CN103266302A - Method for preparing AZO film texture structure used for film solar cell - Google Patents
Method for preparing AZO film texture structure used for film solar cell Download PDFInfo
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- CN103266302A CN103266302A CN2013100572063A CN201310057206A CN103266302A CN 103266302 A CN103266302 A CN 103266302A CN 2013100572063 A CN2013100572063 A CN 2013100572063A CN 201310057206 A CN201310057206 A CN 201310057206A CN 103266302 A CN103266302 A CN 103266302A
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Abstract
The invention discloses a method for preparing an AZO film texture structure used for film solar cells. The method comprises the steps of: (1) cleaning a glass substrate, etching the surface of the glass substrate by using the dual-frequency capacitively coupled plasma discharge technology to make the surface of the glass substrate to have a texture structure; and (2) depositing an AZO film on the texture structure of the glass substrate by the magnetron sputtering technology to obtain the AZO film texture structure. Experiments show that, the light reflection loss of the textured structure of the film solar cell prepared by the method is less than 9%, fully meeting the requirements of the solar cell for a front electrode light trapping structure.
Description
Technical field
The present invention relates to a kind of preparation method of the AZO film suede structure for thin-film solar cells.
Background technology
At present, because energy shortage, global warming and environmental pollution is serious day by day, promoted the fast development of renewable energy source, and sun power has cleaning, pollution-free, outstanding advantage such as inexhaustible grade becomes one of future ideality energy.Wherein, thin-film solar cells can be used at cheap glass, plastics, pottery, graphite, and differing materials such as tinsel are made when substrate, and the film thickness that formation can produce voltage only needs several microns, and the Gao Yike of efficiency of conversion reaches 13% at present.The some of building body can be combined or become to the hull cell solar cell also because having pliability can be made into on-plane surface to construct its range of application big, with buildings except the plane, use very extensive.
In recent years, AZO film (mixing the zinc-oxide film of aluminium) is applied to thin-film solar cells owing to have distinguishing features such as resistivity is low, transmittance height as preceding electrode materials.But improve the luminous efficiency of solar cell, its surface also must have suitable suede structure, because suitable suede structure and surfaceness be scatter incident light effectively, especially long wavelength's light (ruddiness and near infrared ray), allow light in battery, form light trapping, thereby increase light at effective light path of active coating, finally make the light-absorption layer of battery catch more rays, improve the photoelectric transformation efficiency of thin-film solar cells.At present, the preparation method of the AZO film suede structure of thin-film solar cells mainly contains following 2 kinds: (1) utilizes magnetron sputtering technique to deposit smooth AZO film at glass surface, carries out chemical acid system etching then, obtains matte AZO film; It is 0.5% dilute hydrochloric acid that the acid system etching generally adopts volume fraction, and etching time is 10 ~ 30 seconds, and the film surface r.m.s. roughness is 20 ~ 150 nm, and performance index can satisfy the preceding electrode requirement of thin-film solar cells.Yet there is following shortcoming in the method for acid system etching after the above-mentioned first film forming: (a) the acid system etching approximately will consume the AZO film more than 1/3rd, and only remaining AZO film less than 2/3rds can become suede structure, causes production cost to increase; (b) need a large amount of reaction soln and deionized waters that use higher cost; (c) the wet etching thickness that degrades silicon generally reaches micron dimension, is not suitable for using in hull cell; Operator faced very big safety problem when (d) pharmaceutical chemicals was handled; (e) etching process can produce a large amount of waste gas, spent acid, brings environmental pollution.(2) by the control experiment parameter, directly go out the AZO film of suede structure at the smooth glass surface sputtering; Yet the suede structure that this method obtains is not remarkable, can't satisfy solar cell to the requirement of preceding electrode light trapping structure.
Summary of the invention
The object of the invention provides a kind of preparation method of the AZO film suede structure for thin-film solar cells.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of the AZO film suede structure for thin-film solar cells comprises the steps:
(1) cleans glass substrate, adopt double frequency capacitively coupled plasma discharge technology that etching is carried out on the surface of described glass substrate then, make glass baseplate surface have suede structure;
(2) adopt magnetron sputtering technique at the suede structure deposition AZO of above-mentioned glass substrate film, can obtain AZO film suede structure.
Above, the glass selected for use of described glass substrate can be that (oxide mass per-cent is SiO to alumina silicate glass
2: 64.4%; Al
2O
3: 13.6%; MgO:4.5%; Na
2O:12.5%; K
2O:2%; CaO:1%).
Described cleaning can be to put into Ultrasonic Cleaners to carry out, and in acetone and ethanol, ultrasonic cleaning 10 minutes cleans up with deionized water then respectively in elder generation, takes out back nitrogen and dries up.
The purpose of cleaning is for the oil stain of removing glass surface and impurity etc., for follow-up etching is prepared.
In the technique scheme, in the described step (1), etching gas is Ar
2And C
4F
8Mixed gas, its flow is respectively 10 ~ 20 sccm and 1 ~ 3 sccm.
In the technique scheme, what described step (1) adopted is double frequency capacitively coupled plasma equipment, and its base vacuum is 9 * 10
-4~ 3 * 10
-3Pa; Operating air pressure is 15 ~ 35Pa; High frequency frequency and power are respectively 60MHz and 200 ~ 300W, and low frequency frequency and power are respectively 2MHz and 200 ~ 300W, and etching time is 10 ~ 30min.Be double frequency capacitively coupled plasma (DF-CCP) equipment.
In the technique scheme, in the described step (2), the used target of magnetron sputtering technique is the Zn/Al alloy; Sputter gas is the mixed gas of argon gas and oxygen, and argon flow amount is 10 ~ 30 sccm, and oxygen flow is 2 ~ 10 sccm.
Because technique scheme is used, the present invention compared with prior art has following advantage:
1. the present invention has developed a kind of preparation method of new a kind of AZO film suede structure for thin-film solar cells, adopt double frequency capacitively coupled plasma (Dual-frequency Capacitively Coupled Plasma earlier, DF-CCP) discharge technology, substrate of glass is carried out surface etching treatment, obtain the glass surface of suede structure, at glass surface, has the AZO film of suede structure with the magnetically controlled sputter method deposition then; Avoided acid system etching technics problem in the prior art the problem includes: spent acid to the thickness waste problem of pollution, safety and the AZO film of environment; It is not remarkable to have avoided directly going out the suede structure that the AZO film of suede structure exists at the smooth glass surface sputtering yet, can't satisfy solar cell to the problem of the requirement of preceding electrode light trapping structure.
2. the light reflection loss that experiment showed, the suede structure of the thin-film solar cells that employing method of the present invention prepares is lower than 9%, satisfies solar cell fully to the requirement of preceding electrode light trapping structure.
3. the present invention has adopted double frequency capacitively coupled plasma discharge technology that etching is carried out on the surface of glass substrate, thereby have that lateral encroaching is little, undercutting is little, no chemical waste fluid, the resolving power height, operational safety, easy, advantages such as treating processes is not introduced pollution, easily is automated, and surface damage is little.
4. preparation method of the present invention is simple to operate, pollutes for a short time, does not have dangerously, has active operation significance.
Description of drawings
Fig. 1 is the AFM figure of DF-CCP etching front glass surface topography in the embodiment of the invention one;
Fig. 2 is the AFM of glass surface pattern figure after the DF-CCP etching in the embodiment of the invention one;
Fig. 3 is the suede structure figure behind the deposition on glass AZO film after the etching processing in the embodiment of the invention one.
Embodiment
Be further described below in conjunction with the present invention of embodiment:
Embodiment one
A kind of preparation method of the AZO film suede structure for thin-film solar cells comprises the steps:
(1) cleaning of glass baseplate surface: the glass of selecting for use is that (oxide mass per-cent is SiO to alumina silicate glass
2: 64.4%; Al
2O
3: 13.6%; MgO:4.5%; Na
2O:12.5%; K
2O:2%; CaO:1%), thickness of glass is 3mm, and size is 25mm ' 25mm; Put into Ultrasonic Cleaners, in acetone and ethanol, ultrasonic cleaning 10 minutes cleans up with deionized water then respectively in elder generation, takes out back nitrogen and dries up;
(2) cleaned glass is positioned on the bottom crown of vacuum chamber in double frequency capacitively coupled plasma (DF-CCP) equipment, the substrate of glass temperature is room temperature, and vacuum is evacuated to base vacuum, feeds etching gas then, carry out etching, make glass baseplate surface have suede structure;
Etching gas component and flow: etching gas is Ar
2And C
4F
8Mixed gas, flow is respectively 10 sccm and 1 sccm;
Base vacuum: 1 * 10
-3Pa;
Operating air pressure: 20Pa;
High frequency frequency and power: 60MHz, 200W;
Low frequency frequency and power: 2MHz, 200W;
Etching time: 20min;
After etching finishes, close radio frequency power source, close gas, utilize vacuum system to extract residual gas in the chamber out, close vacuum system at last, shutdown;
(3) after cooling for some time, open chamber, take out the glass through etching;
(4) glass substrate with suede structure after the DF-CCP etching processing is taken out from vacuum cavity after, be put into the CS-400 three target radio frequency magnetron sputtering coating equipments deposition AZO film that Changshu Yuhua Vacuum Equipment Co., Ltd. makes, the substrate of glass temperature is room temperature, makes AZO film suede structure at last;
The magnetron sputtering deposition processing parameter:
Base vacuum reaches: 7.0 * 10
-4Pa;
Operating air pressure 2Pa;
Sputter gas: argon gas (Ar) and oxygen (O
2) mixed gas;
The flow of argon gas and oxygen: Ar flow 15 sccm; O
2Flow 3 sccm;
Radio frequency power: 170W;
Sputtering time: 60min;
Depositing temperature: room temperature.
Use atomic force microscope (AFM) that the surface topography of glass before and after the etching is characterized then, the result is: etching front glass surface particles is evenly distributed, the maximum (High that rises and falls in surface
Max) and r.m.s. roughness (RMS) only be respectively 70.4 nm and 9 nm, referring to accompanying drawing 1.
After the DF-CCP etching, very big variation has taken place in the surface topography of sample, presented good pyramid-like shape pattern, the maximum fluctuating of sample surfaces and r.m.s. roughness have also risen to 1055.8 nm and 159.5 nm respectively, see accompanying drawing 2, illustrate that the substrate of glass after the etching processing has good matte pattern.
Behind the deposition on glass AZO film after the etching processing, the maximum fluctuating of sample surfaces and r.m.s. roughness are respectively 680 nm and 133 nm, and suede structure is remarkable.Referring to accompanying drawing 3.
Show that through the optical reflectivity test light reflection loss of this suede structure is lower than 9%, satisfies solar cell fully to the requirement of preceding electrode light trapping structure.
Claims (4)
1. a preparation method who is used for the AZO film suede structure of thin-film solar cells is characterized in that, comprises the steps:
(1) cleans glass substrate, adopt double frequency capacitively coupled plasma discharge technology that etching is carried out on the surface of described glass substrate then, make glass baseplate surface have suede structure;
(2) adopt magnetron sputtering technique at the suede structure deposition AZO of above-mentioned glass substrate film, can obtain AZO film suede structure.
2. preparation method according to claim 1, it is characterized in that: in the described step (1), etching gas is Ar
2And C
4F
8Mixed gas, its flow is respectively 10 ~ 20 sccm and 1 ~ 3 sccm.
3. preparation method according to claim 1 is characterized in that: what described step (1) adopted is double frequency capacitively coupled plasma equipment, and its base vacuum is 9 * 10
-4~ 3 * 10
-3Pa; Operating air pressure is 15 ~ 35Pa; High frequency frequency and power are respectively 60MHz and 200 ~ 300W, and low frequency frequency and power are respectively 2MHz and 200 ~ 300W, and etching time is 10 ~ 30min.
4. preparation method according to claim 1 is characterized in that, in the described step (2), the used target of magnetron sputtering technique is the Zn/Al alloy; Sputter gas is the mixed gas of argon gas and oxygen, and argon flow amount is 10 ~ 30 sccm, and oxygen flow is 2 ~ 10 sccm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104465890A (en) * | 2014-12-25 | 2015-03-25 | 中国建材国际工程集团有限公司 | Preparation method for textured AZO thin film used for thin film solar cell front electrode |
| 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 |
| CN115295636A (en) * | 2022-08-19 | 2022-11-04 | 信利半导体有限公司 | AZO texturing method |
Citations (3)
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|---|---|---|---|---|
| CN101308882A (en) * | 2008-07-22 | 2008-11-19 | 东莞宏威数码机械有限公司 | Preparing method of transparent electricity conductive oxide suede |
| CN101497992A (en) * | 2009-03-18 | 2009-08-05 | 江苏秀强玻璃工艺有限公司 | Method for preparing pile face zinc oxide transparent conductive film coating glass by plasma bombardment |
| CN102863156A (en) * | 2012-09-21 | 2013-01-09 | 蚌埠玻璃工业设计研究院 | Preparation method of textured AZO (aluminum-doped zinc oxide) transparent conductive film |
-
2013
- 2013-02-22 CN CN2013100572063A patent/CN103266302A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101308882A (en) * | 2008-07-22 | 2008-11-19 | 东莞宏威数码机械有限公司 | Preparing method of transparent electricity conductive oxide suede |
| CN101497992A (en) * | 2009-03-18 | 2009-08-05 | 江苏秀强玻璃工艺有限公司 | Method for preparing pile face zinc oxide transparent conductive film coating glass by plasma bombardment |
| CN102863156A (en) * | 2012-09-21 | 2013-01-09 | 蚌埠玻璃工业设计研究院 | Preparation method of textured AZO (aluminum-doped zinc oxide) transparent conductive film |
Non-Patent Citations (1)
| Title |
|---|
| 王文娜等: "绒面AZO干法制备及性能研究", 《光电工程》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104465890A (en) * | 2014-12-25 | 2015-03-25 | 中国建材国际工程集团有限公司 | Preparation method for textured AZO thin film used for thin film solar cell front electrode |
| 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 |
| CN115295636A (en) * | 2022-08-19 | 2022-11-04 | 信利半导体有限公司 | AZO texturing method |
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Application publication date: 20130828 |