CN113097345B - Processing method of chalcogenide solar thin film - Google Patents

Processing method of chalcogenide solar thin film Download PDF

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CN113097345B
CN113097345B CN202110383661.7A CN202110383661A CN113097345B CN 113097345 B CN113097345 B CN 113097345B CN 202110383661 A CN202110383661 A CN 202110383661A CN 113097345 B CN113097345 B CN 113097345B
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film
chalcogenide
thin film
sulfur
solar
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CN113097345A (en
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梁广兴
郑壮豪
范平
陈跃星
李甫
陈烁
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Shenzhen University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor 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
    • H01L31/0248—Semiconductor 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 characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor 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 characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor 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
    • H01L31/0248—Semiconductor 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 characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor 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 characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor 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
    • H01L31/0248—Semiconductor 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 characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor 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 characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a processing method of a chalcogenide solar thin film, wherein the chalcogenide thin film is used for manufacturing a solar cell, and the processing method comprises the following steps: providing a chalcogenide solar thin film; providing a sulfur-series simple substance film, wherein the sulfur-series elements in the sulfur-series simple substance film are the same as the sulfur-series elements in the sulfur-series compound solar film; superposing the chalcogenide simple substance film and the chalcogenide compound solar film to obtain a superposed film layer; and heating the superposed film layer in vacuum or inert atmosphere to make the sulfur elements in the sulfur simple substance film enter the sulfur compound solar film. The processing method of the chalcogenide solar thin film provided by the invention is simple and convenient, has low cost, is easy to control the components of the thin film and the growth mode of the thin film, and is easier to realize industrialized popularization.

Description

Processing method of chalcogenide solar thin film
Technical Field
The invention relates to the technical field of post-treatment of chalcogenide films, in particular to a treatment method of a chalcogenide solar film.
Background
The chalcogenide thin-film solar cell has the advantages of no toxicity, low cost, simple structure and the like, and is paid attention and favored by researchers. Therefore, obtaining a high-quality chalcogenide thin film for a solar cell is one of the leading research subjects in this field.
In the preparation process of the chalcogenide thin film, the chalcogenide material with high saturated steam is easy to volatilize and lose, and the chalcogenide thin film with high quality is synthesized by heat treatment, so that the chalcogenide element in the chalcogenide thin film formed in one step is often insufficient, and post treatment is needed to increase the combination of the chalcogenide element in the thin film material. At present, most of technologies are to heat treat a once-formed thin film material in a chalcogen atmosphere to increase the chalcogen component, but the method has poor controllability and repeatability and wastes raw materials greatly.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a treatment method of a chalcogenide solar thin film, and aims to solve the problems of poor controllability and repeatability and more waste of raw materials of the post-treatment method of the chalcogenide thin film in the prior art.
The technical scheme of the invention is as follows:
a method for processing a chalcogenide solar thin film for manufacturing a solar cell, comprising the steps of:
providing a chalcogenide solar thin film;
providing a sulfur-series simple substance film, wherein the sulfur-series element in the sulfur-series simple substance film is the same as at least one of the sulfur-series elements in the sulfur-series compound solar film;
superposing the chalcogenide simple substance film and the chalcogenide compound solar film to obtain a superposed film layer;
and heating the superposed film layer in vacuum or inert atmosphere to make the sulfur elements in the sulfur simple substance film enter the sulfur compound solar film.
The processing method of the chalcogenide solar thin film comprises the step of processing the chalcogenide solar thin film, wherein the chalcogenide solar thin film is one of an SbSe thin film, a CuZnSnSe thin film and a CuInGaSe thin film.
The processing method of the chalcogenide compound solar thin film comprises the following steps of preparing a chalcogenide compound solar thin film, and processing the chalcogenide compound solar thin film by using a chemical method.
The method for treating the chalcogenide solar thin film is characterized in that the temperature of the heating treatment is 300-500 ℃.
The processing method of the chalcogenide solar thin film is characterized in that the heating processing time is 15-120 min.
The processing method of the chalcogenide compound solar thin film comprises the following steps of preparing a chalcogenide compound solar thin film, and preparing a chalcogenide elemental thin film.
The processing method of the chalcogenide solar thin film comprises the following steps of preparing a chalcogenide solar thin film, and preparing a chalcogenide elemental thin film.
The processing method of the chalcogenide solar thin film, wherein the step of heating the superposed film layer in vacuum or inert atmosphere to obtain the thermoelectric thin film, further comprises the following steps:
pressure is applied in a direction perpendicular to the stacked film layers.
The processing method of the chalcogenide solar thin film adopts a physical vapor deposition method or a chemical vapor deposition method to prepare the chalcogenide simple substance thin film.
The processing method of the chalcogenide solar thin film is characterized in that the chalcogenide solar thin film is prepared by a physical vapor deposition method or a chemical vapor deposition method.
Has the advantages that: firstly, superposing the chalcogenide elementary substance film and the chalcogenide compound solar film to obtain a superposed film, and then heating the superposed film in vacuum or inert atmosphere to ensure that chalcogenide elements in the chalcogenide elementary substance film enter the chalcogenide compound solar film, thereby realizing the increase of chalcogenide elements in the chalcogenide compound solar film material. The processing method of the chalcogenide solar thin film provided by the invention is simple and convenient, has low cost, is easy to control the components of the thin film and the growth mode of the thin film, and is easier to realize industrialized popularization.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of a method for processing a chalcogenide solar thin film according to the present invention.
FIG. 2 is a schematic diagram illustrating a method for treating a chalcogenide solar thin film according to the present invention.
Detailed Description
The present invention provides a method for treating a chalcogenide solar thin film, and the present invention will be described in further detail below in order to make the objects, technical solutions, and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the preparation process of the chalcogenide thin film, the chalcogenide material with high saturated steam is easy to volatilize and lose, and the chalcogenide thin film with high quality is synthesized by heat treatment, so that the chalcogenide element in the chalcogenide thin film formed in one step is often insufficient, and post treatment is needed to increase the combination of the chalcogenide element in the thin film material. At present, most of technologies are to heat treat a once-formed thin film material in a chalcogen atmosphere to increase the chalcogen component, but the method has poor controllability and repeatability and wastes raw materials greatly.
Based on this, the invention provides a method for processing a chalcogenide solar thin film, as shown in fig. 1, which comprises the following steps:
s10, providing a chalcogenide solar thin film;
s20, providing a chalcogenide simple substance film, wherein the chalcogenide element in the chalcogenide simple substance film is the same as at least one of chalcogenide elements in the chalcogenide compound solar film;
s30, overlapping the chalcogenide simple substance film and the chalcogenide compound solar film to obtain an overlapped film layer;
and S40, heating the superposed film layer in vacuum or inert atmosphere to make the sulfur elements in the sulfur simple substance film enter the sulfur compound solar film.
With reference to fig. 2, in this embodiment, a chalcogenide solar thin film and a corresponding chalcogenide elemental thin film may be prepared first by using various thin film preparation methods, where a chalcogenide element in the chalcogenide solar thin film is the same as at least one of chalcogenide elements in the chalcogenide solar thin film, the two thin films are stacked, and the stacked thin films are heated under a vacuum condition or in an inert gas atmosphere, so that the chalcogenide element in the chalcogenide elemental thin film enters the chalcogenide solar thin film, thereby increasing a chalcogen component in the chalcogenide solar thin film material. The treatment method of the chalcogenide solar thin film provided by the embodiment is simple and convenient, has low cost, is easy to control the components of the thin film and the growth mode of the thin film, and is easier to realize industrialized popularization.
In some embodiments, the chalcogenide solar thin film is one of an SbSe thin film, a cuznsns thin film, and a CuInGaSe thin film, but is not limited thereto.
In some embodiments, the chalcogenide elemental film is one of a elemental sulfur film, an elemental selenium film, and an elemental tellurium film, but is not limited thereto.
In some specific embodiments, as shown in fig. 2, for example, in the case of processing an SbSe compound solar thin film, a elemental selenium thin film 20 is first prepared on the first substrate 10 by a physical vapor deposition method or a chemical vapor deposition method, and an SbSe compound solar thin film 40 is prepared on the second substrate 30 by a physical vapor deposition method or a chemical vapor deposition method; superposing a selenium elementary substance film 20 on the first substrate and an SbSe compound solar film 40 on the second substrate, wherein the selenium elementary substance film and the SbSe compound solar film are in contact with each other; and heating the superposed film layer in a vacuum or inert atmosphere, and finally enabling selenium in the elemental selenium film on the first substrate to enter the SbSe compound solar film on the second substrate, so that the selenium in the SbSe compound solar film is increased.
In some embodiments, the temperature of the heating treatment is 300-. In the temperature range, the chalcogenide elements in the chalcogenide simple substance film can rapidly and efficiently enter the chalcogenide compound solar film, so that the processing efficiency is improved.
In some embodiments, the time of the heat treatment is 15 to 120min, but is not limited thereto.
In some specific embodiments, the chalcogenide solar thin film is a cuznsse thin film, and the elemental chalcogenide thin film is an elemental selenium thin film. In this embodiment, if selenium needs to be added to the cuznsns film, the elemental selenium film and the cuznsns film are stacked and then heated in an inert atmosphere, so that the selenium in the elemental selenium film can enter the cuznsns film.
In some embodiments, the step of heating the stacked film layer in a vacuum or an inert atmosphere to obtain the thermoelectric thin film further includes: pressure is applied in a direction perpendicular to the stacked film layers. By applying pressure to the superposed film layer, the processing efficiency of the chalcogenide solar thin film can be further improved.
The method for treating a chalcogenide solar thin film according to the present invention is further illustrated by the following specific examples:
example 1
Post-treatment of SbSe compound solar thin films:
preparing an SbSe compound solar thin film on a glass substrate by a thermal evaporation technology, and preparing the glass substrate by a Se thin film by thermal evaporation;
after deposition, the SbSe compound solar thin film and the Se thin film are tightly attached and placed on a heating table to be heated for 30min at 450 ℃, wherein the Se content of a sample originally deposited with the SbSe compound solar thin film is increased, and Se in the original simple substance Se thin film is not found or the thickness of the simple substance Se thin film is reduced.
Example 2
Post-treatment of the Cu-Zn-Sn-Se compound solar thin film:
preparing a Cu-Zn-Sn-Se film on a glass substrate by a magnetron sputtering technology, and preparing the Se film on the glass substrate by thermal evaporation;
after deposition, the Cu-Zn-Sn-Se film and the Se film are tightly attached, and are placed on a heating table to be heated for 40min at 450 ℃, wherein the Se content of the original sample deposited with the Cu-Zn-Sn-Se film is increased, and Se in the original simple substance Se film is not found or the thickness of the original simple substance Se film is reduced.
Example 3
Post-treatment of the CuInGaSe compound solar thin film:
preparing a Se film on a glass substrate by a CuInGaSe film through a thermal evaporation technology, and preparing the glass substrate by the Se film through thermal evaporation;
after deposition, the CuInGaSee film and the Se film are tightly attached, and are placed on a heating table to be heated for 40min at 400 ℃, wherein the Se content of a sample with the originally deposited CuInGaSe film is increased, and Se in the originally simple substance Se film is not seen or the thickness of the Se film is reduced.
It will be understood that the invention is not limited to the examples described above, but that modifications and variations will occur to those skilled in the art in light of the above teachings, and that all such modifications and variations are considered to be within the scope of the invention as defined by the appended claims.

Claims (5)

1. A method for processing a chalcogenide solar thin film is characterized by comprising the following steps:
providing a chalcogenide solar thin film;
providing a sulfur-series simple substance film, wherein the sulfur-series elements in the sulfur-series simple substance film are the same as the sulfur-series elements in the sulfur-series compound solar film;
superposing the chalcogenide simple substance film and the chalcogenide compound solar film to obtain a superposed film layer;
heating the superposed film layer in a vacuum or inert atmosphere to enable sulfur elements in the sulfur simple substance film to enter the sulfur compound solar film, and simultaneously applying pressure in a direction vertical to the superposed film layer;
wherein the chalcogenide solar film is one of an SbSe film and a CuZnSnSe film;
the sulfur-series simple substance film is one of a sulfur-series simple substance film, a selenium-series simple substance film and a tellurium-series simple substance film;
the temperature of the heating treatment is 400-450 ℃;
the time of the heating treatment is 15-120 min.
2. The method for processing the chalcogenide compound solar thin film according to claim 1, wherein the chalcogenide compound solar thin film is an SbSe thin film, and the chalcogenide simple substance thin film is a selenium simple substance thin film.
3. The method for processing the chalcogenide solar thin film according to claim 1, wherein the chalcogenide solar thin film is a CuZnSnSe thin film, and the chalcogenide elemental thin film is an elemental selenium thin film.
4. The method of claim 1, wherein the chalcogenide thin film is prepared by physical vapor deposition or chemical vapor deposition.
5. The method for processing the chalcogenide solar thin film according to claim 1, wherein the chalcogenide solar thin film is prepared by a physical vapor deposition method or a chemical vapor deposition method.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102906299A (en) * 2010-05-20 2013-01-30 陶氏环球技术有限责任公司 Chalcogenide-based materials and methods of making such materials under vacuum using post-chalcogenization techniques
CN103107243A (en) * 2013-02-03 2013-05-15 电子科技大学 Copper zinc tin sulfur thin film preparation method with doping process adopted
CN107406965A (en) * 2015-01-12 2017-11-28 纽升股份有限公司 High-speed sputtering deposition available for the precursor film of the alkali metal containing of manufacture chalcogenide semiconductor
CN107924959A (en) * 2015-08-05 2018-04-17 陶氏环球技术有限责任公司 Include the photovoltaic devices and relative manufacturing process of the photovoltaic light absorber containing chalkogenide
KR102015985B1 (en) * 2018-04-17 2019-08-29 한국과학기술연구원 Method for manufacturing CIGS thin film for solar cell

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5137796B2 (en) * 2008-11-26 2013-02-06 京セラ株式会社 Compound semiconductor thin film manufacturing method and thin film solar cell manufacturing method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102906299A (en) * 2010-05-20 2013-01-30 陶氏环球技术有限责任公司 Chalcogenide-based materials and methods of making such materials under vacuum using post-chalcogenization techniques
CN103107243A (en) * 2013-02-03 2013-05-15 电子科技大学 Copper zinc tin sulfur thin film preparation method with doping process adopted
CN107406965A (en) * 2015-01-12 2017-11-28 纽升股份有限公司 High-speed sputtering deposition available for the precursor film of the alkali metal containing of manufacture chalcogenide semiconductor
CN107924959A (en) * 2015-08-05 2018-04-17 陶氏环球技术有限责任公司 Include the photovoltaic devices and relative manufacturing process of the photovoltaic light absorber containing chalkogenide
KR102015985B1 (en) * 2018-04-17 2019-08-29 한국과학기술연구원 Method for manufacturing CIGS thin film for solar cell

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