WO2013022234A2 - Method of manufacturing czt(s,se)-based thin film for solar cell and czt(s,se)-based thin film manufactured thereby - Google Patents

Method of manufacturing czt(s,se)-based thin film for solar cell and czt(s,se)-based thin film manufactured thereby Download PDF

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WO2013022234A2
WO2013022234A2 PCT/KR2012/006198 KR2012006198W WO2013022234A2 WO 2013022234 A2 WO2013022234 A2 WO 2013022234A2 KR 2012006198 W KR2012006198 W KR 2012006198W WO 2013022234 A2 WO2013022234 A2 WO 2013022234A2
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thin film
czt
based thin
solar cell
selenization
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WO2013022234A3 (en
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Jihye Gwak
Jae-Ho Yun
Sejin Ahn
Kyung-Hoon Yoon
Sunghun JUNG
Kee-Shik Shin
SeoungKyu AHN
Ara Cho
Sang-Hyun Park
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Korea Institute Of Energy Research
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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
    • H01L31/0248—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
    • 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
    • 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
    • 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

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Abstract

This invention relates to a method of manufacturing a CZT(S,Se)-based thin film for a solar cell and a CZT(S,Se)-based thin film manufactured thereby. This method includes depositing Sn, Zn and Cu on a substrate in a predetermined order using evaporation method to form a CZT-based precursor thin film and subjecting the CZT-based precursor thin film to selenization or sulfurization, thereby suppressing Sn loss during the manufacturing process and increasing the energy efficiency of the solar cell using the same.

Description

METHOD OF MANUFACTURING CZT(S,SE)-BASED THIN FILM FOR SOLAR CELL AND CZT(S,SE)-BASED THIN FILM MANUFACTURED THEREBY
The present invention relates to a method of manufacturing a CZT(S,Se)-based thin film for a solar cell and a CZT(S,Se)-based thin film manufactured thereby, and, more particularly, to a method of manufacturing a CZT(S,Se)-based thin film using co-evaporation process which facilitates the control of a composition, so that Sn loss is suppressed during the manufacturing process thus increasing conversion efficiency.
Recently, the need to develop next-generation clean energy is gaining in importance in light of severe environmental contamination problems and the exhaustion of fossil energy. In particular, solar cells, which are used to directly convert solar energy into electric energy, are expected to become an energy source able to solve the energy problems of the future because they generate less pollution, utilize an unlimited resource and have a semi-permanent lifetime.
Solar cells are classified into a variety of types depending on the material used in a light absorption layer. Currently particularly useful is a Si solar cell. However, as the price of Si is skyrocketing attributable to a shortage of the Si supply these years, thin-film solar cells are receiving increasing attention. Thin-film solar cells are manufactured to be thin thus enabling smaller amounts of materials to be consumed, and also are lightweight and have a wide field of application. Thorough research is ongoing into using amorphous Si and CdTe or CIS type (CuInSe2, CuIn1-xGaxSe2, CuIn1-xGaxS2, etc.) as materials of such thin-film solar cells.
The CIS-based thin film corresponds to a Group I-III-IV compound semiconductor, and in particular a CIGS solar cell achieves the greatest conversion efficiency (about 20.3%) among thin-film solar cells which have been experimentally produced. Furthermore, this thin film may be manufactured to a thickness of 10 ㎛ or less and is stable even upon extended use, and is thereby expected to be used instead of Si to fabricate an inexpensive high-efficiency solar cell.
In particular, the CIS-based thin film is a direct transition type semiconductor and may thus be provided in the form of a thin film, and has a band gap that is comparatively adapted for light conversion, and the coefficient of light absorption thereof is the greatest amongst the materials used in solar cells.
However, the In used therein is a rare element which is comparatively low in reserves and the price thereof is increasing due to the demand for ITO materials employed in the display industry, making it difficult to carry out mass production. To overcome such problems and to develop inexpensive solar cells, the preparation of compound semiconductors such as Cu2ZnSnSe4 (CZTSe) and Cu2ZnSnS4 (CZTS) wherein the rare elements of In and Ga are replaced with the general-purpose elements of Zn and Sn is being actively studied as alternatives to CIGS-based thin film materials, and the compound semiconductors thus prepared are known to have an energy band gap ranging from about 1.0 eV (CZTSe) to 1.5 eV (CZTS). Hence, these are favorable for the manufacture of high-efficiency solar cells adapted for the solar light spectrum and allow a ZnS layer (which is a low toxic buffer) to be easily applied to ensure pn junctions, and thus many of the defects of the CIGS-based solar cells are considered to also be overcome.
Research related thereto is actively ongoing these days, and research papers have been drastically increasing since 2009. Among CZT(S,Se)-based thin film solar cells to date, the world’s greatest conversion efficiency that has been achieved without using S and Se together includes the 6.77% achieved by Nagaoka National Technical University (Appl. Phys. Express 1, 2008, 041201, H. Katagiri et al.) and the 3.2% achieved by Northumbria University (Prog. Photovolt: Res. Appl. 2009; 17: 315-319, G. Zoppi et al.), using sputtering. Recently, the preparation of CZT(S, Se)-based thin film using S and Se together is carried out in a non-vacuum process to thus achieve the world’s greatest efficiency of 9.66% by IBM (Adv. Mater. 22, 2010, 1, T.K. Todorov et al.), but is limited in terms of using hydrazine, which is explosive and toxic, and the CZT(S, Se)-based thin film has not yet provided better efficiency than the highest efficiency of CIS or CIGS thin films.
Although the co-evaporation process is advantageous because the maximum efficiency of CIS-based solar cells may be obtained, research results thereof are fewer compared to two-step methods including sputtering and then sulfurization or selenization. This is because Sn evaporates rather than deposits with Se during the co-evaporation process, thus causing Sn loss in the thin film, resulting in decreased energy conversion efficiency.
Accordingly, the present invention has been made keeping in mind the above problems occurring in the related art, and an object of the present invention is to provide a method of manufacturing a CZT(Se,S)-based thin film having high energy conversion efficiency for a solar cell, wherein co-evaporation may be performed via multi-steps so that Sn loss may be suppressed during co-evaporation which facilitates the control of a composition.
In order to accomplish the above object, an aspect of the present invention provides a method of manufacturing a CZT(S,Se)-based thin film for a solar cell, comprising depositing Sn, Zn and Cu on a substrate in a predetermined order using evaporation method to form a CZT-based precursor thin film (step a); and subjecting the CZT-based precursor thin film to selenization or sulfurization (step b).
In this aspect, step a may be performed by depositing Sn, Zn and Cu, Sn+Zn and Cu or Sn, Cu and Zn, in that order.
In this aspect, a Zn source may be one selected from the group consisting of Zn, ZnSe and ZnS.
In this aspect, the temperature of the substrate may be 15 ~ 200℃ upon depositing.
In this aspect, the temperature of the substrate may be 350 ~ 550℃ upon selenization or sulfurization.
Another aspect of the present invention provides a CZT(S,Se)-based thin film for a solar cell, manufactured by depositing Sn, Zn and Cu on a substrate in a predetermined order using evaporation method to form a CZT-based precursor thin film and subjecting the CZT-based precursor thin film to selenization or sulfurization.
In this aspect, the CZT-based precursor thin film may be formed by depositing Sn, Zn and Cu, Sn+Zn and Cu, or Sn, Cu and Zn, in that order.
In this aspect, the CZT(S,Se)-based thin film may be one selected from the group consisting of Cu2ZnSnS4, Cu2ZnSnSe4 and Cu2ZnSn(S,Se)4.
A further aspect of the present invention provides a solar cell using the CZT(S,Se)-based thin film manufactured by depositing Sn, Zn and Cu on a substrate in a predetermined order using evaporation method to form a CZT-based precursor thin film and subjecting the CZT-based precursor thin film to selenization or sulfurization.
In this aspect, the CZT-based precursor thin film may be formed by depositing Sn, Zn and Cu, Sn+Zn and Cu, or Sn, Cu and Zn, in that order.
The present invention provides a CZT(S,Se)-based thin film for a solar cell, wherein Sn loss can be suppressed during the manufacturing process thus achieving improved conversion efficiency, compared to when using conventional co-evaporation process for manufacturing CZT(S,Se)-based thin films, and a method of manufacturing the same, and thus can be utilized to fabricate inexpensive solar cells having superior efficiency.
FIG. 1 illustrates an energy efficiency curve of a solar cell using a CZTSe-based thin film of Example 1 according to the present invention;
FIG. 2 illustrates a relation between the Cu ratio depending on the temperature of Cu effusion cells upon co-evaporation in the comparative examples and the energy efficiency of solar cells using the same;
FIG. 3 illustrates energy efficiency curves of the solar cells of FIG. 2;
FIG. 4 illustrates external quantum efficiency (EQE) curves of the solar cells using CZTSe thin films of Example 1 and Comparative Example 1;
FIG. 5 illustrates the distribution of the amounts of respective elements of the CZTSe-based thin films of Examples 1 to 3 according to the present invention; and
FIG. 6 illustrates the distribution of the amounts of respective elements of the CZTSe-based thin films of Comparative Examples 1, and 6 to 9.
Hereinafter, a method of manufacturing a CZT(Se,S)-based thin film for a solar cell according to the present invention will be described.
As such, the CZT(Se,S)-based thin film is a concept including thin films of CuZnSnS4, CuZnSnSe4, CuZnSn(S,Se)4, etc.
First, a CZT-based precursor thin film is formed on a substrate using evaporation method (step a).
The CZT-based thin film indicates a thin film including Cu, Zn and Sn.
In the formation of the CZT-based thin film, Sn, Zn and Cu on a substrate in a predetermined order may be deposited. Preferably, Sn, Zn and Cu, Sn+Zn and Cu, or Sn, Cu and Zn, in that order, may be deposited.
Upon deposition, the substrate temperature is preferably maintained at 15 ~ 200℃. As such, the Zn source may be Zn, ZnSe or ZnS, and the amounts of deposited Sn, Zn and Cu may be set depending on the deposition rate based on changes in temperature of the effusion cell to obtain the desired composition.
Next, the CZT-based precursor thin film formed in step a is subjected to selenization or sulfurization to prepare a CZT(S,Se)-based thin film (step b).
The selenization or sulfurization is carried out by supplying Se vapor or S vapor. The effusion cell temperature of Se or S is preferably adjusted so that the deposition rate is 5 ~ 60 Å/s at room temperature.
The selenization or sulfurization is preferably performed for 0.1 ~ 3 hr under conditions of the substrate temperature being maintained in the range of 350 ~ 550℃. If the substrate temperature is lower than 350℃, a large amount of impurities may be generated. In contrast, if the substrate temperature is higher than 550℃, it is hard to suppress Sn loss, making it difficult to obtain a thin film having an appropriate composition.
Also, the selenization or sulfurization may be performed using the same co-evaporation process as that used in step a, or a RTA (Rapid Thermal Annealing) process. In addition, any heat treatment process for sulfurization/selenization may be applied within the scope of the present invention.
The present invention provides a CZT(S,Se)-based thin film manufactured using the above method.
In addition, the present invention provides a solar cell including the CZT(S,Se)-based thin film manufactured using the above method as a light absorption layer.
Example 1
A Mo back electrode was deposited to a thickness of about 1 ㎛ on a soda-lime glass substrate using DC sputtering.
Subsequently, Sn, Zn and Cu, in that order, were deposited on the glass substrate using evaporation method to form a CZT-based precursor thin film. As such, the substrate temperature was set to room temperature, and the temperatures and deposition times of respective effusion cells were Sn 1450℃, 96 min, Zn 380℃, 46 min, and Cu 1450℃, 100 min.
Subsequently, the CZT-based thin film was subjected to selenization by supplying Se vapor for 2 hr at a substrate temperature of 430℃ thus completing a Cu2ZnSnSe4 thin film. As such, selenization was performed using the co-evaporation process wherein the above evaporation had been conducted, and the temperature of the Se effusion cell was 140℃.
Example 2
A CZTSe-based thin film was manufactured in the same manner as in Example 1, with the exception that the substrate temperature was 400℃ upon selenization.
Example 3
A CZTSe-based thin film was manufactured in the same manner as in Example 1, with the exception that the substrate temperature was 370℃ upon selenization.
Comparative Example 1
The same substrate as in the above examples was prepared, and Cu, Zn, Sn and Se were co-evaporated so that a thin film was produced and selenization was conducted at the same time. As such, the substrate temperature was 320℃, and the deposition time was 80 min, and the ratio of respective elements was optimized by adjusting the temperature of the effusion cells, and thus the temperature of the Cu effusion cell was 1380℃.
Comparative Example 2
This comparative example was conducted in the same manner as in Comparative Example 1, with the exception that the temperature of the Cu effusion cell was 1330℃.
Comparative Example 3
This comparative example was conducted in the same manner as in Comparative Example 1, with the exception that the temperature of the Cu effusion cell was 1430℃.
Comparative Example 4
This comparative example was conducted in the same manner as in Comparative Example 1, with the exception that the temperature of the Cu effusion cell was 1480℃.
Comparative Example 5
This comparative example was conducted in the same manner as in Comparative Example 1, with the exception that the temperature of the Cu effusion cell was 1550℃.
Comparative Example 6
This comparative example was conducted in the same manner as in Comparative Example 1, with the exception that the substrate temperature was 200℃ upon co-evaporation.
Comparative Example 7
This comparative example was conducted in the same manner as in Comparative Example 1, with the exception that the substrate temperature was 260℃ upon co-evaporation.
Comparative Example 8
This comparative example was conducted in the same manner as in Comparative Example 1, with the exception that the substrate temperature was 370℃ upon co-evaporation.
Comparative Example 9
This comparative example was conducted in the same manner as in Comparative Example 1, with the exception that the substrate temperature was 500℃ upon co-evaporation.
Energy Efficiency Comparison of Solar Cells
Using the CZTSe-based thin film of Example 1 of the present invention, typical CIS-based solar cell formation procedures comprising forming a 60 nm CdS buffer layer, forming a 400 nm ZnO window layer and forming an Al electrode were performed, thus completing a solar cell.
The efficiency curve of the solar cell using the CZTSe-based thin film of Example 1 of the present invention is illustrated in FIG. 1.
As shown in FIG. 1, the energy conversion efficiency of the CZTSe-based thin film of Example 1 of the present invention was 5.1%, which was higher than 3.2% that is the maximum efficiency of a quaternary Cu2ZnSnSe4 solar cell resulting from conventional two steps of sputtering and selenization.
Using the CZTSe-based thin films of Comparative Examples 1 to 5, the typical CIS-based solar cell formation procedures were performed as above, thus completing solar cells.
FIG.2 is a depiction of the relation between the temperature of the Cu effusion cell upon co-evaporation and the energy efficiency of the solar cell using the same for Comparative Examples 1 to 5. The energy efficiency curves of the solar cells of FIG. 2 are shown in FIG. 3.
As shown in FIGS. 2 and 3, the energy conversion efficiency of the CZTSe-based thin film of Comparative Example 1 was 2.9%, which was the greatest among the comparative examples and was similar to 3.2% which is the maximum efficiency of a quaternary Cu2ZnSnSe4 solar cell resulting from the conventional two steps of sputtering and selenization.
The EQE curves of the solar cell using the CZTSe-based thin film of Example 1 and of the solar cell using the CZTSe-based thin film of Comparative Example 1 are compared and shown in FIG. 4.
As shown in FIGS. 1 to 4, the efficiency of the solar cells using the CZTSe-based thin film of Example 1 was higher than that of the solar cells using the CZTSe-based thin films of the comparative examples.
Analysis of Sn Loss depending on Substrate Temperature
The distribution of the amounts of respective elements of the CZTSe-based thin films of Examples 1 to 3 of the present invention is shown in FIG. 5, and the distribution of the amounts of respective elements of the CZTSe-based thin films of Comparative Examples 1 and 6 to 9 is shown in FIG. 6.
As shown in FIGS. 5 and 6, it was observed that for the CZTSe-based thin films of the examples of the present invention, the loss of Sn gradually occurred in proportion to an increase in the temperature of the substrate upon selenization and that the amount ratio with respect to other elements was not greatly decreased even at 430℃. However, for the CZTSe-based thin films of the comparative examples, it was observed that Sn loss was drastic in the thin film at 370℃ or higher, which is the substrate temperature upon co-evaporation. Such Sn loss resulted in phase separation of the thin film and the decreased thickness.
Accordingly, the method of manufacturing the CZTSe-based thin film according to the present invention can be seen to greatly reduce the Sn loss in proportion to an increase in the substrate temperature in the manufacturing process, compared to conventional methods.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (10)

  1. A method of manufacturing a CZT(S,Se)-based thin film for a solar cell, comprising:
    depositing Sn, Zn and Cu on a substrate in a predetermined order using evaporation method to form a CZT-based precursor thin film (step a); and
    subjecting the CZT-based precursor thin film to selenization or sulfurization (step b).
  2. The method of claim 1, wherein step a is performed by depositing Sn, Zn and Cu, Sn+Zn and Cu, or Sn, Cu and Zn, in that order.
  3. The method of claim 1, wherein a Zn source is one selected from the group consisting of Zn, ZnSe and ZnS.
  4. The method of claim 1, wherein a temperature of the substrate is 15 ~ 200℃ upon depositing.
  5. The method of claim 1, wherein a temperature of the substrate is 350 ~ 550℃ upon selenization or sulfurization.
  6. A CZT(S,Se)-based thin film for a solar cell, manufactured by depositing Sn, Zn and Cu on a substrate in a predetermined order using evaporation method to form a CZT-based precursor thin film and subjecting the CZT-based precursor thin film to selenization or sulfurization.
  7. The CZT(S,Se)-based thin film of claim 6, wherein the CZT-based precursor thin film is formed by depositing Sn, Zn and Cu, Sn+Zn and Cu, or Sn, Cu and Zn, in that order.
  8. The CZT(S,Se)-based thin film of claim 6, wherein the CZT(S,Se)-based thin film is one selected from the group consisting of Cu2ZnSnS4, Cu2ZnSnSe4 and Cu2ZnSn(S,Se)4.
  9. A solar cell using a CZT(S,Se)-based thin film manufactured by depositing Sn, Zn and Cu on a substrate in a predetermined order using evaporation method to form a CZT-based precursor thin film and subjecting the CZT-based precursor thin film to selenization or sulfurization.
  10. The solar cell of claim 9, wherein the CZT-based precursor thin film is formed by depositing Sn, Zn and Cu, Sn+Zn and Cu, or Sn, Cu and Zn, in that order.
PCT/KR2012/006198 2011-08-08 2012-08-03 Method of manufacturing czt(s,se)-based thin film for solar cell and czt(s,se)-based thin film manufactured thereby WO2013022234A2 (en)

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KR101449576B1 (en) * 2013-04-04 2014-10-16 한국에너지기술연구원 Fabrication method of czts-based absorber layers by non-vacuum process
KR101406704B1 (en) * 2013-04-18 2014-06-12 한국에너지기술연구원 FABRICATION METHOD OF CZTSe ABSORBER LAYERS BY CO-EVAPORATION PROCESS
KR101465209B1 (en) * 2013-06-10 2014-11-26 성균관대학교산학협력단 LIGHT ABSORBING LAYER CONTAINING CZTSSe-BASED THIN FILM AND PREPARING METHOD OF THE SAME
WO2016053016A1 (en) * 2014-09-29 2016-04-07 이화여자대학교 산학협력단 Cztse-based thin film and manufacturing method therefor, and solar cell using cztse-based thin film
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KR102025091B1 (en) * 2018-05-28 2019-09-25 한국에너지기술연구원 CZT(S,Se) FILM, FORMING METHOD FOR CZT(S,Se) FILM, CZT(S,Se) SOLAR CELL AND MANUFACTURING METHOD FOR CZT(S,Se) SOLAR CELL

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