CN103515484A - Textured transparent conductive thin film with periodic structure and preparation method thereof - Google Patents

Textured transparent conductive thin film with periodic structure and preparation method thereof Download PDF

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CN103515484A
CN103515484A CN201310416643.XA CN201310416643A CN103515484A CN 103515484 A CN103515484 A CN 103515484A CN 201310416643 A CN201310416643 A CN 201310416643A CN 103515484 A CN103515484 A CN 103515484A
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transparent conductive
periodic
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thin film
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CN103515484B (en
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张晓丹
梁雪娇
赵颖
梁俊辉
高海波
黄茜
侯国付
许盛之
魏长春
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Nankai University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/02Details
    • H01L31/0236Special surface textures
    • H01L31/02366Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/02Details
    • H01L31/0224Electrodes
    • H01L31/022466Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H01L31/022483Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/04Semiconductor devices sensitive to infra-red 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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06Semiconductor devices sensitive to infra-red 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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/072Semiconductor devices sensitive to infra-red 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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
    • H01L31/074Semiconductor devices sensitive to infra-red 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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a heterojunction with an element of Group IV of the Periodic System, e.g. ITO/Si, GaAs/Si or CdTe/Si solar cells
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884Manufacture of transparent electrodes, e.g. TCO, ITO
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

Provided is textured transparent conductive thin film with a periodic structure. The textured transparent conductive thin film with the periodic structure comprises a glass substrate layer, first layer ZnO thin film which plays a role in a template, and second layer ZnO thin film which plays a role in modification, wherein a laminated structure is formed by the glass substrate layer, the first layer ZnO thin film and the second layer ZnO thin film in sequence, the thickness of the first layer ZnO thin film is 300-1500nm, the thickness of the second layer ZnO thin film is 400-1000nm, and the textured transparent conductive thin film which has the scattering effect and is of the periodic structure is formed. A preparation method of the textured transparent conductive thin film with the periodic structure comprises the steps of using the water bath method to assemble PS microspheres, using O2 to carry out plasma etching on the PS microspheres, and obtaining the light-trapping ZnO transparent conductive thin film with the periodic structure through the template effect of the PS microspheres. The textured transparent conductive thin film with the periodic structure and the preparation method of the textured transparent conductive thin film with the periodic structure have the advantages that the prepared ZnO transparent conductive thin film has the good light-trapping effect, can serve as a front electrode to be applied to a thin film solar cell, and have a good scattering effect within the range of the wavelength which can be used by cells with the size of 400-1100nm, the optical distance of incident light in silicon-based thin-film cells can be increased, and the use ratio of light can be improved.

Description

Matte transparent conductive film of a kind of periodic structure and preparation method thereof
Technical field
The invention belongs to the technology of preparing of the transparent conductive film of thin film solar cell, matte transparent conductive film of especially a kind of periodic structure and preparation method thereof.
Background technology
Enter 21 century, energy security and environmental protection have become the problem of globalization.The important measures of world many countries using Renewable Energy Development as alleviation energy supply contradiction, reply climate change, and formulated development strategy, clear and definite developing goal and corresponding incentive policy have been proposed.Photovoltaic generation is that the internationally recognized solution energy lacks one of effective way with problem of environmental pollution.The carrier of photovoltaic generation is solar cell, and the key that can make solar cell become future source of energy important component part be photovoltaic generation cost to be dropped to conventional energy resource suitable.
Transparent conductive film is as the important component part of solar cell, and its suede degree characteristic is most important to the performance impact of battery.The transparent conductive oxide being most widely used in current hull cell (TCO) film is F doping SnO 2film (SnO 2: F) with Sn doping In 2o 3film (In 2o 3: Sn).The F SnO that adulterates 2film normally utilizes the preparation of atmospheric pressure cvd (APCVD) technology, growth temperature higher (~ 500 ℃), there is certain suede structure, but this type of TCO is unfavorable for the hull cell material of growing in low temperature depositing and strong H plasma environment, limited it and further applied.And Sn doping In 2o 3film, In element during its film forms is rare and cost is higher, and is not easy to obtain coarse surface topography, at strong H plasma environment performance, easily worsens, and has also limited its extensive use in thin film solar cell.Than In 2o 3and SnO 2thin-film material, it is abundant that ZnO film has source material, nontoxic and relative growth temperature is low and obtained broad research and application in features such as strong H plasma environment performance are stable.Research shows: for Si base thin film solar battery (amorphous silicon battery, microcrystal silicon battery and silica-base film are tied laminated cell more), the light trapping effect of TCO film is particularly important on the impact of device performance.The structure that falls into light can improve light scattering ability, increases the light path of incident light.Therefore, the application of light trapping structure can effectively strengthen the optical absorption of intrinsic layer, improves short-circuit current density, thereby raising battery efficiency, and what is more important: fall into the introducing of light, thickness that can attenuate battery active layer, this is very important to reducing costs.
Preparation is at present mainly the transparent conductive film of random matte with the method for the transparent conductive film of light trapping structure, random matte is mainly that doping ZnO (ZnO:Al, ZnO:Ga, ZnO:B, ZnO:H, ZnO:Mo or the ZnO:W) film by sputter is produced carries out the light trapping structure that wet etching processing obtains " cratering ", thereby improve incident scattering of light, increase the absorption of active layer to light.But, for sputtering technology making ZnO film, to carry out wet method post-etching and will expect well sunken light, the characteristic size of its " cratering " and roughness need very large, and such ZnO film can only high temperature sputter (being greater than 250oC).Limit so on the one hand the substrate of battery applications, also improved on the other hand the cost of preparing battery.
Summary of the invention
The present invention seeks to as overcoming the above-mentioned deficiency of prior art, matte transparent conductive film of a kind of periodic structure and preparation method thereof is provided, the zinc oxide transparent conductive film of the periodic structure in the method has good sunken light effect, increase the light path of incident light in silicon-base thin-film battery, to reach raising light utilization efficiency, and then the object of raising battery efficiency.
Technical scheme of the present invention:
A kind of matte transparent conductive film of periodic structure, comprise substrate layer, the second layer ZnO film of the ground floor ZnO film of lifting plate effect and a modification also forms laminated construction successively, substrate layer is hard substrates glass, ZnO film is doping zinc-oxide N-shaped semi-conducting material, comprise ZnO:H, ZnO:Al, ZnO:Ga, ZnO:B, ZnO:H, at least one in ZnO:Mo and ZnO:W, wherein ground floor ZnO film thickness is 300-1500nm, the thickness of second layer ZnO film is 400-1000nm, form the matte transparent conductive film of the periodic structure with wide spectral dispersion effect, the r.m.s. roughness of the ZnO matte transparent conductive film of periodic structure is 30-250 nm.
A preparation method for the matte transparent conductive film of periodic structure, utilizes water-bath method assembling PS microballoon, uses O 2plasma etching PS microballoon, utilizes the template action of PS microballoon, obtains having the sunken light ZnO transparent conductive film of periodic structure, and step is as follows:
1) glass substrate is immersed in to H 2sO 4with H 2o 2the volume ratio mixed solution that is 2:1 in carry out hydrophilic treated, the processing time is 2-10 hour;
2) above-mentioned glass substrate is placed on horizontal stand, by particle diameter, be that the polystyrene microsphere latex solution that 1-5 μ m, concentration are 5wt% vertically drops in glass substrate, solution slowly spreads apart and makes that ethene microballoon is inhomogeneous to be interspersed among in glass substrate, then glass substrate is placed on and on steam, carries out self assembly, through the water-bath of 30min, the polystyrene microsphere of the formation individual layer six side's solid matters in glass substrate;
3) by the polystyrene microsphere of above-mentioned individual layer six side's solid matters, carry out O 2plasma etching (RIE), after etching, the size of polystyrene microsphere is 0.5-4 μ m;
4) on the polystyrene microsphere after etching, adopt the ZnO film that magnetically controlled sputter method deposition ground floor thickness is 300-1500nm, then glass substrate is placed in water and carries out ultrasonic processing until ethene bead is processed totally completely;
5) adopt the method for magnetron sputtering to deposit again the ZnO film that second layer thickness is 400-1000nm, can make the matte transparent conductive film with periodic structure.
A kind of application of matte transparent conductive film of described periodic structure, for making electrode before the electrically conducting transparent of thin film solar cell, described thin film solar cell is that amorphous is silica-based, microcrystalline silicon, nano silicon-based thin film solar cell or tie laminated silicon-base film solar cell more.
Advantage of the present invention and good effect:
The present invention utilizes the ZnO film of template action and the deposition of PS microballoon, has realized the preparation of the ZnO film of high suede degree periodic structure, and has good sunken light effect; Using zinc oxide conductive film as front electrode, for thin film solar cell, in the wave-length coverage that can utilize 400-1100nm battery, there is good scattering process, can increase the light path of incident light in silicon-base thin-film battery, improve light utilization efficiency.
 
Accompanying drawing explanation
Fig. 1 is the structural representation of the ZnO film of periodic structure.
Fig. 2 is the shape appearance figure of the Textured ZnO Transparent Conductive Thin Film of the periodic structure prepared of template for adopting PS bead.
Fig. 3 is integrated reflection and the suede degree of the Textured ZnO Transparent Conductive Thin Film of the periodic structure prepared of template for adopting PS bead.
 
Embodiment
embodiment 1:
A kind of matte transparent conductive film of periodic structure, as shown in Figure 1, comprise substrate layer, the second layer ZnO film of the ground floor ZnO film of lifting plate effect and a modification also forms laminated construction successively, substrate layer is hard substrates glass, ZnO film is doping zinc-oxide N-shaped semi-conducting material ZnO:H, wherein ground floor ZnO film thickness is 800nm, the thickness of second layer ZnO film is 400nm, form the matte transparent conductive film of the periodic structure with wide spectral dispersion effect, the r.m.s. roughness of the ZnO matte transparent conductive film of periodic structure is 80 nm.
A preparation method for the matte transparent conductive film of periodic structure, utilizes water-bath method assembling PS microballoon, uses O 2plasma etching PS microballoon, utilizes the template action of PS microballoon, obtains having the sunken light ZnO transparent conductive film of periodic structure, and step is as follows:
1) glass substrate is immersed in to H 2sO 4with H 2o 2the volume ratio mixed solution that is 2:1 in carry out hydrophilic treated, the processing time is 6 hours;
2) above-mentioned glass substrate is placed on horizontal stand, by particle diameter, be that the polystyrene microsphere latex solution that 2 μ m, concentration are 5wt% vertically drops in glass substrate, solution slowly spreads apart and makes that ethene microballoon is inhomogeneous to be interspersed among in glass substrate, then glass substrate is placed on and on steam, carries out self assembly, through the water-bath of 30min, the polystyrene microsphere of the formation individual layer six side's solid matters in glass substrate;
3) by the polystyrene microsphere of above-mentioned individual layer six side's solid matters, carry out O 2plasma etching (RIE), oxygen flow 10 Sccm, air pressure 11pa, radio-frequency power 150W, etch period 6min, the particle diameter of microballoon is 1.8 μ m;
4) on the ethene microballoon after etching, adopt ZnO:H (HZO) film that magnetically controlled sputter method deposition ground floor thickness is 800nm: target is ZnO ceramic target, the zinc-oxide film of preparing low-resistivity and high transmission: underlayer temperature is room temperature, base vacuum is 5 * 10 -5pa, hydrogen flowing quantity is 3sccm, argon flow amount is 52sccm, sputtering pressure is 4.5mTorr, electrode spacing is 30 mm, and sputtering power is 380 W, and sputtering time is 40 min, obtain the ZnO:H transparent conductive film that thickness is about 800 nm, then glass substrate is placed in water and carries out ultrasonic processing until ethene bead is processed totally completely;
5) adopt the method for magnetron sputtering to deposit again the ZnO:H film that second layer thickness is 400nm: underlayer temperature is room temperature, and base vacuum is 5 * 10 -5pa, hydrogen flowing quantity is 3sccm, argon flow amount is 52sccm, and sputtering pressure is 4.5mTorr, and electrode spacing is 30 mm, sputtering power is 380 W, sputtering time is 20min, and thickness is 400 nm, can make the matte transparent conductive film with periodic structure, its r.m.s. roughness is 80nm, and square resistance is 16.5 .
Fig. 2 for adopt PS bead be the periodic structure prepared of template the shape appearance figure of Textured ZnO Transparent Conductive Thin Film.From shape appearance figure, show: the ZnO film of this periodic structure can access larger matte roughness, and periodic structure is obvious.
Fig. 3 for adopt PS bead be the periodic structure prepared of template integrated reflection and the suede degree of shape appearance figure of Textured ZnO Transparent Conductive Thin Film.In figure, show: this periodic structure transparent conductive film at 800nm and 1100nm place the suede degree factor has reached respectively 58% and 28%, there is good light trapping effect.
Before the matte transparent conductive film of prepared periodic structure can be used as electrically conducting transparent, electrode is for microcrystalline silicon film solar cell, in the wave-length coverage that can utilize 400-1100nm battery, there is good scattering process, can increase the light path of incident light in silicon-base thin-film battery, improve light utilization efficiency.
embodiment 2:
A kind of matte transparent conductive film of periodic structure, as shown in Figure 1, comprise substrate layer, the second layer ZnO film of the ground floor ZnO film of lifting plate effect and a modification also forms laminated construction successively, substrate layer is hard substrates glass, ZnO film is doping zinc-oxide N-shaped semi-conducting material ZnO:Al (AZO) film, wherein ground floor ZnO film thickness is 700nm, the thickness of second layer ZnO film is 400nm, form the matte transparent conductive film of the periodic structure with wide spectral dispersion effect, the r.m.s. roughness of the ZnO matte transparent conductive film of periodic structure is 85 nm.
A preparation method for the matte transparent conductive film of periodic structure, utilizes water-bath method assembling PS microballoon, uses O 2plasma etching PS microballoon, utilizes the template action of PS microballoon, obtains having the sunken light ZnO transparent conductive film of periodic structure, and step is as follows:
1) glass substrate is immersed in to H 2sO 4with H 2o 2the volume ratio mixed solution that is 2:1 in carry out hydrophilic treated, the processing time is 5 hours;
2) above-mentioned glass substrate is placed on horizontal stand, by particle diameter, be that the polystyrene microsphere latex solution that 2 μ m, concentration are 5wt% vertically drops in glass substrate, solution slowly spreads apart and makes that ethene microballoon is inhomogeneous to be interspersed among in glass substrate, then glass substrate is placed on and on steam, carries out self assembly, through the water-bath of 30min, the polystyrene microsphere of the formation individual layer six side's solid matters in glass substrate;
3) by the polystyrene microsphere of above-mentioned individual layer six side's solid matters, carry out O 2plasma etching (RIE), oxygen flow 10 Sccm, air pressure 11pa, radio-frequency power 150W, etch period 8min, the particle diameter of microballoon is 1.6 μ m;
4) adopt ZnO:Al (AZO) film that magnetically controlled sputter method deposition ground floor thickness is 700nm, adopt ZnO:Al 2o 3ceramic target, wherein Al 2o 3mass fraction is 2 wt.%; Adopt pure argon sputter, prepare the polycrystalline zinc oxide film of low-resistivity: underlayer temperature is room temperature, and base vacuum is 5 * 10 -5pa, argon flow amount is 55 sccm, sputtering pressure is 3.3 mTorr, electrode spacing is 50 mm, and sputtering power is 460W, sputter 30min, obtaining thickness is the ZnO:Al transparent conductive film of 700nm, then glass substrate is placed in water and carries out ultrasonic processing until ethene bead is processed totally completely;
5) adopt the method for magnetron sputtering to deposit again the ZnO:Al transparent conductive film that second layer thickness is 400nm: underlayer temperature is room temperature, and base vacuum is 5 * 10 -5pa, argon flow amount is 55 sccm, and sputtering pressure is 3.3 mTorr, and electrode spacing is 50 mm, and sputtering power is 460W, and sputter 17min obtains the ZnO:Al transparent conductive film of thickness 400nm, and its r.m.s. roughness is 85nm, and square resistance is 15 .
The shape appearance figure of the sunken light ZnO transparent conductive film of employing periodic structure and integrated reflection and suede degree and embodiment 1 are roughly the same.
embodiment 3:
A kind of matte transparent conductive film of periodic structure, as shown in Figure 1, comprise substrate layer, the second layer ZnO film of the ground floor ZnO film of lifting plate effect and a modification also forms laminated construction successively, substrate layer is hard substrates glass, ZnO film is doping zinc-oxide N-shaped semi-conducting material ZnO:H (HZO) film, wherein ground floor ZnO film thickness is 900nm, the thickness of second layer ZnO film is 400nm, form the matte transparent conductive film of the periodic structure with wide spectral dispersion effect, the r.m.s. roughness of the ZnO matte transparent conductive film of periodic structure is 120 nm.
A preparation method for the matte transparent conductive film of periodic structure, utilizes water-bath method assembling PS microballoon, uses O 2plasma etching PS microballoon, utilizes the template action of PS microballoon, obtains having the sunken light ZnO transparent conductive film of periodic structure, and step is as follows:
1) glass substrate is immersed in to H 2sO 4with H 2o 2the volume ratio mixed solution that is 2:1 in carry out hydrophilic treated, the processing time is 5 hours;
2) above-mentioned glass substrate is placed on horizontal stand, by particle diameter, be that the polystyrene microsphere latex solution that 3 μ m, concentration are 5wt% vertically drops in glass substrate, solution slowly spreads apart and makes that ethene microballoon is inhomogeneous to be interspersed among in glass substrate, then glass substrate is placed on and on steam, carries out self assembly, through the water-bath of 30min, the polystyrene microsphere of the formation individual layer six side's solid matters in glass substrate;
3) by the polystyrene microsphere of above-mentioned individual layer six side's solid matters, carry out O 2plasma etching (RIE), oxygen flow 10 Sccm, air pressure 11pa, radio-frequency power 150W, etch period 10min, the particle diameter of microballoon is 2.4 μ m;
4) adopt ZnO:H (HZO) film that magnetically controlled sputter method deposition ground floor thickness is 900nm, target is ZnO ceramic target, prepares the zinc-oxide film of low-resistivity and high transmission: underlayer temperature is room temperature, and base vacuum is 5 * 10 -5pa, hydrogen flowing quantity is 3sccm, and argon flow amount is 52sccm, and sputtering pressure is 4.5mTorr, and electrode spacing is 30 mm, and sputtering power is 380 W, and sputtering time is 45 min, and obtaining thickness is the ZnO:H transparent conductive film of 900 nm; , then glass substrate is placed in water and carries out ultrasonic processing until ethene bead is processed totally completely;
5) adopt the method for magnetron sputtering to deposit again the ZnO:H transparent conductive film that second layer thickness is 400nm: underlayer temperature is room temperature, and base vacuum is 5 * 10 -5pa, hydrogen flowing quantity is 3sccm, argon flow amount is 52sccm, and sputtering pressure is 4.5mTorr, and electrode spacing is 30 mm, sputtering power is 380 W, sputtering time is 20 min, and thickness is 400nm, so just obtains having the transparent conductive film of periodic structure, its r.m.s. roughness is 120nm, and square resistance is 10 .
The shape appearance figure of the sunken light ZnO transparent conductive film of employing periodic structure and integrated reflection and suede degree and embodiment 1 are roughly the same.
embodiment 4:
A kind of matte transparent conductive film of periodic structure, as shown in Figure 1, comprise substrate layer, the second layer ZnO film of the ground floor ZnO film of lifting plate effect and a modification also forms laminated construction successively, substrate layer is hard substrates glass, ZnO film is doping zinc-oxide N-shaped semi-conducting material ZnO:Ga (GZO) film, wherein ground floor ZnO film thickness is 1200nm, the thickness of second layer ZnO film is 500nm, form the matte transparent conductive film of the periodic structure with wide spectral dispersion effect, the r.m.s. roughness of the ZnO matte transparent conductive film of periodic structure is 160 nm.
A preparation method for the matte transparent conductive film of periodic structure, utilizes water-bath method assembling PS microballoon, uses O 2plasma etching PS microballoon, utilizes the template action of PS microballoon, obtains having the sunken light ZnO transparent conductive film of periodic structure, and step is as follows:
1) glass substrate is immersed in to H 2sO 4with H 2o 2the volume ratio mixed solution that is 2:1 in carry out hydrophilic treated, the processing time is 7 hours;
2) above-mentioned glass substrate is placed on horizontal stand, by particle diameter, be that the polystyrene microsphere latex solution that 4 μ m, concentration are 5wt% vertically drops in glass substrate, solution slowly spreads apart and makes that ethene microballoon is inhomogeneous to be interspersed among in glass substrate, then glass substrate is placed on and on steam, carries out self assembly, through the water-bath of 30min, the polystyrene microsphere of the formation individual layer six side's solid matters in glass substrate;
3) by the polystyrene microsphere of above-mentioned individual layer six side's solid matters, carry out O 2plasma etching (RIE), oxygen flow 10 Sccm, air pressure 9pa, radio-frequency power 150W, etch period 8min, the particle diameter of microballoon is 3.4 μ m;
4) adopt ZnO:Ga (GZO) film that magnetically controlled sputter method deposition ground floor thickness is 1200nm, adopt ZnO:Ga 2o 3ceramic target, wherein Ga 2o 3mass fraction is 2 wt.%; Adopt pure argon sputter, prepare the polycrystalline zinc oxide film of low-resistivity: underlayer temperature is room temperature, and base vacuum is 5 * 10 -5pa, argon flow amount is 55 sccm, sputtering pressure is 3.3 mTorr, electrode spacing is 50 mm, and sputtering power is 460W, sputter 50min, obtain the GZO transparent conductive film that thickness is about 1200nm, then glass substrate is placed in water and carries out ultrasonic processing until ethene bead is processed totally completely;
5) adopt the method for magnetron sputtering to deposit again the GZO transparent conductive film that second layer thickness is 500nm: underlayer temperature is room temperature, and base vacuum is 5 * 10 -5pa, argon flow amount is 55 sccm, and sputtering pressure is 3.3 mTorr, and electrode spacing is 50 mm, sputtering power is 460W, and sputtering time is 21 min, and thickness is 500nm, so just obtain having the transparent conductive film of periodic structure, its r.m.s. roughness is 160nm, and square resistance is 8 .
The shape appearance figure of the sunken light ZnO transparent conductive film of employing periodic structure and integrated reflection and suede degree and embodiment 1 are roughly the same.
embodiment 5:
A kind of matte transparent conductive film of periodic structure, as shown in Figure 1, comprise substrate layer, the second layer ZnO film of the ground floor ZnO film of lifting plate effect and a modification also forms laminated construction successively, substrate layer is hard substrates glass, ZnO film is doping zinc-oxide N-shaped semi-conducting material ZnO:H (HZO) film, wherein ground floor ZnO film thickness is 1000nm, the thickness of second layer ZnO film is 500nm, form the matte transparent conductive film of the periodic structure with wide spectral dispersion effect, the r.m.s. roughness of the ZnO matte transparent conductive film of periodic structure is 140 nm.
A preparation method for the matte transparent conductive film of periodic structure, utilizes water-bath method assembling PS microballoon, uses O 2plasma etching PS microballoon, utilizes the template action of PS microballoon, obtains having the sunken light ZnO transparent conductive film of periodic structure, and step is as follows:
1) glass substrate is immersed in to H 2sO 4with H 2o 2the volume ratio mixed solution that is 2:1 in carry out hydrophilic treated, the processing time is 4 hours;
2) above-mentioned glass substrate is placed on horizontal stand, by particle diameter, be that the polystyrene microsphere latex solution that 3 μ m, concentration are 5wt% vertically drops in glass substrate, solution slowly spreads apart and makes that ethene microballoon is inhomogeneous to be interspersed among in glass substrate, then glass substrate is placed on and on steam, carries out self assembly, through the water-bath of 30min, the polystyrene microsphere of the formation individual layer six side's solid matters in glass substrate;
3) by the polystyrene microsphere of above-mentioned individual layer six side's solid matters, carry out O 2plasma etching (RIE), oxygen flow 10 Sccm, air pressure 9pa, radio-frequency power 150W, etch period 12min, the particle diameter of microballoon is 2.2 μ m;
4) adopt ZnO:H (HZO) film that magnetically controlled sputter method deposition ground floor thickness is 1000nm, target is ZnO ceramic target, prepares the zinc-oxide film of low-resistivity and high transmission: underlayer temperature is room temperature, and base vacuum is 5 * 10 -5pa, hydrogen flowing quantity is 3sccm, argon flow amount is 52sccm, sputtering pressure is 4.5mTorr, electrode spacing is 30 mm, and sputtering power is 380 W, and sputtering time is 50min, obtain the ZnO:H transparent conductive film that ground floor thickness is about 1000 nm, then glass substrate is placed in water and carries out ultrasonic processing until ethene bead is processed totally completely;
5) adopt the method for magnetron sputtering to deposit again the ZnO:H transparent conductive film that second layer thickness is 500nm: underlayer temperature is room temperature, and base vacuum is 5 * 10 -5pa, hydrogen flowing quantity is 3sccm, argon flow amount is 52sccm, and sputtering pressure is 4.5mTorr, and electrode spacing is 30 mm, sputtering power is 380 W, sputtering time is 25 min, and obtaining second layer thickness is the ZnO:H transparent conductive film of 500 nm, so just obtains having the transparent conductive film of periodic structure, its r.m.s. roughness is 140nm, and square resistance is 9 .
The shape appearance figure of the sunken light ZnO transparent conductive film of employing periodic structure and integrated reflection and suede degree and embodiment 1 are roughly the same.
embodiment 6:
A kind of matte transparent conductive film of periodic structure, as shown in Figure 1, comprise substrate layer, the second layer ZnO film of the ground floor ZnO film of lifting plate effect and a modification also forms laminated construction successively, substrate layer is hard substrates glass, ZnO film is doping zinc-oxide N-shaped semi-conducting material ZnO:W (WZO) film, wherein ground floor ZnO film thickness is 700nm, the thickness of second layer ZnO film is 350nm, form the matte transparent conductive film of the periodic structure with wide spectral dispersion effect, the r.m.s. roughness of the ZnO matte transparent conductive film of periodic structure is 70 nm.
A preparation method for the matte transparent conductive film of periodic structure, utilizes water-bath method assembling PS microballoon, uses O 2plasma etching PS microballoon, utilizes the template action of PS microballoon, obtains having the sunken light ZnO transparent conductive film of periodic structure, and step is as follows:
1) glass substrate is immersed in to H 2sO 4with H 2o 2the volume ratio mixed solution that is 2:1 in carry out hydrophilic treated, the processing time is 5 hours;
2) above-mentioned glass substrate is placed on horizontal stand, by particle diameter, be that the polystyrene microsphere latex solution that 2 μ m, concentration are 5wt% vertically drops in glass substrate, solution slowly spreads apart and makes that ethene microballoon is inhomogeneous to be interspersed among in glass substrate, then glass substrate is placed on and on steam, carries out self assembly, through the water-bath of 30min, the polystyrene microsphere of the formation individual layer six side's solid matters in glass substrate;
3) by the polystyrene microsphere of above-mentioned individual layer six side's solid matters, carry out O 2plasma etching (RIE), oxygen flow 10 Sccm, air pressure 9pa, radio-frequency power 100W, etch period 15min, the particle diameter of microballoon is 1.4 μ m;
4) adopt ZnO:W (WZO) film that magnetically controlled sputter method deposition ground floor thickness is 700nm, target is ZnO ceramic target, adopts pure argon sputter, prepares the zinc-oxide film of low-resistivity and high transmission: underlayer temperature is room temperature, and base vacuum is 5 * 10 -5pa, argon flow amount is 55sccm, sputtering pressure is 4.5mTorr, electrode spacing is 30 mm, sputtering power is 430 W, sputtering time is 20 min, obtains the ground floor WZO transparent conductive film that thickness is about 700 nm, then glass substrate is placed in water and carries out ultrasonic processing until ethene bead is processed totally completely;
5) adopt the method for magnetron sputtering to deposit again the WZO transparent conductive film that second layer thickness is 350nm: underlayer temperature is room temperature, and base vacuum is 5 * 10 -5pa, argon flow amount is 55sccm, and sputtering pressure is 4.5mTorr, and electrode spacing is 30 mm, sputtering power is 430 W, and sputtering time is 10min, and thickness is 350 nm, so just obtain having the transparent conductive film of periodic structure, its r.m.s. roughness is 70nm, and square resistance is 14 .
The shape appearance figure of the sunken light ZnO transparent conductive film of employing periodic structure and integrated reflection and suede degree and embodiment 1 are roughly the same.
To sum up, the invention provides a kind of effective ways that the front electrode of silicon-based thin film solar cell falls into light effect that improve, before the method and traditional silicon-base thin-film battery, technology for preparing electrode is completely compatible, and be generally applicable to that amorphous is silica-based, microcrystalline silicon, nano silicon-based film unijunction and multijunction solar cell.
The above; be only the present invention's embodiment preferably, but protection scope of the present invention is not limited to this, is anyly familiar with in technical scope that those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claim.

Claims (3)

1. the matte transparent conductive film of a periodic structure, it is characterized in that: comprise substrate layer, the second layer ZnO film of the ground floor ZnO film of lifting plate effect and a modification also forms laminated construction successively, substrate layer is hard substrates glass, ZnO film is doping zinc-oxide N-shaped semi-conducting material, comprise ZnO:H, ZnO:Al, ZnO:Ga, ZnO:B, ZnO:H, at least one in ZnO:Mo and ZnO:W, wherein ground floor ZnO film thickness is 300-1500nm, the thickness of second layer ZnO film is 400-1000nm, form the matte transparent conductive film of the periodic structure with wide spectral dispersion effect, the r.m.s. roughness of the ZnO matte transparent conductive film of periodic structure is 30-250 nm.
2. a preparation method for the matte transparent conductive film of periodic structure as claimed in claim 1, is characterized in that: utilize water-bath method assembling PS microballoon, use O 2plasma etching PS microballoon, utilizes the template action of PS microballoon, obtains having the sunken light ZnO transparent conductive film of periodic structure, and step is as follows:
1) glass substrate is immersed in to H 2sO 4with H 2o 2the volume ratio mixed solution that is 2:1 in carry out hydrophilic treated, the processing time is 2-10 hour;
2) above-mentioned glass substrate is placed on horizontal stand, by particle diameter, be that the polystyrene microsphere latex solution that 1-5 μ m, concentration are 5wt% vertically drops in glass substrate, solution slowly spreads apart and makes that ethene microballoon is inhomogeneous to be interspersed among in glass substrate, then glass substrate is placed on and on steam, carries out self assembly, through the water-bath of 30min, the polystyrene microsphere of the formation individual layer six side's solid matters in glass substrate;
3) by the polystyrene microsphere of above-mentioned individual layer six side's solid matters, carry out O 2plasma etching (RIE), after etching, the size of polystyrene microsphere is 0.5-4 μ m;
4) on the polystyrene microsphere after etching, adopt the ZnO film that magnetically controlled sputter method deposition ground floor thickness is 300-1500nm, then glass substrate is placed in water and carries out ultrasonic processing until ethene bead is processed totally completely;
5) adopt the method for magnetron sputtering to deposit again the ZnO film that second layer thickness is 400-1000nm, can make the matte transparent conductive film with periodic structure.
3. the application of the matte transparent conductive film of periodic structure as claimed in claim 1, it is characterized in that: for making electrode before the electrically conducting transparent of thin film solar cell, described thin film solar cell is that amorphous is silica-based, microcrystalline silicon, nano silicon-based thin film solar cell or tie laminated silicon-base film solar cell more.
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