ 1 part, and described weak base is 0.35 ~ 3.26 part, described dispersant is 0.1 ~ 1 part, and described water is 85.42 ~ 99.15 parts.
6. the preparation method of the composite transparent conductive oxide film according to any one of claim 3 ~ 5, it is characterized in that, in described step (2), the process conditions of described lift plated film are: lift temperature is 20 DEG C ~ 35 DEG C, decrease speed is 6mm/min ~ 10mm/min, pull rate is 0.6mm/min ~ 3mm/min, is 5min ~ 8min during the stop of described substrate in ITO precursor solution; The temperature of described drying is 100 DEG C ~ 200 DEG C, and the time of described drying is 2min ~ 15min, and the atmosphere of described drying is air atmosphere; Described coating and dry number of repetition are 5 times ~ 10 times.
7. the preparation method of the composite transparent conductive oxide film according to any one of claim 3 ~ 5, it is characterized in that, in described step (2), described heat temperature raising carries out in air atmosphere, heating rate is 45 DEG C/min ~ 55 DEG C/min, and described constant temperature roasted time is 0.5 hour ~ 2 hours; In described step (3), the time of described hydro-thermal reaction is 5h ~ 42h, and the temperature of described drying is 100 ~ 200 DEG C, and the time of described drying is 2min ~ 15min.
8. the preparation method of the composite transparent conductive oxide film according to any one of claim 3 ~ 5, is characterized in that, in described step (1), described indium salt is inidum chloride and/or indium nitrate; Described pink salt is stannic chloride and/or nitric acid tin; Described thickener is one or more in methylcellulose, carboxymethyl cellulose, carboxyethyl cellulose and carboxylic propyl methocel; Described levelling agent is one or more in polyether silicones oxygen alkane levelling agent, Sodium Polyacrylate and polyacrylamide; Described dispersant is one or more in polyvinylpyrrolidone, cetane trimethyl ammonium bromide, calgon, sodium polyphosphate, cetomacrogol 1000 and silane coupler.
9. the preparation method of the composite transparent conductive oxide film according to any one of claim 3 ~ 5, is characterized in that, in described step (3), described zinc salt is zinc acetate and/or zinc nitrate; Described indium salt is inidum chloride and/or indium nitrate; Described weak base is one or more in triethylamine, pyridine, urea, cyclohexylamine, aniline, hexamethylenetetramine and ammoniacal liquor; Described dispersant is one or more in polyvinylpyrrolidone, neopelex, calgon, sodium polyphosphate, cetomacrogol 1000 and silane coupler.
10. the preparation method of the composite transparent conductive oxide film according to any one of claim 3 ~ 5, it is characterized in that, in described step (1), the process of described dispersion comprises first mechanical dispersion, then ultrasonic disperse, shear agitation dispersion again, wherein, the operating frequency of described ultrasonic disperse is 20KHz ~ 30KHz, the time of described ultrasonic disperse is 5min ~ 10min, the rotating speed of described shear agitation dispersion is 500r/min ~ 6000r/min, and the time of described shear agitation dispersion is 2min ~ 20min;
In described step (3), the process of described dispersion comprises first mechanical dispersed with stirring, then ultrasonic disperse, and wherein, the operating frequency of described ultrasonic disperse is 20KHz ~ 30KHz, and the time of described ultrasonic disperse is 5min ~ 30min.
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