CN106835012A - A kind of preparation method of matte aluminum-doped zinc oxide films - Google Patents

A kind of preparation method of matte aluminum-doped zinc oxide films Download PDF

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Publication number
CN106835012A
CN106835012A CN201611188162.8A CN201611188162A CN106835012A CN 106835012 A CN106835012 A CN 106835012A CN 201611188162 A CN201611188162 A CN 201611188162A CN 106835012 A CN106835012 A CN 106835012A
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China
Prior art keywords
azo
zinc oxide
doped zinc
preparation
oxide films
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CN201611188162.8A
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Chinese (zh)
Inventor
汤永康
金良茂
姚婷婷
马立云
甘治平
王东
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China Triumph International Engineering Co Ltd
CNBM Bengbu Design and Research Institute for Glass Industry Co Ltd
Bengbu Glass Industry Design and Research Institute
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China Triumph International Engineering Co Ltd
Bengbu Glass Industry Design and Research Institute
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Priority to CN201611188162.8A priority Critical patent/CN106835012A/en
Publication of CN106835012A publication Critical patent/CN106835012A/en
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02Pretreatment of the material to be coated
    • C23C14/024Deposition of sublayers, e.g. to promote adhesion of the coating
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • C23C14/086Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/35Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02Details
    • H01L31/0216Coatings
    • H01L31/02161Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Sustainable Development (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Glass (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The present invention discloses a kind of preparation method of matte aluminum-doped zinc oxide films, comprises the following steps:S1, substrate of glass is taken, hydroxylating treatment is carried out to glass basic surface;S2, with the polystyrene sphere microemulsion of solid content 0.01~0.10% hydroxylated glass basic surface prepare polystyrene moulding layer;S3, using DC magnetron sputtering process, prepare the AZO films that thickness is 500~900nm on polystyrene moulding layer;S4, by be heat-treated removal polystyrene moulding layer, AZO films is divided into the upper AZO film layers and lower AZO film layers of hollow out;S5, gluing oxidant layer is prepared in upper AZO thin-film surfaces, upper AZO film layers are transferred to another substrate surface, finally give matte aluminum-doped zinc oxide films;Give up traditional matte preparation method, it is to avoid the shortcoming that conventional etch process is difficult to control to, environmental pollution is larger, process is simple, low cost.

Description

A kind of preparation method of matte aluminum-doped zinc oxide films
Technical field
The present invention relates to solar battery thin film technical field, specifically a kind of preparation of matte aluminum-doped zinc oxide films Method.
Background technology
Aluminium-doped zinc oxide (AZO) film is a kind of transparent conductive film material with excellent photoelectric properties, and is had Raw material is easy to get, price is relatively low, less pollution, preferable thermo-chemical stability the advantages of so that turn into preferable ito thin film substitute material Material.
AZO has in silica-based solar cell, thin-film solar cells as preceding electrode and is widely applied, solar-electricity Absorption of the absorbed layer in pond to incident light is limited, therefore it is very necessary that one layer of sunken light suede structure is designed on transparent front electrode. Suede structure increases incident sunshine light path in solar cells by strengthening refraction and scattering to incident light, improves Film to the absorptivity of light, so as to improve the photoelectric transformation efficiency of solar cell.
At present, traditional AZO film matte preparation methods are divided into pre-etching of film etching and plated film front glass substrate etc., The film for preparing is performed etching to form matte or first perform etching glass substrate, the coarse matte knot of substrate is formed Plated film forms matte on the glass substrate of matte after structure.Lithographic method mainly has wet etching and dry etching, i.e., using one Determine acid solution corrosion or the laser plasma etching of concentration.These traditional matte preparation methods have complex procedures, energy Source consumes the shortcomings of larger, etching process is difficult to control to, environmental pollution is larger.
The content of the invention
It is an object of the invention to provide a kind of preparation method of matte aluminum-doped zinc oxide films, the letter of the method technique Single, process is easily controlled, low cost.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of preparation method of matte aluminum-doped zinc oxide films, comprises the following steps:
S1, substrate of glass is taken, hydroxylating treatment is carried out to glass basic surface;
S2, polyphenyl is prepared in hydroxylated glass basic surface with the polystyrene sphere microemulsion of solid content 0.01~0.10% Ethene template layer;
S3, using DC magnetron sputtering process, prepare the AZO films that thickness is 500~900nm on polystyrene moulding layer;
S4, by be heat-treated removal polystyrene moulding layer, AZO films is divided into the upper AZO film layers and lower AZO films of hollow out Layer;
S5, gluing oxidant layer is prepared in upper AZO thin-film surfaces, upper AZO film layers are transferred to another substrate surface, finally given Matte aluminum-doped zinc oxide films.
Further, the hydroxylating in the step S1 is processed as substrate of glass being placed in volume ratio 7:3 concentrated sulfuric acid with In the mixed solution of hydrogen peroxide, 1~3h is soaked in the environment of 50~70 DEG C, it is repeatedly clear with absolute ethyl alcohol with deionized water afterwards Wash and obtain hydroxylated substrate of glass.
Further, the step S2 polystyrene mouldings layer can be using spin coating, blade coating or vertical dipping self-assembly method work It is prepared by skill.
Further, the step S3 DC magnetron sputtering process is with the mixed oxide ceramic target of Al and Zn as sputtering target Material, target 5~10cm of spacing, 20~50sccm of argon flow amount, 150~400W of sputtering power, 0.1~1.0Pa of operating pressure.
Further, the temperature of the step S4 heat treatments is 400~600 DEG C, 1.5~4.0h of heat treatment time.
The beneficial effects of the invention are as follows, give up traditional matte preparation method, polystyrene moulding is prepared by liquid phase method Layer, AZO films are prepared by magnetron sputtering, after removal polystyrene moulding layer, the medial surface self-assembling formation suede of upper AZO film layers Face, after it is separated with lower AZO film layers 3b, upper AZO film layers medial surface upset is changed into lateral surface, that is, obtain the doping of matte aluminium Zinc-oxide film AZO films, it is to avoid the shortcoming that conventional etch process is difficult to control to, environmental pollution is larger, process is simple, cost It is low.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples:
Fig. 1 is the schematic diagram of step S2 of the present invention;
Fig. 2 is the schematic diagram of step S3 of the present invention;
Fig. 3 is the schematic diagram of step S4 of the present invention;
Fig. 4 is the schematic diagram of step S5 of the present invention.
Specific embodiment
The present invention provides a kind of preparation method of matte aluminum-doped zinc oxide films, comprises the following steps:
S1, substrate of glass is taken, substrate of glass is placed in volume ratio 7:In 3 concentrated sulfuric acid and the mixed solution of hydrogen peroxide, 50~ 1~3h is soaked in the environment of 70 DEG C, afterwards with deionized water and absolute ethyl alcohol cleaning repeatedly, is realized to glass basic surface Hydroxylating treatment;
S2, as shown in figure 1, with the polystyrene sphere microemulsion of solid content 0.01~0.10% in the table of hydroxylated substrate of glass 1 Face prepares polystyrene moulding layer 2;Polystyrene moulding layer 2 can be using spin coating, blade coating or vertical dipping self-assembly method technique system It is standby;
S3, with reference to shown in Fig. 2, using DC magnetron sputtering process, prepared on polystyrene moulding layer 2 thickness for 500~ The AZO films 3 of 900nm;DC magnetron sputtering process with the mixed oxide ceramic target of Al and Zn as sputtering target material, zinc oxide with The mass ratio of aluminum oxide is 98:2, can directly be bought by market, target 5~10cm of spacing, 20~50sccm of argon flow amount, sputter work( 150~400W of rate, 0.1~1.0Pa of operating pressure;
S4, with reference to shown in Fig. 3, by be heat-treated removal polystyrene moulding layer, AZO films is divided into the upper AZO films of hollow out Layer 3a and lower AZO film layers 3b;Heat treatment temperature is 400~600 DEG C, 1.5~4.0h of heat treatment time;
S5, with reference to shown in Fig. 4, prepare gluing oxidant layer 4 on upper AZO film layers 3a surfaces, be covered in gluing oxidant layer with another substrate 5 On 4, then substrate 5 is picked up, AZO film layers 3a is separated with lower AZO film layers 3b, upper AZO film layers 3a is transferred to base The surface of plate 5, finally gives matte aluminum-doped zinc oxide films, and gluing oxidant layer 4 be able to can be made using polyurethane adhesive, substrate 5 With glass substrate or pet substrate.
After removal polystyrene moulding layer, the medial surface self-assembling formation matte of upper AZO film layers 3a, by it with After AZO film layers 3b is separated, then the medial surface of upper AZO film layers 3a is turned into lateral surface, that is, obtains the doping oxidation of matte aluminium Zinc film.
The above, is only presently preferred embodiments of the present invention, and any formal limitation is not made to the present invention;Appoint What those of ordinary skill in the art, in the case where technical solution of the present invention ambit is not departed from, all using the side of the disclosure above Method and technology contents make many possible variations and modification, or the equivalent reality for being revised as equivalent variations to technical solution of the present invention Apply example.Therefore, every content without departing from technical solution of the present invention, is done according to technical spirit of the invention to above example Any simple modification, equivalent, equivalence changes and modification, still fall within the range of technical solution of the present invention protection.

Claims (5)

1. a kind of preparation method of matte aluminum-doped zinc oxide films, it is characterised in that comprise the following steps:
S1, substrate of glass is taken, hydroxylating treatment is carried out to glass basic surface;
S2, polyphenyl is prepared in hydroxylated glass basic surface with the polystyrene sphere microemulsion of solid content 0.01~0.10% Ethene template layer;
S3, using DC magnetron sputtering process, prepare the AZO films that thickness is 500~900nm on polystyrene moulding layer;
S4, by be heat-treated removal polystyrene moulding layer, AZO films is divided into the upper AZO film layers and lower AZO films of hollow out Layer;
S5, gluing oxidant layer is prepared in upper AZO thin-film surfaces, upper AZO film layers are transferred to another substrate surface, finally given Matte aluminum-doped zinc oxide films.
2. a kind of preparation method of matte aluminum-doped zinc oxide films according to claim 1, it is characterised in that the step Hydroxylating in rapid S1 is processed as substrate of glass being placed in volume ratio 7:In 3 concentrated sulfuric acid and the mixed solution of hydrogen peroxide, 50 1~3h is soaked in the environment of~70 DEG C, is cleaned repeatedly with deionized water and absolute ethyl alcohol obtain hydroxylated glass base afterwards Bottom.
3. a kind of preparation method of matte aluminum-doped zinc oxide films according to claim 1 and 2, it is characterised in that institute Stating step S2 polystyrene mouldings layer can be prepared using spin coating, blade coating or vertical dipping self-assembly method technique.
4. a kind of preparation method of matte aluminum-doped zinc oxide films according to claim 3, it is characterised in that the step Rapid S3 DC magnetron sputtering process with the mixed oxide ceramic target of Al and Zn as sputtering target material, target 5~10cm of spacing, argon gas stream Amount 20~50sccm, 150~400W of sputtering power, 0.1~1.0Pa of operating pressure.
5. a kind of preparation method of matte aluminum-doped zinc oxide films according to claim 4, it is characterised in that the step The temperature of rapid S4 heat treatments is 400~600 DEG C, 1.5~4.0h of heat treatment time.
CN201611188162.8A 2016-12-21 2016-12-21 A kind of preparation method of matte aluminum-doped zinc oxide films Pending CN106835012A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107611188A (en) * 2017-09-06 2018-01-19 蚌埠玻璃工业设计研究院 A kind of multilayer film transparent conducting glass preparation method with micro-structural
CN107611187A (en) * 2017-09-06 2018-01-19 蚌埠玻璃工业设计研究院 A kind of matte multilayer film transparent conducting glass
CN108165939A (en) * 2017-12-25 2018-06-15 中建材蚌埠玻璃工业设计研究院有限公司 A kind of preparation method of matte AZO films
CN108767020A (en) * 2018-06-04 2018-11-06 中建材蚌埠玻璃工业设计研究院有限公司 A kind of sunken light transparent conducting glass of silicon-based film solar cells
CN110300495A (en) * 2018-03-23 2019-10-01 睿明科技股份有限公司 Substrate film coating method
CN111574066A (en) * 2020-06-23 2020-08-25 中建材蚌埠玻璃工业设计研究院有限公司 Rapidly-heated anti-virus glass and preparation method thereof
CN114318264A (en) * 2021-12-29 2022-04-12 福建富兰光学股份有限公司 Method for preparing ITO film based on magnetron sputtering and etching treatment

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CN103508406A (en) * 2012-06-29 2014-01-15 无锡华润上华半导体有限公司 AZO thin film, preparing method and MEMS device comprising AZO thin film

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CN103508406A (en) * 2012-06-29 2014-01-15 无锡华润上华半导体有限公司 AZO thin film, preparing method and MEMS device comprising AZO thin film
CN103515484A (en) * 2013-09-13 2014-01-15 南开大学 Textured transparent conductive thin film with periodic structure and preparation method thereof

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黄鹤: "聚苯乙烯及AZO微结构薄膜的制备及其光学性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107611188A (en) * 2017-09-06 2018-01-19 蚌埠玻璃工业设计研究院 A kind of multilayer film transparent conducting glass preparation method with micro-structural
CN107611187A (en) * 2017-09-06 2018-01-19 蚌埠玻璃工业设计研究院 A kind of matte multilayer film transparent conducting glass
CN108165939A (en) * 2017-12-25 2018-06-15 中建材蚌埠玻璃工业设计研究院有限公司 A kind of preparation method of matte AZO films
CN110300495A (en) * 2018-03-23 2019-10-01 睿明科技股份有限公司 Substrate film coating method
CN108767020A (en) * 2018-06-04 2018-11-06 中建材蚌埠玻璃工业设计研究院有限公司 A kind of sunken light transparent conducting glass of silicon-based film solar cells
CN111574066A (en) * 2020-06-23 2020-08-25 中建材蚌埠玻璃工业设计研究院有限公司 Rapidly-heated anti-virus glass and preparation method thereof
CN114318264A (en) * 2021-12-29 2022-04-12 福建富兰光学股份有限公司 Method for preparing ITO film based on magnetron sputtering and etching treatment

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