CN102220562B - Preparation method of zinc oxide transparent conductive film with sueded structure - Google Patents
Preparation method of zinc oxide transparent conductive film with sueded structure Download PDFInfo
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Abstract
The invention discloses a preparation method of a zinc oxide transparent conductive film with a sueded structure. The preparation method includes the step of adopting a magnetic control sputtering method and by taking zinc oxide ceramic doped with doping elements as a target and argon as sputtering gas, preparing the zinc oxide transparent conductive film with the sueded structure, wherein the vacuum degree of a background is 4*10<-3> to 1*10<-4> Pa, the pressure of the sputtering gas is 0.2 to 1.5 Pa and the temperature of a substrate is 150 to 350 DEG C, thus preparing the zinc oxide transparent conductive film with the sueded structure. The preparation method is simple in technology, low in production cost and suitable for large-scale industrialized production; the thickness of the prepared film is 300 to 1200 nm and the suede degree is 3% to 10%, the square resistance is 5 to 50 Omega/square, and the roughness is 10 to 50 nm; and the zinc oxide transparent conductive film with the sueded structure has high suede degree, high roughness and excellent electrooptic properties, is suitable for the preparation of thin film solar cells and can improve the photoelectric conversion efficiency of the solar cells.
Description
Technical field
The present invention relates to thin film solar cell core starting material fields, particularly a kind of preparation method of suede structure zinc oxide transparent conductive film.
Background technology
Recently, (comprise that mainly non-crystalline silicon (α-Si:H), microcrystal silicon (μ c-Si:H) and amorphous silicon/microcrystalline silicon tandem) is developed fast as the thin film solar cell of representative take Si base, because silicon is non-direct band gap material, to sun Optical Absorption a little less than, therefore utilize and fall into light (light trapping) structure the performance that promotes battery is seemed particularly important.In Si base film battery structure, be plated in transparent conductive oxide film (the Transparent conductive oxide on glass substrate, TCO) as Window layer and the front electrode of battery, be responsible for seeing through of light and transporting of photo-generated carrier, its structure and performance have close impact to the lifting of cell integrated performance.Usually the investigator makes suede structure with the TCO film, so just can allow light form ligh trap in battery, extends the travel path of light in absorption layer with the utilization ratio of increase light, and then improves battery efficiency.The criterion of matte is suede degree (Haze) and the surfaceness (δ of matte
RMS); The suede degree refers to lambda1-wavelength when 550nm, the ratio of thin films scattering transmitance and total transmitance; Surfaceness generally adopts root-mean-square deviation roughness (root mean square roughness, δ
RMS).
At present, the TCO film that the Si base thin film solar battery is commonly used is fluorine-doped tin oxide (SnO
2: F, FTO) film and different element doping zinc-oxide film (as ZnO:Al, AZO etc.), formed industrialization production.But the FTO film is poisonous, deposits spray pyrolysis technology temperature used higher, is difficult to the Large-Area-Uniform deposition, and is expensive, and easily is subject to the reductive action of hydrogen plasma.And Zinc oxide based film, particularly aluminium-doped zinc oxide (AZO) film have nontoxic, abundant raw materials, low price, higher and the photoelectric characteristic of stability is better than the advantages such as FTO in hydrogen plasma, is progressively replacing FTO and is being widely applied in the Si base thin film solar battery.
At present, the ZnO thin film doped main flow preparation method of Large-Area-Uniform is magnetically controlled sputter method, but its surface is very smooth smooth usually, in order to obtain better light trapping structure, people generally adopt follow-up wet process acid etching obtain suede structure (referring to O.Kluth, B.Rech, L.Houben, et.al., Thin Solid Films, 351 (1999) 247 and S.Calnan, J.Hupkes, et.al., Thin Solid Films, 516 (2008) 1242 report).Yet this two step processes that first deposit post-etching prepare the suede structure film complex steps, increase operation and cost, and homogeneity repeatability is relatively poor and cause the waste (corrosion rear film thickness reduces) of material during the big area corrosion.Therefore, there is the investigator to explore and prepares ZnO film with suede structure by one step of magnetron sputtering.For example, in Chinese invention patent ZL03137254.6, a kind of method that magnetron sputtering prepares the suede structure zinc oxide transparent conductive film is disclosed.The suede degree of the zinc oxide transparent conductive film that the method is prepared is 3.0～31.6%, and roughness is 10.8～50.2nm.Larger (the 3Pa～15Pa), and air pressure easily causes greatly the damage of film, and then have influence on the electric property of film of the method sputtering pressure.Document (Dongyun Wan, Fuqiang Huang, and Yaoming Wang, AC S Applied Materials ﹠amp; Interfaces, 2147-2152 (2010) 2) the homemade anoxic AZO ceramic target of employing, air pressure by adjusting magnetron sputtering and power were divided into for two steps (nucleation and growth) and prepare AZO film with matte, and obtaining roughness is 40.2nm, electroconductibility matte AZO film preferably.Although this method can be prepared the AZO transparent conductive film of suede structure, sputter procedure is also more loaded down with trivial details, is not suitable for the big area industrial production.Chinese invention patent application Publication Specification 201010202111.2 also discloses a kind of glass substrate matte structure ZnO film and application, and this invention utilizes magnetron sputtering technique equipment, with Zn-Al alloy target and O
2Be starting material, grow surfaceness～70nm on glass substrate, the transparent conductive film of square resistance～5 Ω, the sputtering target material that the method adopts is alloys target, is especially easily poisoned in sputter procedure, causes the inhomogeneous of sputter procedure.Therefore develop a kind of new zinc oxide transparent conductive film that utilizes one step of ceramic sputtering target material uniform deposition suede structure and seem and be necessary very much, this helps to reduce operation and reduces production costs in the process of industrialization.
Summary of the invention
The invention provides a kind of preparation method of suede structure zinc oxide transparent conductive film, the method is take doping zinc-oxide as target, adopt magnetically controlled sputter method directly to prepare the zinc oxide transparent conductive film that has simultaneously good electrical characteristic and suede structure, can realize good sunken light effect.
Through a large amount of research, the present invention finds, the suede structure of the transparent conductive film that magnetron sputtering is prepared and the factor of following two types have close related: one, doped element kind and the doping content in target; Two, the process parameter of sputter is as sputtering pressure, underlayer temperature, sputtering power etc.This be due to certain element doping condition and sputtering parameter and under, film is followed the three dimensional growth pattern, namely the film forming initial stage very easily forms many three-dimensional nucleus on substrate, then continues to grow up to form the polycrystal film of uneven surface.Therefore in the situation that above-mentioned two kinds of factors are suitable, can direct growth go out to have the transparent conductive film of suede structure, this is that forefathers do not have to report.The sputtering target material that adopts in the present invention is that to adopt the doped zinc oxide nano powder of preparation method's preparation of disclosed a kind of doped zinc oxide nano powder in Chinese patent application CN201010166473.0 be raw material and makes according to the middle temperature preparation method of disclosed a kind of zinc oxide-based ceramic sputtering target material in Chinese patent application CN200910098518.2.
A kind of preparation method of suede structure zinc oxide transparent conductive film comprises step:
Adopt magnetically controlled sputter method, take the zinc oxide ceramics of doped element doping as target, take argon gas as sputter gas, the base vacuum degree is 4 * 10
-3Pa～1 * 10
-4Pa, the pressure of sputter gas are 0.2Pa～1.5Pa, and underlayer temperature is 150 ℃～350 ℃, makes the suede structure zinc oxide transparent conductive film.
In order to reach better invention effect, preferably:
Described doped element is selected one or both in Al, Ga, Y, B, Sn, Ti, V.
In described target, the mole percent concentration of doped element is 0.5%～6%.
Molar ratio in described doped element between two kinds of doped elements is 0.05～1: 1.
The pressure of described sputter gas is 0.3Pa～1.0Pa, and underlayer temperature is 250 ℃～350 ℃.
Described sputtering power is 70W～120W, and sputtering time is 15 minutes～30 minutes.
Described magnetically controlled sputter method can adopt this area magnetically controlled sputter method commonly used, as dc magnetron sputtering method or radio frequency magnetron sputtering method etc.
Described substrate can adopt this area magnetron sputtering substrate commonly used, as simple glass or silica glass etc.
Compared with prior art, the present invention has following beneficial effect:
The present invention adopt magnetically controlled sputter method directly to prepare to have " pyramid ' pile face doped zinc oxide transparent conductive film of shape, preparation technology is simple, production cost is low, is suitable for large-scale industrial production.
The thickness of the pile face doped zinc oxide transparent conductive film of the inventive method preparation is generally 300nm～1200nm, the suede degree is at 3%～10% (wavelength is at the 550nm place), square resistance is at 5 Ω/～50 Ω/, roughness is at 10nm～50nm, has higher suede degree, higher surfaceness and good electrooptics performance are suitable for the preparation of thin film solar cell, can improve the photoelectric transformation efficiency of solar cell.
Description of drawings
Fig. 1 is that the matte AZO transparent conductive film that makes of embodiment 1 and embodiment 2 is at transmitted spectrum and the suede degree figure of visible region;
Fig. 2 is atomic force microscope (Atomic Force Microscopy, the AFM) figure of the matte AZO transparent conductive film that makes of embodiment 1;
Fig. 3 is scanning electron microscope diagram (Scanning Electron Microscope, the SEM) figure of the matte AZO transparent conductive film that makes of embodiment 1;
Fig. 4 is the AFM figure of the matte AZO transparent conductive film that makes of embodiment 2;
Fig. 5 is the SEM figure of the matte AZO transparent conductive film that makes of embodiment 2.
Embodiment
Following embodiment further illustrates of the present invention, yet, should be appreciated that and consider this disclosure, those skilled in the art can make in the scope that the present invention relates to and revise and improve.
As target, wherein the doping ratio of Al is 1at% (molar percentage) with ZnO doping Al compound (ZnO:Al); As sputter gas, the argon gas operating air pressure is 0.5Pa with high-purity (purity＞99.999%) argon gas; Substrate is common glass sheet, and underlayer temperature is 300 ℃.Adopt the magnetically controlled DC sputtering preparation method, the base vacuum degree is 4 * 10
-4Pa, sputtering power are 100W, and sputtering time is 15 minutes.
Result obtains matte AZO transparent conductive film, and its thickness is 300nm ± 5nm, and square resistance is 50 Ω/, and the total transmitance of visible light is 85.2%, and the suede degree is 6.3%, and surfaceness is 25.5nm.
The matte AZO transparent conductive film that makes is at transmitted spectrum and suede degree figure such as Fig. 1 of visible region; Atomic force microscope figure such as Fig. 2 can calculate roughness of film; SEM figure demonstrates the concrete coarse surface tissue of film as Fig. 3, presents " pyramid " shape.
As target, wherein the doping ratio of Al is 1at% with ZnO doping Al compound (ZnO:Al); As sputter gas, the argon gas operating air pressure is 0.5Pa with high-purity argon gas (purity＞99.999%); Substrate is common glass sheet, and underlayer temperature is 300 ℃.Adopt the magnetically controlled DC sputtering preparation method, the base vacuum degree is 4 * 10
-4Pa, sputtering power are 100W, and sputtering time is 30 minutes.
Result obtains matte AZO transparent conductive film, and its thickness is 600nm ± 8nm, and square resistance is 8 Ω/, and the total transmitance of visible light is 86.7%, and the suede degree is 8.9%, and surfaceness is 41.2nm.
The matte AZO transparent conductive film that makes is at transmitted spectrum and suede degree figure such as Fig. 1 of visible region; Atomic force microscope figure such as Fig. 4 can calculate roughness of film, can find out that this film surface is more coarse than the matte AZO transparent conductive film that embodiment 1 makes; SEM figure demonstrates film and presents typically " pyramid " shape as Fig. 5.
As target, wherein the doping ratio of Y is 1.5at% with ZnO doping Y compound (ZnO:Y); As sputter gas, the argon gas operating air pressure is 0.3Pa with high-purity argon gas (purity＞99.999%); Substrate is common glass sheet, and underlayer temperature is 350 ℃.Adopt the magnetically controlled DC sputtering preparation method, the base vacuum degree is 1 * 10
-4Pa, sputtering power are 100W, and sputtering time is 30 minutes.
Result obtains the YZO transparent conductive film, and its thickness is 600nm ± 5nm, and square resistance is 15 Ω/, and the total transmitance of visible light is 87.5%, and the suede degree is 4.9%, and surfaceness is 13.3nm.
As target, wherein the doping ratio of Al, Ti is 3at% with ZnO doping Al and Ti compound (ZnO:Al:Ti); As sputter gas, the argon gas operating air pressure is 1.0Pa with high-purity argon gas (purity＞99.999%); Substrate is common glass sheet, and underlayer temperature is 250 ℃.Adopt the rf magnetron sputtering preparation method, the base vacuum degree is 4 * 10
-3Pa, sputtering power are 100W, and sputtering time is 15 minutes.
Result obtains matte TAZO transparent conductive film, and its thickness is 300nm ± 7nm, and square resistance is 22 Ω/, and the total transmitance of visible light is 84.8%, and the suede degree is 4.1%, and surfaceness is 10.1nm.
To sum up, the present invention adopts magnetically controlled sputter method directly to prepare pile face doped zinc oxide transparent conductive film, the transparent conductive film that obtains having the good electrical optical characteristics and fall into light characteristic, thereby the photoabsorption that is conducive to improve battery, the photoelectric transformation efficiency of raising solar cell.
Claims (2)
1. the preparation method of a suede structure zinc oxide transparent conductive film, is characterized in that, as target, wherein the molar percentage doping ratio of Al is 1at% with ZnO doping Al compound; With purity〉99.999% high-purity argon gas is as sputter gas, and the argon gas operating air pressure is 0.5Pa; Substrate is common glass sheet, and underlayer temperature is 300 ℃, adopts the magnetically controlled DC sputtering preparation method, and the base vacuum degree is 4 * 10
-4Pa, sputtering power are 100W, and sputtering time is 15 minutes;
Result obtains matte AZO transparent conductive film, and its thickness is 300nm ± 5nm, and square resistance is 50 Ω/, and the total transmitance of visible light is 85.2%, and the suede degree is 6.3%, and surfaceness is 25.5nm.
2. the preparation method of a suede structure zinc oxide transparent conductive film, is characterized in that, as target, wherein the molar percentage doping ratio of Al is 1at% with ZnO doping Al compound; With purity〉99.999% high-purity argon gas is as sputter gas, and the argon gas operating air pressure is 0.5Pa; Substrate is common glass sheet, and underlayer temperature is 300 ℃, adopts the magnetically controlled DC sputtering preparation method, and the base vacuum degree is 4 * 10
-4Pa, sputtering power are 100W, and sputtering time is 30 minutes;
Result obtains matte AZO transparent conductive film, and its thickness is 600nm ± 8nm, and square resistance is 8 Ω/, and the total transmitance of visible light is 86.7%, and the suede degree is 8.9%, and surfaceness is 41.2nm.
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| CN102676994B (en) * | 2012-06-07 | 2014-07-16 | 上海硅酸盐研究所中试基地 | ZnO base diluted magnetic semiconductor film with intrinsic ferromagnetism and preparation method thereof |
| CN103046013A (en) * | 2012-12-30 | 2013-04-17 | 青海天誉汇新能源开发有限公司 | Method for preparing photovoltaic cell transparent oxide film with flexible substrate |
| CN104060232A (en) * | 2014-06-20 | 2014-09-24 | 江阴恩特莱特镀膜科技有限公司 | Method for preparing hafnium-doped zinc oxide transparent conductive thin film |
| CN106591789B (en) * | 2016-12-21 | 2019-03-12 | 蚌埠玻璃工业设计研究院 | A method of directly preparing flannelette AZO film |
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| CN101845614A (en) * | 2010-05-07 | 2010-09-29 | 中国科学院宁波材料技术与工程研究所 | Method for preparing zinc oxide-based sputtering target material |
| CN101885609A (en) * | 2009-05-14 | 2010-11-17 | 中国科学院宁波材料技术与工程研究所 | Method for preparing zinc oxide-based ceramic sputtering target material at intermediate temperature |
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| CN101885609A (en) * | 2009-05-14 | 2010-11-17 | 中国科学院宁波材料技术与工程研究所 | Method for preparing zinc oxide-based ceramic sputtering target material at intermediate temperature |
| CN101845614A (en) * | 2010-05-07 | 2010-09-29 | 中国科学院宁波材料技术与工程研究所 | Method for preparing zinc oxide-based sputtering target material |
Non-Patent Citations (2)
| Title |
|---|
| Dongyun Wan,et al.."Highly Surface-Textured ZnO:Al Films Fabricated by Controlling the Nucleation and Growth Separately for Solar Cell Applications".《APPLIED MATERIALS & INTERFACES》.2010,第2卷(第7期),第2147-2153页. * |
| 付恩刚,等."绒面ZnO:Al(ZAO)透明导电薄膜的制备".《太阳能学报》.2003,第24卷(第5期),第672-676页. * |
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