CN114068737B - Preparation method of p-type semiconductor layer for inorganic thin film solar cell - Google Patents
Preparation method of p-type semiconductor layer for inorganic thin film solar cell Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 98
- 239000004065 semiconductor Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 66
- 238000004544 sputter deposition Methods 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims description 72
- 239000002184 metal Substances 0.000 claims description 71
- 238000010438 heat treatment Methods 0.000 claims description 48
- 229910045601 alloy Inorganic materials 0.000 claims description 46
- 239000000956 alloy Substances 0.000 claims description 46
- 229910052711 selenium Inorganic materials 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 27
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 16
- 229910052718 tin Inorganic materials 0.000 claims description 16
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 13
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 12
- 229910017518 Cu Zn Inorganic materials 0.000 claims description 11
- 229910017752 Cu-Zn Inorganic materials 0.000 claims description 11
- 229910017943 Cu—Zn Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910017755 Cu-Sn Inorganic materials 0.000 claims description 10
- 229910017927 Cu—Sn Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 7
- 229910017482 Cu 6 Sn 5 Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 230000005764 inhibitory process Effects 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000001704 evaporation Methods 0.000 abstract description 5
- 238000004904 shortening Methods 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 57
- 239000011669 selenium Substances 0.000 description 32
- 239000011135 tin Substances 0.000 description 25
- 238000007740 vapor deposition Methods 0.000 description 21
- 239000011701 zinc Substances 0.000 description 20
- 239000002243 precursor Substances 0.000 description 18
- 239000010408 film Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000006798 recombination Effects 0.000 description 9
- 238000005215 recombination Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910016347 CuSn Inorganic materials 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000001017 electron-beam sputter deposition Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000012691 Cu precursor Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- -1 cu—zn Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 230000003746 surface roughness Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BUVBYQUZAIPDHT-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S.NC(N)=S BUVBYQUZAIPDHT-UHFFFAOYSA-N 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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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
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
-
- 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
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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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
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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
- H01L31/1864—Annealing
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/543—Solar cells from Group II-VI materials
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- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Sustainable Energy (AREA)
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- Physical Vapour Deposition (AREA)
Abstract
The present invention relates to an inorganic thin film solar cell using a vacuum sputtering evaporation method and a method for manufacturing the same, and more particularly, to a method for manufacturing a p-type compound semiconductor layer for an inorganic thin film solar cell capable of improving the quality of a p-type compound semiconductor layer known as an absorption layer and shortening a process time, and an inorganic thin film solar cell including the p-type compound semiconductor layer manufactured by the above method.
Description
Technical Field
The present invention relates to an inorganic thin film solar cell using a vacuum sputtering evaporation method and a method for manufacturing the same, and more particularly, to a method for manufacturing a p-type compound semiconductor layer for an inorganic thin film solar cell capable of improving the quality of a p-type compound semiconductor layer known as an absorption layer and shortening a process time, and an inorganic solar cell including the p-type compound semiconductor layer manufactured by the above method.
Background
Solar cells are classified into various types according to the substance used as a light absorbing layer, and silicon solar cells using silicon are currently very widely used. However, recently, the price has been increased due to insufficient supply of silicon, and thus, attention to thin film solar cells has been increased.
Thin film solar cells are manufactured with a thin thickness, consume little material, and are lightweight, thus having a wide range of applications. An inorganic thin film solar cell is formed of a multi-layered structure in which an active layer known as an absorption layer (absorber layer) made of a p-type compound thin film type semiconductor functions as a central for generating charges (carriers) through photo-generation, and when sufficient photons are absorbed, a large amount of charges can be generated, thereby improving the conversion efficiency of the solar cell element.
As described above, in the conventional method for producing a light absorbing layer of a solar cell based on CZT (CuZnSn), which is one type of compound semiconductor, a metal precursor formed of Cu, zn, sn is first evaporated, and then heat-treated with sulfur (S) or selenium (Se) element. The light absorbing layer as described above may be a CZTS (CuZnSnS), CZTSe (CuZnSnSe), CZTSS (CuZnSnSSe) solar cell light absorbing layer.
In this case, in the process of vapor deposition of a metal precursor composed of Cu, zn, and Sn, unit films of Cu, zn, and Sn are typically vapor deposited in this order using a Sputtering (Sputtering) method. However, when vapor deposition is performed in this order, since Sn is crystallized to form a very rough surface of the metal precursor film, the roughness is not improved even after heat treatment with sulfur or selenium, and there is a problem that the solar cell efficiency is limited due to the uneven composition ratio at a local position and the decrease in series resistance in the process after the absorption layer.
In order to overcome the above problems, there is a method of vapor deposition of a precursor using a CuS, znS, snS target (target), but the method has the following problems: the vapor deposition rate was lowered, contamination and corrosion of the vapor deposition machine caused by sulfur or selenium, and the surface roughness improvement characteristics were relatively low.
That is, this is because the absorption layer is prepared by selectively synthesizing substances of copper, zinc, tin, gallium, indium, sulfur, and selenium, and the quality of the thin film may vary depending on the process of synthesis. In particular, due to the heat treatment property at high temperature, the thin film cannot be densely synthesized, voids are generated, or a complete phase cannot be formed, and as a result, the properties of the solar cell are adversely affected.
Therefore, there is a need to develop a novel technique capable of improving the electrical characteristics of a solar cell by improving the quality of a synthesized thin film through an improvement process.
Prior art literature
Patent literature
Patent document 0001: korean patent laid-open No. 10-2011-0001814
Disclosure of Invention
The present inventors have developed a technique for improving the film quality of an absorber layer of an inorganic thin film solar cell to improve the electrical characteristics of the solar cell, as a result of a large number of studies, and completed the present invention.
It is therefore an object of the present invention to provide a method for producing a p-type compound semiconductor layer for an inorganic thin film solar cell and a p-type compound semiconductor layer for an inorganic thin film solar cell produced by the method, as follows: a thin film having high crystallinity and no voids can be formed by co-sputtering and a preheating treatment.
Another object of the present invention is to provide an inorganic thin film solar cell as follows: including a p-type compound semiconductor for an inorganic thin film solar cell, which improves film quality, whereby electrical characteristics can be improved.
The object of the present invention is not limited to the above-mentioned object, but the object of the present invention includes the object of the present invention which can be recognized by those skilled in the art to which the present invention pertains by the description of the detailed description of the invention described later, although not explicitly described.
In order to achieve the object of the present invention as described above, the present invention provides a method for producing a p-type compound semiconductor layer for an inorganic thin film solar cell, comprising: a first metal mixed layer forming step of forming a first metal mixed layer of mixed Cu-Zn or Cu-Sn by vapor-depositing Zn and Cu or Sn and Cu on a substrate by co-sputtering; a second metal mixed layer forming step of forming a second metal mixed layer of mixed Cu-Sn or Cu-Zn by vapor-depositing Sn and Cu or Zn and Cu on the first metal mixed layer by co-sputtering; a step of forming a first alloy layer and a second alloy layer by performing a first heat treatment on the first metal mixed layer and the second metal mixed layer, thereby forming a first alloy layer composed of a cu—zn alloy or a cu—sn alloy on the first metal mixed layer, and forming a second alloy layer composed of a cu—sn alloy or a cu—zn alloy on the second metal mixed layer; and a CZTSSe thin film forming step including a step of performing a second heat treatment on the first alloy layer and the second alloy layer together with the S and Se powders.
In a preferred embodiment, the step of forming the first metal mixed layer or the second metal mixed layer is performed by applying a direct current power of 60W to 80W to Zn, applying a direct current power of 20W to 40W to Cu, and simultaneously performing vapor deposition under a process pressure of 7 milliTorr (mTorr) to 9 milliTorr for 800 seconds to 1000 seconds.
In a preferred embodiment, the step of forming the first metal mixed layer or the second metal mixed layer is performed by applying a direct current power of 60 to 80W to Sn, applying a direct current power of 35 to 55W to Cu, and vapor-depositing for 1400 to 1600 seconds at the same time under a process pressure of 7 to 9 mtorr.
In a preferred embodiment, the forming steps of the first alloy layer and the second alloy layer include: in argon (Ar) or nitrogen (N) 2 ) A step of performing a first heat treatment for 80 to 100 minutes on the first metal mixed layer and the second metal mixed layer under an atmospheric pressure atmosphere and a temperature condition of 200 to 400 ℃; and a step of performing natural cooling for 150 minutes to 210 minutes.
In a preferred embodiment, the CZTSSe thin film forming step includes: a second heat treatment step of performing a second heat treatment of the first alloy layer and the second alloy layer together with S and Se powder for 7 minutes to 8 minutes under an argon atmosphere at a pressure of 450 Torr to 550 Torr and a temperature of 500 ℃ to 600 ℃; and naturally cooling to normal temperature.
In a preferred embodiment, the second heat treatment is performed by filling the first and second alloy layers and the S and Se powders into a graphite box.
In a preferred embodiment, the above S and Se powders are contained in a weight ratio of 1:90 to 1:120.
In a preferred embodiment, the Cu-Zn alloy contains Cu 6 Zn 8 The Cu-Sn alloy contains Cu 3 Sn and Cu 6 Sn 5 。
In a preferred embodiment, the substrate is a transparent substrate having a lower electrode layer formed thereon, and the first metal mixed layer is formed on the lower electrode layer.
In a preferred embodiment, the CZTSSe thin film inhibition comprises SnS (e) 2 、ZnS(e)、Cu 2 S(e)、Cu 2 SnS(e) 3 Is composed of Cu 2 ZnSn(S，Se) 4 The composition is formed.
Also, the present invention provides a p-type compound semiconductor layer for an inorganic thin film solar cell comprising the CZTSSe thin film prepared by any one of the above-mentioned preparation methods.
Also, the present invention provides an inorganic thin film solar cell comprising: a transparent substrate; a lower electrode layer formed on the transparent substrate in a stacked manner; a p-type compound semiconductor layer formed on the lower electrode layer; an n-type compound semiconductor layer formed on the p-type compound semiconductor layer; a transparent electrode layer formed on the n-type compound semiconductor layer; and an upper electrode layer formed on the transparent electrode layer.
In a preferred embodiment, the n-type compound thin film semiconductor layer comprises a material selected from the group consisting of CdS, znS, zn (O, S), snO 2 、In 2 S 3 In 2 O 3 At least one of the group consisting of.
In a preferred embodiment, the transparent electrode layer contains at least one selected from the group consisting of ZnO and Al-ZnO, gaZnO, mgZnO, inSnO.
In a preferred embodiment, the upper electrode includes at least one selected from the group consisting of Mo, pt, ni, au, ag and Al.
The above-described method for producing a p-type compound semiconductor layer for an inorganic thin film solar cell of the present invention can form a thin film having no voids and high crystallinity by co-sputtering and a pre-heating treatment.
Also, the inorganic thin film solar cell of the present invention includes a p-type compound semiconductor layer for an inorganic thin film solar cell, the film quality of which is improved, whereby the electrical characteristics can be improved.
The technical effects of the present invention are not limited to the above-mentioned ranges, but include the effects of the invention that can be recognized by those skilled in the art to which the present invention pertains by the following description of the detailed description of the invention, even if not explicitly mentioned.
Drawings
Fig. 1 is a schematic view showing a process of preparing a p-type compound semiconductor layer for an inorganic thin film solar cell according to an embodiment of the present invention.
Fig. 2 is a schematic view illustrating an inorganic thin film solar cell including a p-type compound semiconductor layer prepared by the method shown in fig. 1 according to still another embodiment of the present invention.
Fig. 3 is a schematic flow chart showing a process for manufacturing the inorganic thin film solar cell shown in fig. 2 according to another embodiment of the present invention.
Fig. 4 is a scanning electron microscope cross-sectional photograph of a thin film obtained by vapor deposition of a metal precursor by co-sputtering and single sputtering.
Fig. 5 is a scanning electron microscope cross-sectional photograph of a thin film after the preheating treatment after the vapor deposition of a metal precursor.
Fig. 6 is a scanning electron microscope cross-sectional photograph of a light absorbing layer film obtained by heat-treating a film subjected to a preheating treatment together with powders of mixed S and Se at a high temperature.
Fig. 7 is a graph showing the results of electrical characteristics of a solar cell element to which an absorber layer synthesized by a conventional process and a preheating process is applied.
Fig. 8a to 8d are graphs showing the results of electrical characteristics of solar cell elements to which the CZTSSe thin film prepared by co-sputtering, single sputtering is applied.
Detailed Description
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular reference includes the plural reference unless the context clearly indicates otherwise. In this application, it should be understood that the terms "comprises" and "comprising," etc. are used to specify the presence of stated features, integers, steps, operations, elements, components, or groups thereof, but do not preclude the presence or addition of one or more other features or integers, steps, operations, elements, components, or groups thereof.
The terms "first", "second", etc. may be used to describe various structural elements, but the structural elements are not limited to the above terms. The above terms are used only to distinguish one structural element from other structural elements. For example, a first structural element may be named a second structural element, and similarly, a second structural element may also be named a first structural element, without departing from the scope of the claimed invention.
Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms having the same definition as in a dictionary generally used should be construed to have the same meaning as that of the related art text, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
In the explanation of the structural elements, the error range should be interpreted as being included even if no additional explicit description is made. In particular, where the terms "about", "substantially" and the like are used to refer to the degree, they may be interpreted as being used in the sense of or approaching the value at which the meaning is presented as an inherent preparation and material acceptable error.
In the case of describing the time relationship, for example, in the case of describing the time sequence relationship by "— back", "in-middle", "after", "-front", etc., if terms such as "immediate" or "direct" are not used, the case of discontinuity is also included.
The technical structure of the present invention will be described in detail below with reference to the drawings and preferred embodiments.
However, the present invention is not limited to the examples described herein, and in the different embodiments, the same reference numerals denote the same components.
The technical feature of the present invention is that the method for preparing a p-type compound semiconductor layer for an inorganic thin film solar cell is as follows, and an inorganic thin film solar cell comprising the p-type compound semiconductor layer prepared by the above method: in the process of forming the CZTSSe thin film, zn and Cu or Sn and Cu are sequentially evaporated by co-sputtering to form a metal mixed layer, respectively, and then an alloy layer is formed by a preheating treatment, i.e., a first heat treatment, and then a CZTSSe thin film is formed by a process of performing a second heat treatment together with sulfur and selenium, in which a useful two-component system compound is formed, thereby suppressing such as SnS (e) 2 、ZnS(e)、Cu 2 S(e)、Cu 2 SnS(e) 3 The secondary phase of (a) is formed, thereby forming a high-quality CZTSSe thin film having no voids and high crystallinity.
Thus, the method for preparing the p-type compound semiconductor layer for the inorganic thin film solar cell of the present invention comprises: a first metal mixed layer forming step of forming a first metal mixed layer of mixed Cu-Zn or Cu-Sn by vapor-depositing Zn and Cu or Sn and Cu on a substrate by co-sputtering; a second metal mixed layer forming step of forming a second metal mixed layer of mixed Cu-Sn or Cu-Zn by vapor-depositing Sn and Cu or Zn and Cu on the first metal mixed layer by co-sputtering; a first alloy layer and a second alloy layer forming step of performing a first heat treatment on the first metal mixed layer and the second metal mixed layer, thereby forming a first alloy layer composed of a cu—zn alloy or a cu—sn alloy on the first metal mixed layer, and forming a second alloy layer composed of a cu—sn alloy or a cu—zn alloy on the second metal mixed layer; and a CZTSSe thin film forming step including a step of performing a second heat treatment on the first alloy layer and the second alloy layer together with the S and Se powders.
The substrate may be a transparent substrate having a lower electrode layer formed thereon, and the first metal mixture layer may be formed on the lower electrode layer.
The forming step of the first metal mixed layer or the second metal mixed layer may be performed by applying a direct current power of 60W to 80W to Zn, applying a direct current power of 20W to 40W to Cu, simultaneously vapor-depositing for 800 seconds to 1000 seconds under a process pressure of 7 mtorr to 9 mtorr, and applying a direct current power of 60W to 80W to Sn, applying a direct current power of 35W to 55W to Cu, simultaneously vapor-depositing for 1400 seconds to 1600 seconds under a process pressure of 7 mtorr to 9 mtorr. Wherein the sputtering process conditions are experimentally determined by repeated experiments by forming a two-component system compound of a copper-zinc alloy, in particular, cu, by a first heat treatment after co-sputtering copper and zinc or copper and tin, depending on the respective metal elements 6 Zn 8 And, forming a two-component system compound of a copper-tin alloy, in particular, forming Cu 3 Sn and Cu 6 Sn 5 。
The forming step of the first alloy layer and the second alloy layer comprises the following steps: a step of performing a first heat treatment for 80 to 100 minutes on the first metal mixed layer and the second metal mixed layer under an atmosphere of argon or nitrogen and a temperature of 200 to 400 ℃; and a step of performing natural cooling for 150 minutes to 210 minutes. As described above, the conditions for the first heat treatment are the optimal conditions for forming the desired two-component system compound in the copper-zinc alloy and copper-tin alloy, which are experimentally determined through a plurality of repeated experiments.
The CZTSSe thin film forming step includes: a second heat treatment step of carrying out the first and second alloy layers and the S and Se powder together for 7 to 8 minutes under the argon atmosphere, the pressure of 450 to 550 Torr and the temperature of 500 to 600 ℃; and naturally cooling to normal temperature. The second heat treatment may be performed by filling the first and second alloy layers and the S and Se powders into a graphite box, and in particular, the S and Se powders may be contained in a weight ratio of 1:90 to 1:120.
That is, this is because in the present invention, the first alloy layer and the second alloy layer react with S, se to form a CZTSSe absorber film as follows.
4/3Cu 3 Sn+Se 2 (g)→2Cu 2 Se+4/3Sn (1)
2/3Cu 6 Sn 5 +Se 2 (g)→2Cu 2 Se+10/3Sn
Cu 5 Zn 8 +Se→2Cu 2 Se+2ZnSe
4Cu+S 2 (g)→2Cu 2 S
2Sn+S 2 (g)→2Se
SnS+Se→SnSe 2 +SnSe
2SnSe+Se 2 (g)→2SnSe 2
2Cu 2 S(e)+2SnS(e) 2 +S(e) 2 →2Cu 2 SnS(e) 3 (2)
Cu 2 SnS(e) 3 +ZnS(e)→Cu 2 ZnSn(S，Se) 4 (3)
Cu 2 S+SnSe 2 +ZnSe→Cu 2 ZnSn(S，Se) 4
As is clear from the above synthetic chemical formula, the CZTSSe thin film is finally synthesized by the reaction formula (3), and Cu needs to be formed well to obtain a high-quality CZTSSe thin film 2 SnS(e) 3 、Cu 2 S、SnSe 2 ZnSe compounds, if Cu is to be formed well 2 SnS(e) 3 、Cu 2 S、SnSe 2 ZnSe compounds, not only form well as Cu 5 Zn 8 、Cu 3 Sn、Cu 6 Sn 5 Two of (2)The system compound is also a component, and the content ratio of sulfur to selenium added is also important.
Therefore, in the method for producing a p-type compound semiconductor layer for an inorganic thin film solar cell of the present invention as described above, not only the common sputtering conditions, the first heat treatment conditions, and the second heat treatment conditions are closely related to each other, but also all of these conditions need to be precisely controlled to obtain a p-type compound semiconductor for an inorganic thin film solar cell as follows: suppression of inclusion of SnS (e) 2 、ZnS(e)、Cu 2 S(e)、Cu 2 SnS(e) 3 Comprises a second phase of Cu 2 ZnSn(S，Se) 4 High quality CZTSSe thin film is composed.
Next, the inorganic thin film solar cell of the present invention may include: a transparent substrate; a lower electrode layer formed on the transparent substrate in a stacked manner; a p-type compound semiconductor layer formed on the lower electrode layer; an n-type compound semiconductor layer formed on the p-type compound semiconductor layer; a transparent electrode layer formed on the n-type compound semiconductor layer; and an upper electrode layer formed on the transparent electrode layer.
The transparent substrate may be an insulating substrate, and the lower electrode layer may be a metal electrode. The lower electrode layer may be formed on the front surface of the insulating substrate by thermal evaporation, electron beam evaporation, sputtering, or the like.
The n-type compound thin film semiconductor layer may comprise a material selected from CdS, znS, zn (O, S), snO 2 、In 2 S 3 In 2 O 3 The transparent electrode layer may include at least one selected from the group consisting of ZnO, al-ZnO, gaZnO, mgZnO, inSnO, and the upper electrode may include at least one selected from the group consisting of Mo, pt, ni, au, ag and Al. The upper electrode layer may be a metal electrode, and may be formed in a partial region of the upper portion of the transparent electrode by thermal evaporation, electron beam evaporation, sputtering, or the like.
Examples
An inorganic thin film solar cell having the structure shown in fig. 2, which includes a p-type compound semiconductor layer for an inorganic thin film solar cell formed of the high quality CZTSSe thin film of the schematic diagram shown in fig. 1, was prepared according to the flowchart shown in fig. 3.
1. Substrate providing step S1
First, a substrate to be vapor-deposited with a metal mixed precursor by sputtering is cleaned. A glass substrate coated with a Mo lower electrode layer was used as a substrate. When the substrate was cleaned, the Mo substrate was immersed in a beaker containing isopropyl alcohol, then placed in an ultrasonic cleaner for 10 minutes, and then transferred into a beaker containing distilled water to impregnate the Mo substrate, followed by cleaning for 10 minutes. Thereafter, drying was performed with nitrogen.
2. Step S2 of vapor deposition of the first metal mixed layer
After cleaning, zn and Cu were simultaneously vapor-deposited on the Mo-coated rear electrode glass substrate by a co-sputtering method under a process pressure of 8 mtorr and a direct current power supply of 70W and 30W, respectively, for 900 seconds to form a first metal mixed layer of mixed cu—zn metal.
3. Second metal mixed layer evaporation step S3
Then, sn and Cu were simultaneously vapor-deposited under a process pressure of 8 mtorr for 1500 seconds from 70W and 45W dc power supplies, respectively, to form a second metal mixed layer of mixed cu—sn metal.
4. A first alloy layer and a second alloy layer forming step S4
After vapor deposition of the first metal mixed layer and the second metal mixed layer as metal mixed precursors, in order to form a two-component system compound of a desired composition while forming a first alloy layer composed of a cu—zn alloy and a second alloy layer composed of a cu—sn alloy, respectively, the following first heat treatment was performed as a preheating treatment. In the first heat treatment, the heat treatment was carried out at 300℃for 90 minutes in a furnace in which an atmospheric pressure atmosphere of argon or nitrogen was formed. After that, natural cooling was performed for 3 hours.
5.p Compound semiconductor layer Forming step S5
The substrate on which the first alloy layer and the second alloy layer after the first heat treatment were formed was put into a graphite box mixed with S and Se powders at a weight ratio of 1:100 for heat treatment. In the heat treatment step, the initial pressure in the furnace was set to 500 torr in an argon atmosphere, and heat treatment was performed at 520 ℃ for 7 minutes and 30 seconds. And naturally cooling to normal temperature after heating.
N-type compound semiconductor layer and transparent electrode layer formation step S6
After removing the phase shift of Cu by immersing the CZTSSe thin film prepared by the second heat treatment in KCN solution for 2 minutes, the CdS buffer layer was evaporated by chemical vapor deposition as an n-type compound semiconductor layer. In the chemical vapor deposition step, 0.0031M CdSO 4 After 19M ammonia and 0.2M thiourea (thiourea) were mixed with distilled water, the film was immersed therein, and vapor deposition was performed at a predetermined temperature and a rotation speed of 500rpm with stirring for 14 minutes and 30 seconds. The temperature may be 60℃to 90 ℃. Then, the i-ZnO and Al doped ZnO (AZO) layers were evaporated into window layers, which were transparent electrode layers, by sputtering with an AC power source at room temperature and 270 ℃. In the window layer vapor deposition process, the temperature may be from room temperature to 350 ℃, the ac power source may be from 50W to 90W, and the process pressure may be from 1 mtorr to 10 mtorr.
7. Upper electrode layer formation step S7
After aluminum to be used as the upper electrode was evaporated on the surface, a CZTSSe thin film solar cell having a glass/Mo/CZTSSe/i-ZnO/AZO/Al structure was completed. Wherein the thickness of the aluminum layer may be 600nm to 2000nm.
Comparative example
A comparative example inorganic thin film solar cell was prepared in the same manner as in example except that steps S2 to S4 in example were not performed and the thin film obtained by a conventional single sputtering method was used.
Experimental example 1
A thin film obtained after evaporation of a metal precursor for forming a p-type compound semiconductor layer by co-sputtering in the same manner as in the example (performed to step S3) and a thin film obtained by evaporation by single sputtering were observed using a field emission scanning electron microscope (FE-SEM), and a sectional photograph thereof is shown in fig. 4.
As shown in fig. 4, it was confirmed that the thin film deposited by the co-sputtering method was relatively dense in deposition. In the case of vapor deposition by a single sputtering method, cu, zn, and Sn are vapor deposited separately, and thus a layer such as Cu/Zn/Sn is formed to vapor deposit a thin film. In contrast, in the case of vapor deposition by the co-sputtering method, cu and Sn or Cu and Zn are simultaneously vapor deposited, and thus a thin film can be vapor deposited in a form of cu—sn or cu—zn mixed in advance at the same time of vapor deposition. If the thin films are deposited in a mixed state as in the first metal mixed layer and the second metal mixed layer of the embodiment, the energy required for forming cu—sn and cu—sn-based alloys, compounds, or for forming CZTSSe light absorbing layers is reduced, and thus it is expected to obtain a thin film having a higher density of thin films deposited by stacking Cu/Zn/Sn, for example.
Experimental example 2
A thin film obtained by performing the first heat treatment after vapor deposition of the metal precursor for forming the p-type compound semiconductor layer by co-sputtering in the same manner as in the example (step S4 was performed) and a thin film obtained by performing the first heat treatment after vapor deposition by a single sputtering were observed using a field emission scanning electron microscope, and a cross-sectional photograph thereof is shown in fig. 5.
The reason why the first heat treatment is performed after the metal precursor is evaporated is that Cu, zn, sn precursor evaporated by sputtering is formed as Cu by the heat treatment process 6 Sn 5 、CuSn、Cu 6 Zn 8 Two-component system compounds of (2). As shown in fig. 5, it was confirmed from a sectional view of a field emission scanning electron microscope that a relatively dense and uniform thin film was formed in the thin film deposited by co-sputtering. In the case of vapor deposition of the precursor by co-sputtering, compounds in the form of Cu-Sn and Cu-Zn can be formed before the preheating treatment is performed, and thus, when the preheating treatment is performed, cu, for example, is easily formed 6 Sn 5 、CuSn、Cu 6 Zn 8 Two-component system compounds of (2). In contrast, in the case of vapor deposition by a single sputtering method, compounds in the form of Cu-Sn or Cu-Zn cannot be formed by forming a layer in a structure such as Cu/Zn/Sn before the preheating treatment, and therefore even if the preheating treatment is performedIs difficult to form as Cu 6 Sn 5 、CuSn、Cu 6 Zn 8 Two-component system compounds of (2). Therefore, if co-sputtering is performed, formation of a two-component system compound is promoted by the preheating treatment, so that a high-quality thin film can be obtained.
Experimental example 3
A film obtained after vapor deposition of a metal precursor for forming a p-type compound semiconductor layer by co-sputtering and performing the first heat treatment together with a powder mixed with S and Se and a film obtained after performing the first heat treatment and the second heat treatment by single sputtering were observed using a field emission scanning electron microscope in the same manner as in the example (performed to step S5), and a photograph of the result thereof is shown in fig. 6.
As shown in fig. 6, in the case of a thin film prepared by vapor deposition by co-sputtering in the same manner as in the example, the size of the upper crystal grains shown is relatively large, while in the lower crystal grains, small particles and voids are reduced. When the precursors are evaporated by single sputtering, the precursors such as Cu, zn, sn are evaporated in an unmixed form before the first heat treatment. In contrast, when the precursors are evaporated by co-sputtering, the Zn, sn, cu precursors form a layer of mixed Cu-Zn, cu-Sn. Thus, when the first heat treatment is performed at a temperature of 200 to 400 ℃, a two-component system compound such as cu—zn, cu—sn is formed better than a thin film evaporated by a single sputtering method. As a result, it was found that when S and Se were added to perform heat treatment at a temperature of 500 to 600 ℃, not only dense shapes and large crystal grains were formed, but also void formation was prevented.
Experimental example 4
The electrical characteristics of the inorganic thin film solar cell element obtained in examples were tested in the following manner, and the results thereof are shown in fig. 7. An electrical characteristic of the element was detected using a solar simulator (solar simulator), and was performed by irradiating artificial light of similar intensity to solar light to a solar cell, detecting a characteristic of the solar cell with respect to the incident light (100 mW/cm 2 ) Conversion ratio of the power output of (a). More specifically, the process is carried out,the rear electrode portion connected to the light absorbing layer of the p-type semiconductor which is the solar cell element is brought into contact with the positive electrode (+) and the front electrode portion connected to the transparent electrode which is the n-type semiconductor is brought into contact with the negative electrode (-) to perform detection. In order to eliminate the influence of temperature on the element as much as possible, the temperature was kept at normal temperature (25 ℃). In the case of detection by the above device, the no-load voltage (V oc ) Density of short-circuit current (J) sc ) A Fill Factor (FF), and a photoelectric conversion efficiency (Power Conversion Efficiency) of the solar cell.
As shown in fig. 7, it was confirmed that no-load voltage (V oc Open Circuit Voltage), short-circuit current density (J) sc Short Circuit Current Density), the Fill Factor (FF) value is all increased.
As can be confirmed from fig. 7, the detection result of the solar cell manufactured by performing the preheating treatment is very different from the detection result without performing the preheating treatment. In the normal case where the preheating treatment is not performed, the second heat treatment is directly performed at a temperature of 500 to 600 ℃ after adding the powder mixed with S and Se to the metal precursor vapor-deposited by co-sputtering. First, it was confirmed that the increase in the no-load voltage in fig. 7 achieved a maximum increase in the no-load voltage of 20 mV. As mentioned many times in the papers and documents published before, the no-load voltage is a very large influencing factor to which the light absorbing layer of the solar cell is subjected, and the result of the reduction of the no-load voltage is shown when many Secondary phases (Secondary phases) and voids (defects), small growth of crystals, and the like exist in the light absorbing layer. When the short-circuit current density increases, the separation of charges becomes smoother, and the more moves toward the solar cell anode in such a manner that there is no recombination. Recombination tends to be inversely proportional to the size of the grains. The fill factor is a factor greatly affected by loss due to recombination (recombination) and resistance, and is improved by showing a decrease in series resistance (series R) and an increase in Shunt resistance (Shunt R). Therefore, it was confirmed that the increase in the no-load voltage, the short-circuit current density, the shunt resistance, and the decrease in the series resistance were all effects caused by improving the film quality of the light absorbing layer by the preheating treatment. Finally, when the preheating treatment was performed, it was confirmed that the photoelectric conversion efficiency was improved due to the rise of the no-load voltage, the short-circuit current density, and the fill factor.
Experimental example 5
The electrical characteristics of the inorganic thin film solar cell element obtained in the example (co-sputtering) and the comparative example inorganic thin film solar cell element obtained in the comparative example (single sputtering) were tested in the following manner, and the results thereof are shown in fig. 8a to 8 d. The detection was performed by a solar simulator in the same manner and under the same conditions as in experimental example 4.
As shown in fig. 8a to 8d, it is known that in the inorganic thin film solar cell element prepared by the co-sputtering method, the no-load voltage, the short circuit current density, and the fill factor value all increase.
The no-load voltage is the maximum voltage that can be obtained from the solar cell, and is a value when the current is 0. In CZTSSe thin film solar cells, the no-load voltage value is due to SnS (e) 2 、ZnS(e)、Cu 2 S(e)、Cu 2 SnS(e) 3 Is different from the formation of the secondary phase of (c). The less secondary phases are formed, the greater the value of the no-load voltage. In the case where co-sputtering and first heat treatment are applied as in the example, a two-component system compound can be well formed, whereby a high-quality CZTSSe thin film can be synthesized. This can be attributed to the inhibition of the formation of the secondary phase during the synthesis of CZTSSe thin films.
The short-circuit current density is the density of the current flowing through the solar cell when the voltage applied to the solar cell is 0. The value of the short-circuit current density differs depending on whether or not there is recombination of charges generated by solar energy. The less recombination of the generated charges, the more the short-circuit current density value increases. It was confirmed that the CZTSSe thin film of the example in which co-sputtering was performed had a relatively large crystal. This can be said to be a reduction in grain boundaries. Grain boundaries are sites where charges generated by sunlight recombine, and when recombination occurs, the charges cannot move smoothly. This becomes a cause of reducing the conversion efficiency of the solar cell. Therefore, when vapor deposition is performed by the same co-sputtering method, dense and large crystal grains are formed, grain boundaries are reduced, recombination of charges is reduced, and conversion efficiency of the solar cell can be improved.
The fill factor is a factor determining the maximum output power of the solar cell, and is expressed as follows:
FF＝I mp *V mp /I sc *V oc
the less photogenerated charge is lost due to recombination and resistance, the more the fill factor value increases. Therefore, when the preheating treatment and the co-sputtering are applied, the filling factor value is improved by suppressing the formation of the secondary phase, forming a CZTSSe absorber film of large crystal grains, suppressing the formation of voids inside the absorber.
From the above experimental results, it was confirmed that when the p-type compound semiconductor layer was prepared, co-sputtering and the first heat treatment were performed in the same manner as in the present invention, the no-load voltage, the short-circuit current density, and the fill factor value could be increased, and the photoelectric conversion efficiency could be improved.
In view of the foregoing, it will be apparent to those skilled in the art that the present invention is not limited to the preferred embodiments described above, but is capable of numerous modifications and variations without departing from the spirit of the invention.
Claims (10)
1. A method for preparing a p-type compound semiconductor layer for an inorganic thin film solar cell is characterized in that,
comprising the following steps:
a first metal mixed layer forming step of forming a first metal mixed layer of mixed Cu-Zn or Cu-Sn by vapor-depositing Zn and Cu or Sn and Cu on a substrate by co-sputtering;
a second metal mixed layer forming step of forming a second metal mixed layer of mixed Cu-Sn or Cu-Zn by vapor-depositing Sn and Cu or Zn and Cu on the first metal mixed layer by co-sputtering;
a first alloy layer and a second alloy layer forming step of performing a first heat treatment on the first metal mixed layer and the second metal mixed layer, thereby forming a first alloy layer composed of a cu—zn alloy or a cu—sn alloy on the first metal mixed layer, and forming a second alloy layer composed of a cu—sn alloy or a cu—zn alloy on the second metal mixed layer; and
a CZTSSe thin film forming step comprising a step of performing a second heat treatment on the first alloy layer and the second alloy layer together with S and Se powder,
the step of forming the first metal mixed layer or the second metal mixed layer is performed by applying a direct current power supply of 60W to 80W to Zn, applying a direct current power supply of 20W to 40W to Cu, vapor-depositing at the same time under a process pressure of 7 mTorr to 9 mTorr for 800 seconds to 1000 seconds,
the step of forming the first metal mixed layer or the second metal mixed layer is performed by applying a direct current power supply of 60W to 80W to Sn, applying a direct current power supply of 35W to 55W to Cu, vapor-depositing at the same time under a process pressure of 7 mTorr to 9 mTorr for 1400 seconds to 1600 seconds,
the forming step of the first alloy layer and the second alloy layer comprises the following steps:
a step of performing a first heat treatment for 80 to 100 minutes on the first metal mixed layer and the second metal mixed layer under an atmosphere of argon or nitrogen and a temperature of 200 to 400 ℃; and
a step of natural cooling for 150 minutes to 210 minutes,
the step of forming the CZTSSe thin film comprises the following steps:
a second heat treatment step of carrying out a second heat treatment for 7 minutes to 8 minutes on the first alloy layer and the second alloy layer together with S and Se powder under an argon atmosphere at a pressure of 450 to 550 Torr and a temperature of 500 to 600 ℃; and
naturally cooling to normal temperature,
the above S and Se powders are contained in a weight ratio of 1:90 to 1:120.
2. The method for producing a p-type compound semiconductor layer for an inorganic thin film solar cell according to claim 1, wherein the second heat treatment is performed by filling the first and second alloy layers and S and Se powders into a graphite box.
3. The method for producing a p-type compound semiconductor layer for an inorganic thin film solar cell according to claim 1, wherein said Cu-Zn alloy comprises Cu 6 Zn 8 The Cu-Sn alloy contains Cu 3 Sn and Cu 6 Sn 5 。
4. The method for producing a p-type compound semiconductor layer for an inorganic thin film solar cell according to claim 1, wherein the substrate is a transparent substrate having a lower electrode layer formed thereon, and the first metal mixed layer is formed on the lower electrode layer.
5. The method for producing a p-type compound semiconductor layer for an inorganic thin film solar cell according to claim 1, wherein said CZTSSe thin film inhibition comprises SnS (e) 2 、ZnS(e)、Cu 2 S(e)、Cu 2 SnS(e) 3 Is composed of Cu 2 ZnSn(S，Se) 4 The composition is formed.
6. A p-type compound semiconductor layer for an inorganic thin film solar cell, characterized by comprising a CZTSSe thin film prepared by the preparation method of any one of claims 1 to 5.
7. An inorganic thin film solar cell, comprising:
a transparent substrate;
a lower electrode layer formed on the transparent substrate in a stacked manner;
the p-type compound semiconductor layer of claim 6, formed on said lower electrode layer;
an n-type compound semiconductor layer formed on the p-type compound semiconductor layer;
a transparent electrode layer formed on the n-type compound semiconductor layer; and
and an upper electrode layer formed on the transparent electrode layer.
8. The inorganic thin film solar cell according to claim 7, wherein the n-type compound thin film semiconductor layer comprises a material selected from the group consisting of CdS, znS, zn (O, S) and SnO 2 、In 2 S 3 In 2 O 3 At least one of the group consisting of.
9. The inorganic thin film solar cell according to claim 7, wherein the transparent electrode layer contains at least one selected from the group consisting of ZnO and Al-ZnO, gaZnO, mgZnO, inSnO.
10. The inorganic thin film solar cell according to claim 7, wherein the upper electrode comprises at least one selected from the group consisting of Mo, pt, ni, au, ag and Al.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201125148A (en) * | 2010-01-12 | 2011-07-16 | Univ Nat Kaohsiung Marine | A simple manufacture process to obtain near stoichiometric CuxZn-SnSy(CZTS) thin films used for solar cells |
| KR20130053897A (en) * | 2011-11-16 | 2013-05-24 | 재단법인대구경북과학기술원 | Metallic precursor for a czt-based solar cell and manufacturing method thereof, photo absorption layer and solar cell comprising it |
| CN103403851A (en) * | 2011-03-10 | 2013-11-20 | 法国圣戈班玻璃厂 | Method for producing the pentanary compound semiconductor CZTSSe, and thin-film solar cell |
| FR2996060A1 (en) * | 2012-09-21 | 2014-03-28 | Saint Gobain Ct Recherches | Manufacturing a semiconductor solar absorbing material of e.g. copper indium gallium selenide type, in a photovoltaic cell, comprises mixing metal elements, dry grinding the mixture, and suspending the powder in an organic solvent |
| CN104247036A (en) * | 2012-04-27 | 2014-12-24 | 法国圣戈班玻璃厂 | Method for producing the pentanary compound semiconductor cztsse doped with sodium |
| KR20150037038A (en) * | 2013-09-30 | 2015-04-08 | 재단법인대구경북과학기술원 | Method for manufacturing porous CZTS-based thin film |
| CN105164815A (en) * | 2013-05-03 | 2015-12-16 | 法国圣戈班玻璃厂 | Back contact substrate for photovoltaic cell or module |
| KR20170095547A (en) * | 2016-02-15 | 2017-08-23 | 영남대학교 산학협력단 | CONTROLLING METHOD OF ZnSe PHASE OF CZTSe SOLAR CELL AND PRODUCING METHOD OF CZTSe SOLAR CELL |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101091495B1 (en) | 2009-06-30 | 2011-12-07 | 엘지이노텍 주식회사 | Solar cell and method of fabricating the same |
| US8426241B2 (en) * | 2010-09-09 | 2013-04-23 | International Business Machines Corporation | Structure and method of fabricating a CZTS photovoltaic device by electrodeposition |
| US8748216B2 (en) * | 2010-10-25 | 2014-06-10 | Imra America, Inc. | Non-vacuum method for fabrication of a photovoltaic absorber layer |
| JP5178904B1 (en) * | 2011-11-25 | 2013-04-10 | 昭和シェル石油株式会社 | CZTS thin film solar cell and method for manufacturing the same |
| US20200015712A1 (en) | 2018-07-13 | 2020-01-16 | Arthrokinetic Institute, Llc | Gathering and Analyzing Posture and Movement Data |
-
2020
- 2020-07-31 KR KR1020200095954A patent/KR102420408B1/en active IP Right Grant
-
2021
- 2021-01-07 CN CN202110018910.2A patent/CN114068737B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201125148A (en) * | 2010-01-12 | 2011-07-16 | Univ Nat Kaohsiung Marine | A simple manufacture process to obtain near stoichiometric CuxZn-SnSy(CZTS) thin films used for solar cells |
| CN103403851A (en) * | 2011-03-10 | 2013-11-20 | 法国圣戈班玻璃厂 | Method for producing the pentanary compound semiconductor CZTSSe, and thin-film solar cell |
| KR20130053897A (en) * | 2011-11-16 | 2013-05-24 | 재단법인대구경북과학기술원 | Metallic precursor for a czt-based solar cell and manufacturing method thereof, photo absorption layer and solar cell comprising it |
| CN104247036A (en) * | 2012-04-27 | 2014-12-24 | 法国圣戈班玻璃厂 | Method for producing the pentanary compound semiconductor cztsse doped with sodium |
| FR2996060A1 (en) * | 2012-09-21 | 2014-03-28 | Saint Gobain Ct Recherches | Manufacturing a semiconductor solar absorbing material of e.g. copper indium gallium selenide type, in a photovoltaic cell, comprises mixing metal elements, dry grinding the mixture, and suspending the powder in an organic solvent |
| CN105164815A (en) * | 2013-05-03 | 2015-12-16 | 法国圣戈班玻璃厂 | Back contact substrate for photovoltaic cell or module |
| KR20150037038A (en) * | 2013-09-30 | 2015-04-08 | 재단법인대구경북과학기술원 | Method for manufacturing porous CZTS-based thin film |
| KR20170095547A (en) * | 2016-02-15 | 2017-08-23 | 영남대학교 산학협력단 | CONTROLLING METHOD OF ZnSe PHASE OF CZTSe SOLAR CELL AND PRODUCING METHOD OF CZTSe SOLAR CELL |
Non-Patent Citations (2)
| Title |
|---|
| 电化学沉积法制备Cu_2ZnSnS_4薄膜电池;杨敏;蒋志;李志山;刘涛;刘思佳;郝瑞亭;王书荣;;材料科学与工程学报(第04期);全文 * |
| 磁控溅射合金靶制备铜锌锡硫（CZTS）薄膜太阳电池;陆熠磊;《中国优秀硕士论文电子期刊网 工程科技Ⅱ辑》(第01期);第20页第1段—第60页第2段及图3.1-3.25 * |
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| CN114068737A (en) | 2022-02-18 |
| KR20220015655A (en) | 2022-02-08 |
| KR102420408B1 (en) | 2022-07-13 |
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