CN102220562A - 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 field, 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 that the thin film solar cell of representative is developed fast with the Si base, because silicon is non-direct band gap material, a little less than the absorption to sunlight, therefore utilize sunken light (light trapping) structure that 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 the glass substrate, TCO) as the Window layer and the preceding electrode of battery, be responsible for seeing through of light and transporting of photo-generated carrier, its structure and performance have close influence 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, prolongs the utilization ratio of the travel path of light in absorption layer with increase light, and then improves battery efficiency.The criterion of matte is the 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.) have formed industrialization production.But the FTO film is poisonous, and it is higher to deposit used spray pyrolysis technology temperature, is difficult to the big area uniform deposition, costs an arm and a leg, and is subjected to the reductive action of hydrogen plasma easily.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 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, big area evenly ZnO thin film doped main flow preparation method is a 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 two step processes of this post-etching of deposition earlier 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 by magnetron sputtering one step and prepares the ZnO film that has suede structure.For example, among the Chinese invention patent ZL03137254.6 method that a kind of magnetron sputtering prepares the suede structure zinc oxide transparent conductive film is disclosed.The suede degree of the zinc oxide transparent conductive film that this method is prepared is 3.0～31.6%, and roughness is 10.8～50.2nm.Bigger (the 3Pa～15Pa), and air pressure causes the damage of film greatly easily, and then have influence on the electric property of film of this 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 the AZO film of being with matte, and obtaining roughness is 40.2nm, better conductivity matte AZO film.Though 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 Shen Qing Publication specification sheets 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, on glass substrate, grow surfaceness～70nm, the transparent conductive film of square resistance～5 Ω, the sputtering target material that this method adopted is an alloys target, is poisoned especially easily in sputter procedure, causes the inhomogeneous of sputter procedure.Therefore developing a kind of new zinc oxide transparent conductive film that utilizes one step of ceramic sputtering target material uniform deposition suede structure seems and is necessary that very 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, this method is target with the doping zinc-oxide, adopt magnetically controlled sputter method directly to prepare the zinc oxide transparent conductive film that has good electrical characteristic and suede structure simultaneously, 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 following two types factor have close related: one, doped element kind and the doping content in the target; Two, the process parameter of sputter is as sputtering pressure, underlayer temperature, sputtering power etc.This is that film is followed the three dimensional growth pattern because at certain element doping condition and sputtering parameter and down, and promptly 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 under the suitable situation of above-mentioned two kinds of factors, 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 is adopted among 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 among the 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 among the Chinese patent application CN200910098518.2.
A kind of preparation method of suede structure zinc oxide transparent conductive film comprises step:
Adopting magnetically controlled sputter method, is target with the adulterated zinc oxide ceramics of doped element, is sputter gas with the argon gas, and 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 among Al, Ga, Y, B, Sn, Ti, the V for use.
The mole percent concentration of doped element is 0.5%～6% in the described target.
Molar ratio in the 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 transmitted spectrum and the suede degree figure of the matte AZO transparent conductive film that makes of embodiment 1 and embodiment 2 at visible region;
Fig. 2 is atomic force microscope (Atomic Force Microscopy, AFM) figure of the matte AZO transparent conductive film that makes of embodiment 1;
Fig. 3 is scanning electron microscope diagram (Scanning Electron Microscope, 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 specifies of the present invention, yet, should be appreciated that and consider this disclosure that those skilled in the art can make and revise and improve in the scope that the present invention relates to.
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 the simple 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.
The 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 the simple 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.
The 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, and this film surface is more coarse than the matte AZO transparent conductive film that embodiment 1 makes as can be seen; 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 the simple 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.
The 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 the simple 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.
The 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 helps improving battery, the photoelectric transformation efficiency of raising solar cell.
Claims (6)
1. the preparation method of a suede structure zinc oxide transparent conductive film is characterized in that, comprises step:
Adopting magnetically controlled sputter method, is target with the adulterated zinc oxide ceramics of doped element, is sputter gas with the argon gas, and 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.
2. the preparation method of suede structure zinc oxide transparent conductive film according to claim 1 is characterized in that, described doped element is one or both among Al, Ga, Y, B, Sn, Ti, the V.
3. the preparation method of suede structure zinc oxide transparent conductive film according to claim 2 is characterized in that, the molar ratio in the described doped element between two kinds of doped elements is 0.05～1: 1.
4. according to the preparation method of claim 1,2 or 3 described suede structure zinc oxide transparent conductive films, it is characterized in that the mole percent concentration of doped element is 0.5%～6% in the described target.
5. the preparation method of suede structure zinc oxide transparent conductive film according to claim 1 is characterized in that, the pressure of described sputter gas is 0.3Pa～1.0Pa, and underlayer temperature is 250 ℃～350 ℃.
6. the preparation method of suede structure zinc oxide transparent conductive film according to claim 1 is characterized in that, described sputtering power is 70W～120W, and sputtering time is 15 minutes～30 minutes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676994A (en) * | 2012-06-07 | 2012-09-19 | 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 |
| CN106591789A (en) * | 2016-12-21 | 2017-04-26 | 蚌埠玻璃工业设计研究院 | Method for directly preparing suede 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 |
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| 《APPLIED MATERIALS & INTERFACES》 20100706 Dongyun Wan，et al. "Highly Surface-Textured ZnO：Al Films Fabricated by Controlling the Nucleation and Growth Separately for Solar Cell Applications" 第2147-2153页 6 第2卷, 第7期 * |
| 《太阳能学报》 20031031 付恩刚，等 "绒面ZnO：Al（ZAO）透明导电薄膜的制备" 第672-676页 1-6 第24卷, 第5期 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676994A (en) * | 2012-06-07 | 2012-09-19 | 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 |
| CN106591789A (en) * | 2016-12-21 | 2017-04-26 | 蚌埠玻璃工业设计研究院 | Method for directly preparing suede AZO film |
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