WO2012011723A2 - Method of manufacturing high density cis thin film for solar cell and method of manufacturing thin film solar cell using the same - Google Patents

Method of manufacturing high density cis thin film for solar cell and method of manufacturing thin film solar cell using the same Download PDF

Info

Publication number
WO2012011723A2
WO2012011723A2 PCT/KR2011/005306 KR2011005306W WO2012011723A2 WO 2012011723 A2 WO2012011723 A2 WO 2012011723A2 KR 2011005306 W KR2011005306 W KR 2011005306W WO 2012011723 A2 WO2012011723 A2 WO 2012011723A2
Authority
WO
WIPO (PCT)
Prior art keywords
thin film
cis
slurry
salt
filling element
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2011/005306
Other languages
French (fr)
Other versions
WO2012011723A3 (en
Inventor
Se-Jin Ahn
Jae-Ho Yun
Ji-Hye Gwak
Ara Cho
Kyung-Hoon Yoon
Kee-Shik Shin
Seoung-Kyu Ahn
Ki-Bong Song
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Korea Institute of Energy Research KIER
Original Assignee
Korea Institute of Energy Research KIER
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Korea Institute of Energy Research KIER filed Critical Korea Institute of Energy Research KIER
Priority to US13/695,627 priority Critical patent/US8569102B2/en
Publication of WO2012011723A2 publication Critical patent/WO2012011723A2/en
Publication of WO2012011723A3 publication Critical patent/WO2012011723A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/14—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies
    • H10F77/143—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies comprising quantum structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C01G15/006—Compounds containing gallium, indium or thallium, with or without oxygen or hydrogen, and containing two or more other elements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/128—Annealing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • Y02E10/541—CuInSe2 material PV cells
    • 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

Definitions

  • the present invention relates to a method of manufacturing a high density CIS thin film for a solar cell and a method of manufacturing a thin film solar cell using the CIS thin film. More particularly, the present invention relates to a method of manufacturing a high density CIS thin film for a solar cell by coating CIS nanopowders, CIGS nanopowders or CZTS nanopowders on a substrate via non-vacuum coating, followed by heat treatment with cavities between the nanopowders filled with filling elements such as copper, indium, gallium, zinc, tin, and the like, and a method of manufacturing a thin film solar cell using the CIS thin film.
  • a CIS or CIGS thin film is al-HI-VI compound semiconductor and has a higher
  • the CIS or CIGS thin film can be formed to a thickness of 10 micrometers or less and is stable after long term use, the thin film is anticipated as an inexpensive, highly efficient solar cell capable of replacing silicon.
  • the CIS thin film is a direct transition type semiconductor and may be formed into a thin film. Further, the CIS thin film has a band-gap energy of 1.04 eV suited to photo conversion and exhibits a higher coefficient of photo absorption than any other solar cell materials known in the art.
  • the CIGS thin film is developed to replace some of indium In by gallium Ga or
  • a CIGS solar cell is formed using a thin film having a thickness of several micrometers by vacuum deposition, or by precursor deposition in a non- vacuum state and heat treatment of the precursor-deposited thin film.
  • Vacuum deposition is advantageous in that it provides a highly efficient absorption layer.
  • vacuum deposition disadvantageously provides low uniformity and requires expensive equipment in forming a large area absorption layer, and causes material loss of about 20% to 50%, which leads to high manufacturing costs.
  • formation of the solar cell through a non- vacuum precursor deposition and heat treatment at high temperature may advantageously reduce manufacturing costs while providing a uniform large area.
  • this process is disadvantageous due to low efficiency of the absorption layer.
  • the CIGS thin film has very high melting point of 1000°C or more, it is difficult even for CIGS particles having a size of dozens of nanometers to allow particle growth and densification through post-heat treatment.
  • the inventors of the present invention carried out diligent studies to obtain a method of manufacturing a high density CIS thin film, CIGS thin film or CZTS thin film through non- vacuum coating.
  • a high density CIS thin film can be formed when heat treating the CIS thin film, CIGS thin film, CZTS thin film, with cavities of the film filled with filling elements such as copper, indium, gallium, zinc, tin, and the like. Accordingly, it was also found that, when such a high density CIS thin film was applied to a photo-absorption layer of a thin film solar cell, it is possible to improve efficiency of the thin film solar cell while reducing manufacturing costs thereof.
  • the present invention was conceived to solve the problems of the related art, and one aspect of the present invention is to provide a high density CIS thin film, which can reduce manufacturing costs using non-vacuum coating, and a method of manufacturing the same.
  • Another aspect of the present invention is to provide an inexpensive thin film solar cell, which has high efficiency, and a method of manufacturing the same.
  • a method of manufacturing a high density CIS thin film includes: preparing CIS nanoparticles (Step 1); dispersing the CIS nanoparticles and dissolving a binder in a solvent to prepare a CIS slurry (Step 2); dissolving a filling element-containing salt and a binder in a solvent to prepare a filling element-containing slurry (Step 3); mixing the CIS slurry and the filling element- containing slurry to prepare a slurry mixture (Step 4); and coating the slurry mixture onto a substrate to form a CIS thin film, followed by heat treatment (Step 5).
  • a method of manufacturing a high density CIS thin film include: preparing CIS nanoparticles (Step A); dispersing the CIS nanoparticles and dissolving a binder in a solvent to prepare a CIS slurry (Step B); coating the CIS slurry onto a substrate to form a CIS thin film (Step C); dissolving a filling element-containing salt and a binder in a solvent to prepare a filling element-containing slurry (Step D); and coating the filling element-containing slurry onto the CIS thin film, followed by heat treatment (Step E).
  • the CIS nanoparticles may include CIS nanoparticles, CIGS nanoparticles, or CZTS nanoparticles.
  • the filling element-containing salt may be a mixed salt of at least two selected from the group consisting of copper salt, indium salt, gallium salt, zinc salt, and tin salt.
  • the filling element-containing slurry may further include a selenium compound.
  • the CIS thin film may be formed by non-vacuum coating including spraying, ultrasonic spraying, spin coating, doctor blade coating, screen printing, and inkjet printing.
  • the heat treatment is selenization heat treatment performed at 400 to 550°C while supplying Se vapor.
  • the selenization heat treatment may make the CIS thin film denser.
  • a further aspect of the present invention provides a high density CIS thin film, which includes a CIS thin film; and filling elements placed in cavities within the CIS thin film.
  • the filling elements are at least two elements selected from the group consisting of copper, indium, gallium, zinc, and tin.
  • the CIS thin film may be a CIS thin film, a CIGS thin film, or a CZTS thin film.
  • the CIS thin film is subjected to heat treatment with cavities of the CIS thin film filled with filling elements such as copper, indium, gallium, zinc, tin, and so on, thereby forming a high density CIS thin film.
  • the high density CIS thin film is applied to a photo-absorption layer of a thin film solar cell, the manufactured thin film solar cell exhibits high efficiency.
  • Fig. 1 is a scanning electronic microscope (SEM) image of a side section of a CIGS thin film manufactured according to Example 2.
  • FIG. 2 is a SEM image of a side section of a CIGS thin film manufactured according to Comparative Example 2.
  • nanoparticles is mixed with a metal salt including copper, indium, gallium, zinc, tin, and the like to prepare a slurry mixture, which is coated onto a substrate, followed by heat treatment, thereby providing a high density CIS thin film.
  • the CIS nanoparticles are prepared in Step 1.
  • CIS means Cu-In-Se-based ternary compounds, which are ⁇ -
  • IIIA-VIA group compound semiconductors such as Cu-In-S, Cu-Ga-S, Cu-Ga-Se, and the like; quaternary compounds such as Cu-In-Ga-Se; and quinary-hexanary compounds such as Cu-In-Ga-Se-(S,Se), Cu-In-Al-Ga-(S,Se), Cu-In-Al-Ga-Se-S, and the like.
  • CIS means CZTS-based compounds such as Cu- Zn-Sn-(Se,S), Cu-In-Ga-Zn-Sn-(Se,S), etc.
  • Cu-Zn-Sn-(Se,S) is formed by substituting all IIIA-group elements such as In, Ga, Al, and the like in the CIS with IIB- group elements (Zn and the like) and IVA-group elements (Sn and the like). Further, Cu-In-Ga-Zn-Sn-(Se,S) is formed by substituting some of the IIIA-group elements in the CIS with the IIB -group elements and the IVA-group elements.
  • the CIS nanoparticles may be prepared by any known method in the art, such as a low temperature colloidal process, a solvent thermal process, or a microwave process, using the CIS.
  • the CIS nanoparticles and a binder are dispersed and dissolved, respectively, in a solvent to prepare a CIS slurry in Step 2.
  • the solvent may be an alcohol-based solvent such as methanol, ethanol, phentanol, propanol, butanol, and the like.
  • the binder may be ethylene glycol, propylene glycol, ethyl cellulose,
  • the amount of binder may be adjusted to control the concentration of the CIS slurry.
  • the CIS slurry may include 20 to 30 parts by weight of the CIS nanoparticles, 80 to
  • the CIS nanoparticles and the binder are sufficiently mixed in the solvent, followed by ultrasonic treatment, so that the prepared CIS slurry is uniformly dispersed.
  • Step 3 a filling element-containing salt and a binder are dissolved in a solvent to prepare a filling element-containing slurry.
  • the term "filling element” means elements to be placed in cavities of the CIS thin film.
  • the filling element may include copper and indium, and for a CIGS thin film, the filling element may include copper and indium or gallium.
  • the filling element may include copper, zinc or tin.
  • the aforementioned filling element-containing salt for example, a mixed salt of at least two selected from the group consisting of copper salt, indium salt, gallium salt, zinc salt and tin salt, is mixed with a binder in a solvent, thereby preparing the filling element-containing slurry.
  • the binder and solvent used for preparing the filling element-containing slurry may be the same as those used in preparation of the CIS slurry.
  • the filling element-containing slurry may include 10 to 20 parts by weight of the filling element-containing salt, 80 to 90 parts by weight of the solvent, and 20 to 30 parts by weight of the binder.
  • the copper salt may include CuCl, Cu-acetate, Cul, CuS0 4 , and the like;
  • the indium salt may include In(N0 3 ) 3 , In 2 (S0 4 ) 3 , In-acetate, and the like;
  • the gallium salt may include
  • the zinc salt may include ZnCl 2 ,
  • the tin salt may include SnCl 4 and the like.
  • the filling element-containing slurry may further include a selenium compound such as Se0 2 , SeCl 4 , selenourea, and the like.
  • the CIS slurry is mixed with the filling element-containing slurry to prepare a slurry mixture in Step 4.
  • the slurry mixture is coated onto a substrate to form a CIS thin film, which in turn is subjected to heat treatment, in Step 5.
  • non- vacuum coating when forming the CIS thin film using the slurry mixture, non- vacuum coating is employed.
  • the non-vacuum coating may be any non-vacuum coating method known in the art, for example, spraying, ultrasonic spraying, spin coating, doctor blade coating, screen printing, inkjet printing, and the like.
  • the CIS thin film may be formed by non-vacuum coating, thereby reducing manufacturing costs.
  • the thin film After forming the CIS thin film by coating the slurry mixture in a non-vacuum state, the thin film may be further subjected to drying to remove the alcohol solvent and the binder. Coating of the slurry mixture and drying are repeated twice or three times, thereby forming a CIS thin film having a desired thickness.
  • the CIS thin film is subjected to heat treatment.
  • heat treatment heat
  • CIS thin film treatment of the CIS thin film is performed at 400 to 550°C, which is lower than the temperature of existing post-heat treatment for CIS thin films, while supplying Se vapor, thereby providing a dense CIS thin film.
  • nanoparticles is prepared and coated onto a substrate to form a CIS thin film. Then, a slurry containing metal salts including copper, indium, gallium, zinc, tin, and the like is prepared and coated onto the CIS thin film, which in turn is subjected to heat treatment, thereby preparing a dense CIS thin film. Next, the method according to the present invention will be described in more detail.
  • CIS nanoparticles are prepared and dispersed together with a binder in a solvent to prepare a CIS slurry in Steps A and B.
  • the prepared CIS slurry is coated onto a substrate to form a CIS thin film in Step C.
  • the CIS slurry is coated onto the substrate by non-vacuum coating.
  • Step D prepare a filling element-containing slurry in Step D.
  • Step E a filling element-containing slurry is coated onto the CIS thin film, followed by heat treatment in Step E.
  • the CIS thin film formed on the substrate has lots of cavities.
  • filling elements such as copper, indium, gallium, zinc, tin, and the like enter the cavities, thereby making it possible to form a dense CIS thin film.
  • the CIS thin film having the filling elements placed in the cavities is subjected to heat treatment, thereby forming a higher density CIS thin film.
  • a CIS thin film manufactured by the method according to this invention has a dense structure through heat treatment of the CIS thin film with the cavities of the thin film filled with the filling elements, as described above.
  • the present invention provides a thin film solar cell, a photo-absorption layer of which is a high density CIS thin film obtained through heat treatment of the CIS thin film with the cavities of the CIS thin film filled with the filling element.
  • the present invention provides a method of manufacturing a thin film solar cell using the CIS thin film according to the embodiments of the invention.
  • the prepared slurry mixture was coated onto a glass substrate by doctor blade coating, followed by drying the substrate at 60°C for 5 minutes and at 180°C for 2 minutes on a hot plate to remove the alcohol solvent and the binder. Such a coating and drying process was repeated three times to form a CIS thin film on the substrate. Then, the film was subjected to heat treatment while supplying Se vapor at a substrate temperature of 400°C, thereby preparing a high density CIS thin film.
  • CIS nanoparticles were prepared by the same process as in Example 1. Then, 0.3 g of the prepared CIS nanoparticles and 0.3 g of propylene glycol was dissolved in 1.2 g of methanol, followed by ultrasonic treatment for 60 minutes, thereby preparing a CIS slurry. The CIS slurry was coated onto a glass substrate by doctor blade coating, followed by drying the substrate at 60°C for 5 minutes and at 180°C for 2 minutes on a hot plate to remove the alcohol solvent and the binder. Such a coating and drying process was repeated three times to form a CIS thin film on the substrate.
  • Fig. 1 is a scanning electronic micrograph (SEM) image of a side section of the CIS thin film manufactured according to Example 2.
  • CIS nanoparticles were prepared by the same process as in Example 1. Then, 0.3 g of the prepared CIS nanoparticles and 0.3 g of propylene glycol were dissolved in 1.2 g of methanol, followed by ultrasonic treatment for 60 minutes, thereby preparing a CIS slurry. The CIS slurry was coated onto a glass substrate by doctor blade coating, followed by drying the substrate at 60°C for 5 minutes and at 180°C for 2 minutes on a hot plate to remove the alcohol solvent and the binder. Such a coating and drying process was repeated three times to form a CIS thin film on the substrate.
  • Fig. 2 is an SEM image of a side section of the CIS thin film manufactured according to Comparative Example 2.
  • the CIS thin film prepared in Example 2 is denser than the CIS thin film prepared in Comparative Example 1 in which the filling element-containing slurry was not coated to the thin film. Therefore, it can be seen that the CIS thin film formed by the method according to the present invention has a denser structure even when the thin film is subjected to heat treatment at a lower temperature than that of existing heat treatment.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Disclosed are a high density CIS thin film and a method of manufacturing the same, which includes coating CIS nanopowders, CIGS nanopowders or CZTS nanopowders on a substrate by non-vacuum coating, followed by heat treatment with cavities between the nanopowders filled with filling elements such as copper, indium, gallium, zinc, tin, and the like. The high density CIS thin film is applied to a photo-absorption layer of a thin film solar cell, thereby providing a highly efficient thin film solar cell.

Description

Description
Title of Invention: METHOD OF MANUFACTURING HIGH DENSITY CIS THIN FILM FOR SOLAR CELL AND METHOD OF MANUFACTURING THIN FILM SOLAR CELL USING THE
SAME
Technical Field
[1] The present invention relates to a method of manufacturing a high density CIS thin film for a solar cell and a method of manufacturing a thin film solar cell using the CIS thin film. More particularly, the present invention relates to a method of manufacturing a high density CIS thin film for a solar cell by coating CIS nanopowders, CIGS nanopowders or CZTS nanopowders on a substrate via non-vacuum coating, followed by heat treatment with cavities between the nanopowders filled with filling elements such as copper, indium, gallium, zinc, tin, and the like, and a method of manufacturing a thin film solar cell using the CIS thin film.
Background Art
[2] Recently, development of next generation clean energy sources has become a crucial issue to overcome severe environmental contamination and depletion of fossil fuels. In particular, solar cells directly converting sunlight into electric energy have various merits such as avoidance of contamination, infinite resource and semi-permanent lifespan, and are thus anticipated as an energy source capable of solving the problem of energy depletion.
[3] Solar cells are classified into five types depending on materials for a photo-absorption layer, and a silicon solar cell is most widely used in the art. Recently, however, a rapid increase in raw material costs due to undersupply of silicon has led to increasing interest in thin film solar cells. Thin film solar cells are manufactured to a low thickness, thereby providing merits such as low consumption of material, light weight, wide application ranges, and the like. As for materials of such a thin film solar cell, studies have been actively conducted on amorphous silicon, CdTe, CIS, CIGS, and the like.
[4] A CIS or CIGS thin film is al-HI-VI compound semiconductor and has a higher
conversion efficiency of about 19.9% than any other thin film solar cells. In particular, since the CIS or CIGS thin film can be formed to a thickness of 10 micrometers or less and is stable after long term use, the thin film is anticipated as an inexpensive, highly efficient solar cell capable of replacing silicon.
[5] Particularly, the CIS thin film is a direct transition type semiconductor and may be formed into a thin film. Further, the CIS thin film has a band-gap energy of 1.04 eV suited to photo conversion and exhibits a higher coefficient of photo absorption than any other solar cell materials known in the art.
[6] The CIGS thin film is developed to replace some of indium In by gallium Ga or
replace selenium Se by sulfur S to improve a low open circuit voltage of the CIS thin film.
[7] Generally, a CIGS solar cell is formed using a thin film having a thickness of several micrometers by vacuum deposition, or by precursor deposition in a non- vacuum state and heat treatment of the precursor-deposited thin film. Vacuum deposition is advantageous in that it provides a highly efficient absorption layer. However, vacuum deposition disadvantageously provides low uniformity and requires expensive equipment in forming a large area absorption layer, and causes material loss of about 20% to 50%, which leads to high manufacturing costs. On the other hand, formation of the solar cell through a non- vacuum precursor deposition and heat treatment at high temperature may advantageously reduce manufacturing costs while providing a uniform large area. However, this process is disadvantageous due to low efficiency of the absorption layer.
[8] Since the CIGS thin film formed by depositing a precursor in a non- vacuum state has lots of pores and exhibits non-dense characteristics, selenization heat treatment is performed. Here, since conventional selenization heat treatment is performed using toxic hydrogen selenide (H2Se) gas, huge installation costs are required to provide a safety system to guarantee safety and the heat treatment is performed for a long duration, thereby causing an increase in the unit cost of the CIGS thin film.
[9] Further, since the CIGS thin film has very high melting point of 1000°C or more, it is difficult even for CIGS particles having a size of dozens of nanometers to allow particle growth and densification through post-heat treatment.
[10] The inventors of the present invention carried out diligent studies to obtain a method of manufacturing a high density CIS thin film, CIGS thin film or CZTS thin film through non- vacuum coating. As a result, the inventors found that a high density CIS thin film can be formed when heat treating the CIS thin film, CIGS thin film, CZTS thin film, with cavities of the film filled with filling elements such as copper, indium, gallium, zinc, tin, and the like. Accordingly, it was also found that, when such a high density CIS thin film was applied to a photo-absorption layer of a thin film solar cell, it is possible to improve efficiency of the thin film solar cell while reducing manufacturing costs thereof.
Disclosure of Invention
Technical Problem
[11] The present invention was conceived to solve the problems of the related art, and one aspect of the present invention is to provide a high density CIS thin film, which can reduce manufacturing costs using non-vacuum coating, and a method of manufacturing the same.
[12] Another aspect of the present invention is to provide an inexpensive thin film solar cell, which has high efficiency, and a method of manufacturing the same.
Solution to Problem
[13] In accordance with one aspect of the invention, a method of manufacturing a high density CIS thin film includes: preparing CIS nanoparticles (Step 1); dispersing the CIS nanoparticles and dissolving a binder in a solvent to prepare a CIS slurry (Step 2); dissolving a filling element-containing salt and a binder in a solvent to prepare a filling element-containing slurry (Step 3); mixing the CIS slurry and the filling element- containing slurry to prepare a slurry mixture (Step 4); and coating the slurry mixture onto a substrate to form a CIS thin film, followed by heat treatment (Step 5).
[14] In accordance with another aspect of the present invention, a method of manufacturing a high density CIS thin film include: preparing CIS nanoparticles (Step A); dispersing the CIS nanoparticles and dissolving a binder in a solvent to prepare a CIS slurry (Step B); coating the CIS slurry onto a substrate to form a CIS thin film (Step C); dissolving a filling element-containing salt and a binder in a solvent to prepare a filling element-containing slurry (Step D); and coating the filling element-containing slurry onto the CIS thin film, followed by heat treatment (Step E).
[15] In one exemplary embodiment, the CIS nanoparticles may include CIS nanoparticles, CIGS nanoparticles, or CZTS nanoparticles.
[16] The filling element-containing salt may be a mixed salt of at least two selected from the group consisting of copper salt, indium salt, gallium salt, zinc salt, and tin salt.
[17] In another exemplary embodiment, the filling element-containing slurry may further include a selenium compound.
[18] In one exemplary embodiment, the CIS thin film may be formed by non-vacuum coating including spraying, ultrasonic spraying, spin coating, doctor blade coating, screen printing, and inkjet printing.
[19] In another exemplary embodiment, the heat treatment is selenization heat treatment performed at 400 to 550°C while supplying Se vapor. The selenization heat treatment may make the CIS thin film denser.
[20] A further aspect of the present invention provides a high density CIS thin film, which includes a CIS thin film; and filling elements placed in cavities within the CIS thin film. Here, the filling elements are at least two elements selected from the group consisting of copper, indium, gallium, zinc, and tin.
[21] The CIS thin film may be a CIS thin film, a CIGS thin film, or a CZTS thin film. Advantageous Effects of Invention
[22] According to the exemplary embodiments, the CIS thin film is subjected to heat treatment with cavities of the CIS thin film filled with filling elements such as copper, indium, gallium, zinc, tin, and so on, thereby forming a high density CIS thin film. When the high density CIS thin film is applied to a photo-absorption layer of a thin film solar cell, the manufactured thin film solar cell exhibits high efficiency.
Brief Description of Drawings
[23] Fig. 1 is a scanning electronic microscope (SEM) image of a side section of a CIGS thin film manufactured according to Example 2.
[24] Fig. 2 is a SEM image of a side section of a CIGS thin film manufactured according to Comparative Example 2.
Best Mode for Carrying out the Invention
[25] Exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
[26] According to the present invention, there are two methods of manufacturing a high density CIS thin film by filling cavities of a CIS thin film with filling elements such as copper, indium, gallium, zinc, tin, and the like.
[27] In one method according to the present invention, a slurry containing CIS
nanoparticles is mixed with a metal salt including copper, indium, gallium, zinc, tin, and the like to prepare a slurry mixture, which is coated onto a substrate, followed by heat treatment, thereby providing a high density CIS thin film. Next, the method according to the present invention will be described in more detail.
[28] First, the CIS nanoparticles are prepared in Step 1.
[29] Herein, the term "CIS" means Cu-In-Se-based ternary compounds, which are ΓΒ-
IIIA-VIA group compound semiconductors, such as Cu-In-S, Cu-Ga-S, Cu-Ga-Se, and the like; quaternary compounds such as Cu-In-Ga-Se; and quinary-hexanary compounds such as Cu-In-Ga-Se-(S,Se), Cu-In-Al-Ga-(S,Se), Cu-In-Al-Ga-Se-S, and the like. More broadly, the term "CIS" means CZTS-based compounds such as Cu- Zn-Sn-(Se,S), Cu-In-Ga-Zn-Sn-(Se,S), etc. Here, Cu-Zn-Sn-(Se,S) is formed by substituting all IIIA-group elements such as In, Ga, Al, and the like in the CIS with IIB- group elements (Zn and the like) and IVA-group elements (Sn and the like). Further, Cu-In-Ga-Zn-Sn-(Se,S) is formed by substituting some of the IIIA-group elements in the CIS with the IIB -group elements and the IVA-group elements.
[30] The CIS nanoparticles may be prepared by any known method in the art, such as a low temperature colloidal process, a solvent thermal process, or a microwave process, using the CIS.
[31] Next, the CIS nanoparticles and a binder are dispersed and dissolved, respectively, in a solvent to prepare a CIS slurry in Step 2.
[32] In one exemplary embodiment, the solvent may be an alcohol-based solvent such as methanol, ethanol, phentanol, propanol, butanol, and the like.
[33] The binder may be ethylene glycol, propylene glycol, ethyl cellulose,
polyvinylpyrrolidone, and the like. The amount of binder may be adjusted to control the concentration of the CIS slurry.
[34] The CIS slurry may include 20 to 30 parts by weight of the CIS nanoparticles, 80 to
100 parts by weight of the solvent, and 20 to 30 parts by weight of the binder.
[35] The CIS nanoparticles and the binder are sufficiently mixed in the solvent, followed by ultrasonic treatment, so that the prepared CIS slurry is uniformly dispersed.
[36] Next, a filling element-containing salt and a binder are dissolved in a solvent to prepare a filling element-containing slurry (Step 3).
[37] Herein, the term "filling element" means elements to be placed in cavities of the CIS thin film. For a CIS thin film, the filling element may include copper and indium, and for a CIGS thin film, the filling element may include copper and indium or gallium.
For a CZTS thin film, the filling element may include copper, zinc or tin.
[38] The aforementioned filling element-containing salt, for example, a mixed salt of at least two selected from the group consisting of copper salt, indium salt, gallium salt, zinc salt and tin salt, is mixed with a binder in a solvent, thereby preparing the filling element-containing slurry.
[39] The binder and solvent used for preparing the filling element-containing slurry may be the same as those used in preparation of the CIS slurry.
[40] The filling element-containing slurry may include 10 to 20 parts by weight of the filling element-containing salt, 80 to 90 parts by weight of the solvent, and 20 to 30 parts by weight of the binder.
[41] In the filling element-containing slurry according to one exemplary embodiment, the copper salt may include CuCl, Cu-acetate, Cul, CuS04, and the like; the indium salt may include In(N03)3, In2(S04)3, In-acetate, and the like; the gallium salt may include
GaCl3, Gal3, Ga(N03)3, Ga-acetate, and the like; the zinc salt may include ZnCl2,
Zn(N03)2, Znl2, and the like; and the tin salt may include SnCl4 and the like.
[42] In another exemplary embodiment, the filling element-containing slurry may further include a selenium compound such as Se02, SeCl4, selenourea, and the like.
[43] Next, the CIS slurry is mixed with the filling element-containing slurry to prepare a slurry mixture in Step 4.
[44] Next, the slurry mixture is coated onto a substrate to form a CIS thin film, which in turn is subjected to heat treatment, in Step 5.
[45] In this invention, when forming the CIS thin film using the slurry mixture, non- vacuum coating is employed. The non-vacuum coating may be any non-vacuum coating method known in the art, for example, spraying, ultrasonic spraying, spin coating, doctor blade coating, screen printing, inkjet printing, and the like. As such, the CIS thin film may be formed by non-vacuum coating, thereby reducing manufacturing costs.
[46] After forming the CIS thin film by coating the slurry mixture in a non-vacuum state, the thin film may be further subjected to drying to remove the alcohol solvent and the binder. Coating of the slurry mixture and drying are repeated twice or three times, thereby forming a CIS thin film having a desired thickness.
[47] Then, the CIS thin film is subjected to heat treatment. In this embodiment, heat
treatment of the CIS thin film is performed at 400 to 550°C, which is lower than the temperature of existing post-heat treatment for CIS thin films, while supplying Se vapor, thereby providing a dense CIS thin film.
[48] In the process of heat treating the thin film while supplying the Se vapor, Se vapor formed by heating Se solid to evaporate the Se solid is supplied. This process can be easily performed by those skilled in the art.
[49] In another method according to the present invention, a slurry containing CIS
nanoparticles is prepared and coated onto a substrate to form a CIS thin film. Then, a slurry containing metal salts including copper, indium, gallium, zinc, tin, and the like is prepared and coated onto the CIS thin film, which in turn is subjected to heat treatment, thereby preparing a dense CIS thin film. Next, the method according to the present invention will be described in more detail.
[50] As in Steps 1 and 2 of the method described above, CIS nanoparticles are prepared and dispersed together with a binder in a solvent to prepare a CIS slurry in Steps A and B.
[51] Next, the prepared CIS slurry is coated onto a substrate to form a CIS thin film in Step C.
[52] Here, the CIS slurry is coated onto the substrate by non-vacuum coating.
[53] Next, a filling element-containing salt and a binder are dissolved in a solvent to
prepare a filling element-containing slurry in Step D.
[54] The method of preparing the filling element-containing slurry is the same as the method described above.
[55] Then, a filling element-containing slurry is coated onto the CIS thin film, followed by heat treatment in Step E.
[56] The CIS thin film formed on the substrate has lots of cavities. Thus, when the filling element-containing slurry is coated thereon, filling elements such as copper, indium, gallium, zinc, tin, and the like enter the cavities, thereby making it possible to form a dense CIS thin film.
[57] Next, the CIS thin film having the filling elements placed in the cavities is subjected to heat treatment, thereby forming a higher density CIS thin film.
[58] A CIS thin film manufactured by the method according to this invention has a dense structure through heat treatment of the CIS thin film with the cavities of the thin film filled with the filling elements, as described above.
[59] Further, the present invention provides a thin film solar cell, a photo-absorption layer of which is a high density CIS thin film obtained through heat treatment of the CIS thin film with the cavities of the CIS thin film filled with the filling element.
[60] Further, the present invention provides a method of manufacturing a thin film solar cell using the CIS thin film according to the embodiments of the invention.
[61]
[62]
[63] Example 1
[64] In a glove box, 0.343 g of Cul and 0.991 g of InI3 were mixed with 30 mi of a
distilled pyridine solvent, followed by stirring for 10 minutes. After stirring for about 10 minutes, the opaque solution became transparent. Then, the mixture of Cu and In was mixed with 0.5 g of Na2Se dissolved in 20 mC of distilled methanol. The resultant has an atomic ratio of Cu : In : Se of 0.9 : 1 : 2. Then, the mixture of methanol/pyridine was reacted for 1 minute while being mechanically stirred in an ice bath at 0°C, thereby preparing CIGS nanoparticles. The prepared CIGS colloid was subjected to cen- trifugation for about 30 minutes at 4000 rpm and ultrasonic treatment for 5 minutes, followed by washing with distilled methanol. This process was repeated to completely remove by-products and pyridine, thereby preparing highly pure CIS nanoparticles.
[65] 0.3 g of the prepared CIS nanoparticles and 0.3 g of propylene glycol was dissolved in 1.2 g of methanol, followed by ultrasonic treatment for 60 minutes, thereby preparing a CIS slurry. Then, 0.15 g of Cu(N03)2, 0.184 g of InCl3, and 2 ml of propylene glycol were mixed in 8 ml of ethanol, and stirred for 60 minutes, thereby preparing a filling element-containing slurry. The CIS slurry was mixed with the filling element-containing slurry, followed by ultrasonic treatment for 60 minutes, thereby preparing a slurry mixture. The prepared slurry mixture was coated onto a glass substrate by doctor blade coating, followed by drying the substrate at 60°C for 5 minutes and at 180°C for 2 minutes on a hot plate to remove the alcohol solvent and the binder. Such a coating and drying process was repeated three times to form a CIS thin film on the substrate. Then, the film was subjected to heat treatment while supplying Se vapor at a substrate temperature of 400°C, thereby preparing a high density CIS thin film.
[66]
[67] Example 2
[68] CIS nanoparticles were prepared by the same process as in Example 1. Then, 0.3 g of the prepared CIS nanoparticles and 0.3 g of propylene glycol was dissolved in 1.2 g of methanol, followed by ultrasonic treatment for 60 minutes, thereby preparing a CIS slurry. The CIS slurry was coated onto a glass substrate by doctor blade coating, followed by drying the substrate at 60°C for 5 minutes and at 180°C for 2 minutes on a hot plate to remove the alcohol solvent and the binder. Such a coating and drying process was repeated three times to form a CIS thin film on the substrate. Then, 0.15 g of Cu(N03)2, 0.184 g of InCl3, and 2 ml of propylene glycol were mixed in 8 ml of ethanol, and stirred for 60 minutes, thereby preparing a filling element-containing slurry, which in turn was coated onto the CIS thin film, followed by drying the thin film at 60°C for 5 minutes and at 180°C for 2 minutes on a hot plate to remove the alcohol solvent and the binder. Then, the thin film was subjected to heat treatment while supplying Se vapor at a substrate temperature of 400°C, thereby preparing a high density CIS thin film. Fig. 1 is a scanning electronic micrograph (SEM) image of a side section of the CIS thin film manufactured according to Example 2.
[69]
[70] Comparative Example 1
[71] CIS nanoparticles were prepared by the same process as in Example 1. Then, 0.3 g of the prepared CIS nanoparticles and 0.3 g of propylene glycol were dissolved in 1.2 g of methanol, followed by ultrasonic treatment for 60 minutes, thereby preparing a CIS slurry. The CIS slurry was coated onto a glass substrate by doctor blade coating, followed by drying the substrate at 60°C for 5 minutes and at 180°C for 2 minutes on a hot plate to remove the alcohol solvent and the binder. Such a coating and drying process was repeated three times to form a CIS thin film on the substrate. Fig. 2 is an SEM image of a side section of the CIS thin film manufactured according to Comparative Example 2.
[72]
[73] Referring to Figs. 1 and 2, it can be seen that the CIS thin film prepared in Example 2 is denser than the CIS thin film prepared in Comparative Example 1 in which the filling element-containing slurry was not coated to the thin film. Therefore, it can be seen that the CIS thin film formed by the method according to the present invention has a denser structure even when the thin film is subjected to heat treatment at a lower temperature than that of existing heat treatment.
[74] Although some embodiments have been described herein, it should be understood by those skilled in the art that these embodiments are given by way of illustration only, and that various modifications, variations, and alterations can be made without departing from the spirit and scope of the invention. Therefore, the scope of the invention should not be limited only by the accompanying claims and equivalents thereof.

Claims

Claims
A method of manufacturing a high density CIS thin film, comprising: preparing CIS nanoparticles;
dispersing the CIS nanoparticles and dissolving a binder in a solvent to prepare CIS slurry;
dissolving a filling element-containing salt and a binder in a solvent to prepare a filling element-containing slurry;
mixing the CIS slurry and the filling element-containing slurry to prepare a slurry mixture; and
coating the slurry mixture onto a substrate to form a CIS thin film, followed by heat treatment.
A method of manufacturing a high density CIS thin film, comprising: preparing CIS nanoparticles;
dispersing the CIS nanoparticles and dissolving a binder in a solvent to prepare CIS slurry;
coating the CIS slurry onto a substrate to form a CIS thin film;
dissolving a filling element-containing salt and a binder in a solvent to prepare a filling element-containing slurry; and
coating the filling element-containing slurry onto the CIS thin film, followed by heat treatment.
The method of claim 1 or 2, wherein the CIS nanoparticles comprise
CIS nanoparticles, CIGS nanoparticles, or CZTS nanoparticles.
The method of claim 1 or 2, wherein the filling element-containing salt is a mixed salt of at least two selected from the group consisting of copper salt, indium salt, gallium salt, zinc salt, and tin salt.
The method of claim 1 or 2, wherein the filling element-containing slurry further comprises a selenium compound.
The method of claim 5, wherein the selenium compound is selected from the group consisting of Se02, SeC , and selenourea.
The method of claim 4, wherein the copper salt is selected from the group consisting of CuCl, Cu-acetate, Cul, and CuS04.
The method of claim 4, wherein the indium salt is selected from the group consisting of In(N03)3, In2(S04)3, and In-acetate.
The method of claim 4, wherein the gallium salt is selected from the group consisting of GaCl3, Gal3, Ga(N03)3 and Ga-acetate, the zinc salt is selected from the group consisting of ZnCl2, Zn(N03)2 and Znl2, and the tin salt is SnCl4. [Claim 10] The method of claim 1 or 2, wherein the solvent is an alcohol-based solvent including methanol, ethanol, phentanol, propanol, and butanol. [Claim 11] The method of claim 1 or 2, wherein the binder is selected from the group consisting of ethylene glycol, propylene glycol, ethyl cellulose, and polyvinylpyrrolidone.
[Claim 12] The method of claim 1 or 2, wherein the CIS thin film is formed by non-vacuum coating selected from the group consisting of spraying, ultrasonic spraying, spin coating, doctor blade coating, screen printing, and inkjet printing.
[Claim 13] The method of claim 1, further comprising:
drying the CIS thin film after forming the CIS thin film and before the heat treatment.
[Claim 14] The method of claim 2, further comprising:
drying the CIS thin film after forming the CIS thin film; and drying the CIS thin film after coating the filling element-containing slurry on the CIS thin film.
[Claim 15] The method of claim 1 or 2, wherein the heat treatment is selenization heat treatment performed at 400 to 550°C while supplying Se vapor. [Claim 16] A high density CIS thin film used for a photo-absorption layer of a solar cell, comprising:
filling elements placed in cavities within the CIS thin film, the filling elements being at least two elements selected from the group consisting of copper, indium, gallium, zinc, and tin.
[Claim 17] The CIS thin film of claim 16, wherein the CIS thin film is a CIS thin film, a CIGS thin film, or a CZTS thin film.
[Claim 18] The CIS thin film of claim 16, wherein the CIS thin film is subjected to heat treatment at 400 to 550°C while supplying Se vapor.
[Claim 19] A thin film solar cell comprising a high density CIS thin film as a
photo-absorption layer, the CIS thin film comprising filling elements placed in cavities within the CIS thin film, the filling elements being at least two elements selected from the group consisting of copper, indium, gallium, zinc, and tin.
[Claim 20] A method of manufacturing a thin film solar cell comprising a CIS thin film as a photo-absorption layer, the CIS thin film being formed by a method comprising:
preparing CIS nanoparticles;
dispersing the CIS nanoparticles and dissolving a binder in a solvent to prepare a CIS slurry; dissolving a filling element-containing salt and a binder in a solvent to prepare a filling element-containing slurry;
mixing the CIS slurry and the filling element-containing slurry to prepare a slurry mixture; and
coating the slurry mixture onto a substrate to form a CIS thin film, followed by heat treatment.
[Claim 21] A method of manufacturing a thin film solar cell comprising a CIS thin film as a photo-absorption layer, the CIS thin film being formed by a method comprising:
preparing CIS nanoparticles;
dispersing the CIS nanoparticles and dissolving a binder in a solvent to prepare a CIS slurry;
coating the CIS slurry onto a substrate to form a CIS thin film;
dissolving a filling element-containing salt and a binder in a solvent to prepare a filling element-containing slurry; and coating the filling element-containing slurry onto the CIS thin film, followed by heat treatment.
PCT/KR2011/005306 2010-07-20 2011-07-19 Method of manufacturing high density cis thin film for solar cell and method of manufacturing thin film solar cell using the same Ceased WO2012011723A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/695,627 US8569102B2 (en) 2010-07-20 2011-07-19 Method of manufacturing high density CIS thin film for solar cell and method of manufacturing thin film solar cell using the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2010-0069923 2010-07-20
KR1020100069923A KR101129194B1 (en) 2010-07-20 2010-07-20 Preparation method for cis-based compound thin film with high density and preparation method for thin film solarcell manufactured by using the cis-based compound thin film

Publications (2)

Publication Number Publication Date
WO2012011723A2 true WO2012011723A2 (en) 2012-01-26
WO2012011723A3 WO2012011723A3 (en) 2012-05-10

Family

ID=45497288

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2011/005306 Ceased WO2012011723A2 (en) 2010-07-20 2011-07-19 Method of manufacturing high density cis thin film for solar cell and method of manufacturing thin film solar cell using the same

Country Status (3)

Country Link
US (1) US8569102B2 (en)
KR (1) KR101129194B1 (en)
WO (1) WO2012011723A2 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103014643A (en) * 2012-12-11 2013-04-03 中国科学院电工研究所 Method for preparing light absorption layer of CIGS (Copper, Indium, Gallium and Selenium) thin film solar cell
CN103060861A (en) * 2013-02-03 2013-04-24 电子科技大学 Method for preparing copper-zinc-tin-sulfur film through co-electrodeposition
WO2013115582A1 (en) * 2012-02-02 2013-08-08 한국에너지기술연구원 Method for manufacturing photovoltaic ci(g)s-based thin film using flux having low melting point, and ci(g)s-based thin film manufactured by same
CN103738928A (en) * 2014-01-16 2014-04-23 广西大学 Method for recycling selenium in electrolytic manganese anode slime through ultrasonic enhancement
WO2015036763A1 (en) * 2013-09-13 2015-03-19 Nanoco Technologies Ltd Inorganic salt-nanoparticle ink for thin film photovoltaic devices and related methods
CN109148625A (en) * 2018-05-17 2019-01-04 中国科学院物理研究所 Copper zinc tin sulfur selenium thin-film solar cells and preparation method thereof

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2949773B1 (en) * 2009-09-10 2016-01-01 Univ Toulouse 3 Paul Sabatier SOLID MATERIAL IN THE DIVIDED STATE, METHOD OF MANUFACTURING SUCH MATERIAL AND USE OF SUCH MATERIAL IN A PHOTOVOLTAIC CELL
KR101322681B1 (en) 2012-04-16 2013-10-30 한국과학기술원 Czts thin film prepared by electrostatic spray and preparing method of the same
KR101388451B1 (en) * 2012-08-10 2014-04-24 한국에너지기술연구원 Preparation method of ci(g)s-based thin film with decreased carbon layers, ci(g)s-based thin film prepared by the same, and solar cell including the same
KR101463327B1 (en) * 2013-01-31 2014-12-03 영남대학교 산학협력단 Preparation Method of Copper Indium Diselenide Thin Film for Solar Cell Using Spray Process
US9105798B2 (en) * 2013-05-14 2015-08-11 Sun Harmonics, Ltd Preparation of CIGS absorber layers using coated semiconductor nanoparticle and nanowire networks
KR101583026B1 (en) * 2013-10-31 2016-01-08 재단법인대구경북과학기술원 A method for preparing CZTS thin film for solar cell
JP6293710B2 (en) 2015-07-22 2018-03-14 国立大学法人名古屋大学 Semiconductor nanoparticles and method for producing the same
CN109205576B (en) * 2018-11-30 2022-01-11 武汉理工大学 Room-temperature ultra-fast preparation method of copper-based chalcogenide solid solution
CN109817733A (en) * 2018-12-26 2019-05-28 北京铂阳顶荣光伏科技有限公司 A kind of preparation method of copper-zinc-tin-sulfur film solar cell absorbed layer
CN112144086B (en) * 2020-09-24 2021-12-14 昆明理工大学 A method for preparing selenide semiconductor by vacuum electrochemical deposition
CN115274998B (en) * 2022-07-11 2024-07-02 上海应用技术大学 Preparation method of flexible Cu-Se nanowire/methylcellulose composite thermoelectric film

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6126740A (en) * 1995-09-29 2000-10-03 Midwest Research Institute Solution synthesis of mixed-metal chalcogenide nanoparticles and spray deposition of precursor films
JPH10150212A (en) 1996-11-20 1998-06-02 Matsushita Electric Ind Co Ltd Precursor for forming semiconductor thin film and method for producing semiconductor thin film
JPH10219472A (en) 1997-02-04 1998-08-18 Shinto Paint Co Ltd Forming method of compound semiconductor thin film
WO2001078154A2 (en) * 2000-04-10 2001-10-18 Davis, Joseph & Negley Preparation of cigs-based solar cells using a buffered electrodeposition bath
FR2849450B1 (en) * 2002-12-26 2005-03-11 Electricite De France METHOD FOR REGENERATING AN ELECTROLYSIS BATH FOR MANUFACTURING THIN FILM COMPOUND I-III-VI2
US7618838B2 (en) * 2005-04-25 2009-11-17 The Research Foundation Of State University Of New York Hybrid solar cells based on nanostructured semiconductors and organic materials
US20070151862A1 (en) * 2005-10-03 2007-07-05 Dobson Kevin D Post deposition treatments of electrodeposited cuinse2-based thin films
CA2652713A1 (en) * 2006-05-19 2008-02-21 Purdue Research Foundation Rapid synthesis of ternary, binary and multinary chalcogenide nanoparticles
KR100909179B1 (en) * 2006-07-24 2009-07-22 주식회사 엘지화학 Method for manufacturing a CIS-based solar cell absorption layer
KR101144807B1 (en) 2007-09-18 2012-05-11 엘지전자 주식회사 Ink For Solar Cell And Manufacturing Method Of The Ink, And CIGS Film Solar Cell Using The Ink And Manufacturing Method Therof
US8236599B2 (en) * 2009-04-09 2012-08-07 State of Oregon acting by and through the State Board of Higher Education Solution-based process for making inorganic materials
KR20110060211A (en) * 2009-11-30 2011-06-08 에스케이이노베이션 주식회사 Method for producing CIS light absorbing layer by selenization
KR20110065596A (en) * 2009-12-10 2011-06-16 에스케이이노베이션 주식회사 Method of manufacturing CIKS light absorbing layer using selenium solution
KR101075873B1 (en) 2010-10-04 2011-10-25 한국에너지기술연구원 Method for producing a copper indium selenium or copper indium gallium selenium thin film using a paste or ink

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013115582A1 (en) * 2012-02-02 2013-08-08 한국에너지기술연구원 Method for manufacturing photovoltaic ci(g)s-based thin film using flux having low melting point, and ci(g)s-based thin film manufactured by same
CN104094412A (en) * 2012-02-02 2014-10-08 韩国能源技术研究院 Method for manufacturing photovoltaic ci(g)s-based thin film using flux having low melting point, and ci(g)s-based thin film manufactured by same
CN103014643A (en) * 2012-12-11 2013-04-03 中国科学院电工研究所 Method for preparing light absorption layer of CIGS (Copper, Indium, Gallium and Selenium) thin film solar cell
CN103060861A (en) * 2013-02-03 2013-04-24 电子科技大学 Method for preparing copper-zinc-tin-sulfur film through co-electrodeposition
WO2015036763A1 (en) * 2013-09-13 2015-03-19 Nanoco Technologies Ltd Inorganic salt-nanoparticle ink for thin film photovoltaic devices and related methods
JP2016533038A (en) * 2013-09-13 2016-10-20 ナノコ テクノロジーズ リミテッド Inorganic salt nanoparticle inks for thin film photovoltaic devices and related methods
US9960314B2 (en) 2013-09-13 2018-05-01 Nanoco Technologies Ltd. Inorganic salt-nanoparticle ink for thin film photovoltaic devices and related methods
CN103738928A (en) * 2014-01-16 2014-04-23 广西大学 Method for recycling selenium in electrolytic manganese anode slime through ultrasonic enhancement
CN109148625A (en) * 2018-05-17 2019-01-04 中国科学院物理研究所 Copper zinc tin sulfur selenium thin-film solar cells and preparation method thereof

Also Published As

Publication number Publication date
US20130045565A1 (en) 2013-02-21
WO2012011723A3 (en) 2012-05-10
KR20120015367A (en) 2012-02-21
KR101129194B1 (en) 2012-03-26
US8569102B2 (en) 2013-10-29

Similar Documents

Publication Publication Date Title
US8569102B2 (en) Method of manufacturing high density CIS thin film for solar cell and method of manufacturing thin film solar cell using the same
Wang et al. Fabrication of a Cu2ZnSn (S, Se) 4 photovoltaic device by a low-toxicity ethanol solution process
CN104704617B (en) Thin-film photovoltaic devices of the manufacture added with potassium
CN103069572B (en) Ink for producing compound semiconductor thin film, compound semiconductor thin film obtained using the ink, solar cell including the compound semiconductor thin film, and method for producing the solar cell
US20090260670A1 (en) Precursor ink for producing IB-IIIA-VIA semiconductors
Liu et al. Butyldithiocarbamate acid solution processing: its fundamentals and applications in chalcogenide thin film solar cells
KR102037130B1 (en) Inorganic Salt-Nanoparticle Ink for Thin Film Photovoltaic Devices and Related Methods
CN102458832A (en) Thin Films for Photovoltaic Cells
CN106233470B (en) The preparation method of the light absorbing layer of thin-film solar cells and the thin-film solar cells for utilizing it
US8815123B2 (en) Fabrication method for ibiiiavia-group amorphous compound and ibiiiavia-group amorphous precursor for thin-film solar cells
Hossain et al. Ecofriendly and nonvacuum electrostatic spray-assisted vapor deposition of Cu (In, Ga)(S, Se) 2 thin film solar cells
KR101865239B1 (en) Cigs nanoparticle ink formulation having a high crack-free limit
JP5874645B2 (en) Compound semiconductor thin film solar cell and method for manufacturing the same
WO2010141863A2 (en) Solution-processed inorganic photo-voltaic devices and methods of production
WO2012161402A1 (en) Method of manufacturing cis-based thin film having high density
Tang et al. In situ preparation of CuInS 2 films on a flexible copper foil and their application in thin film solar cells
US9496449B2 (en) Method for manufacturing CI(G)S-based thin film comprising Cu-Se thin film using Cu-Se two-component nanoparticle flux, and CI(G)S-based thin film manufactured by the method
Xue et al. Fabrication of Cu2ZnSn (SxSe1− x) 4 solar cells by ethanol-ammonium solution process
KR101137434B1 (en) Preparation method for cis-based compound thin film by using rapid thermal processing and preparation method for thin film solarcell manufactured by using the cis-based compound thin film
WO2013008512A1 (en) Compound semiconductor solar cell material, and solar cell using same
Suchikova et al. Thin CIGS Films Obtained by Spray Pyrolysis
HK1222408B (en) Cigs nanoparticle ink formulation having a high crack-free limit
KR20140099346A (en) Preparation Method of Copper Indium Diselenide Thin Film for Solar Cell Using Spray Process
CN105190913A (en) Method for forming chalcopyrite light absorption layer
KR20140099347A (en) Preparation Method of Copper Selenide Thin Film for Solar Cell Using Continuous Flow Reaction Process

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11809850

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 13695627

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11809850

Country of ref document: EP

Kind code of ref document: A2