WO1999010932A1 - A method of manufacturing solar cells, particularly thin film solar cells, and solar cells obtained by using such a method - Google Patents
A method of manufacturing solar cells, particularly thin film solar cells, and solar cells obtained by using such a method Download PDFInfo
- Publication number
- WO1999010932A1 WO1999010932A1 PCT/NL1998/000468 NL9800468W WO9910932A1 WO 1999010932 A1 WO1999010932 A1 WO 1999010932A1 NL 9800468 W NL9800468 W NL 9800468W WO 9910932 A1 WO9910932 A1 WO 9910932A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solar cells
- substrate
- manufacturing solar
- cells according
- layer
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000010409 thin film Substances 0.000 title claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 80
- 238000000151 deposition Methods 0.000 claims abstract description 37
- 230000008021 deposition Effects 0.000 claims abstract description 34
- 239000013077 target material Substances 0.000 claims abstract description 18
- 229910052738 indium Inorganic materials 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 10
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010924 continuous production Methods 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 16
- 239000011787 zinc oxide Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- -1 polyethylene terephthalate Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229910000796 S alloy Inorganic materials 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000011669 selenium Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000004549 pulsed laser deposition Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000003667 anti-reflective effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910003070 TaOx Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
-
- 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
- H01L31/06—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 characterised by potential barriers
- H01L31/072—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 characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0749—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 characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction 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
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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 object of the present invention is to provide a method which overcomes the aforesaid drawbacks, and wherein the choice of substrate is not critical.
- a Cu-In-S alloy is used as the target in step ii).
- a Cu-In-S alloy is used as the target in step ii).
Landscapes
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to a method of manufacturing solar cells, particularly thin film solar cells, comprising a substrate on which a structure consisting of one or more layers is provided, which method comprises the steps of: i) placing the substrate into a deposition chamber; ii) placing one or more targets into said deposition chamber for the purpose of depositing on the substrate a layer consisting of a compound of several elements, namely copper-indium-sulphur (CuInS2) or a related compound wherein indium (In) can be replaced entirely or partially for gallium (Ga); iii) generating a sub-atmospheric pressure in said deposition chamber; and iv) irradiating said target(s), using a pulsed laser, in order to form a layer of target material on said substrate, wherein as the substrate, a material which is flexible at ambient temperature and one or more targets selected from the group consisting of Cu, In, S and Ga and/or alloys thereof are used, wherein steps i) - iv) are carried out in a continuous process, wherein a strip of the substrate present on a roll is led into said deposition chamber, the strip is provided with the layer of target material in said deposition chamber, after which the substrate strip provided with the layer of target material is removed from the deposition chamber. The present invention furthermore relates to a solar cell which is manufactured in this manner.
Description
A method of manufacturing solar cells, more in particular thin film solar cells, and solar cells obtained by using such a method.
The present invention relates to a method of manufacturing solar cells, more in particular thin film solar cells, comprising a substrate on which a structure consisting of one ore more layers is provided, which method comprises the steps of: i) placing the substrate into a deposition chamber; ii) placing one or more targets into said deposition chamber for the purpose of depositing on the substrate a layer consisting of a compound of several elements, namely copper-indium-sulphur (CuInS2) or a related compound wherein indium (In) can be replaced entirely or partially for gallium (Ga); iii) generating a sub-atmospheric pressure in said deposition chamber; and iv) irradiating said target(s), using a pulsed laser, in order to form a layer of target material on said substrate. The present invention furthermore relates to solar cells obtained by using the method according to the present invention.
The manufacture of solar cells by means of a pulsed laser is known per se from the article "Laser Ablation Deposition of CuInSe2 Thin Films on Silicon and Fused Silica" by J. Levoska et al , Jpa. J. Appl. Phys. Vol.32 (1993) suppl .32-3, pp.43-44. According to a method described therein, CuInSe2 thin films were deposited by an in situ process on fused silica and single crystal silicon substrates by means of an eCi excimer laser focussed on a polycrystalline target. A temperature of more than 350 °C is required for obtaining a satisfactory crystal quality, whereby it is also stated in said article that the substrate material and orientation had an effect on the structure of the films.
A similar method of manufacturing thin films for solar cells is known from the article "Preparation and properties of laser evaporated CuGa01In09Se2 thin films" by I.V. Bodnar et al, Thin Solid Films 207 (1992) Jan. 30, 54-56. According to the method described therein, CuGa01In09Se2 films having a thickness of 0.3 - 1.5 μ were deposited on a glass substrate, whereby the substrate temperature was 100 - 350 °C, in particular 250 °C, followed by annealing in air at 220 °C for 30 minutes for the purpose of improving the crystal structure thereof.
The manufacture of solar cells by means of a pulsed laser is also known from the article "Photoelectric properties of laser- deposited p-CuInSe2 layers and structures based on them" by Zaretskaya et al, Journal of Applied Spectroscopy, Vol.60, Nos.3-4, 1994. Thus, CuInSe2 films were deposited on glass substrates in an oxygen atmosphere at a temperature of 620 K, preferably 570 - 590 K, by means of a pulsed laser.
The manufacture of solar cells by means of a pulsed laser is furthermore known from the article "Optical transitions in laser- evaporated thin CuInSe2 films" by V.V. Kindyak et al, Thin Solid Films, 240 (1994) 114-115. According to such a method, CuInSe2 films were deposited in a thickness of 0.6 μm on glass substrates at an optimum substrate temperature of 375 °C in a vacuum chamber.
The manufacture of solar cells by means of a pulsed laser is furthermore known from the article "CuInSe2 thin film solar cells by pulsed laser deposition" by H. Dittrich et al , 23 D IEEE Photovoltaic Specialists Conference, May 1993, Louisville, USA, 617-620. Thus, CuInSe2 thin films were deposited on substrates of soda lime glass and Corning 7059 glass, with and without Mo coating, at a substrate temperature of 500 °C, using a pulsed Nd:YAG laser. The manufacture of solar cells by means of a pulsed laser is furthermore known from the article "Pulsed laser deposition and characterization of CuInSe2 thin films for solar cell applications" by R. Schaffler et al , Material Science Forum Vols.173-174 (1995), pp.135-140. The substrates used, in particular glass, were provided with CuInSe2 thin films at a temperature of 520 - 580 °C, using an Nd:YAG laser.
Such a method of manufacturing solar cells is also known from European patent application No.0581833. According to said method, a glass substrate is placed on a rotatable, generally cylindrical supporting element, which is disposed in a vacuum chamber. The substrate is heated to a temperature of 300 - 600 °C, rotated, and selenium, copper and indium are separately precipitated on the substrate by vapour deposition. During the rotation of the cylindrical supporting element on which the substrate is present, the basic elements selenium, copper and indium are precipitated on the substrate by vapour deposition, whereby the sources of the starting materials copper and indium are passed through the rotating, cylindrical supporting element in axial direction. The location of the source of the starting material selenium is not critical thereby. One drawback of such a method is the fact that the substrate must
be heated to a temperature of at least 300 °C, which rules out the use of thermally instable materials. In addition, the composition of the CuInSe2 layer on the substrate is liable to change, which has an adverse effect on the electric efficiency of the solar cell. Another method of manufacturing solar cells as referred to in the introduction is known from European patent application No. 0 502 148. According to the method described in said European patent application, a CuInSe2 layer is deposited on a metal substrate using electro-deposition technique. First, binary Cu-In layers are electroly- tically deposited in a galvanic bath with a base of sulpha ate, in which Cu and In ions are present and in which the element Se is present in the form of Se-powder, whereby selenium is finely dispersed into the aforesaid binary alloy by dispersion electrolysis. In order to obtain the desired ternary CuInSe2 alloy, the substrate and the layers applied thereto must be subjected to a thermal -chemical reaction. One drawback of this method is the fact that the suspended Se powder in the galvanic bath tends to settle, as a result of which the composition of the CuInSe2 layer on the substrate material will be liable to change. Another drawback is the fact that said method requires two steps, namely the galvanic deposition and the subjection to a heat treatment, so that from an economic point of view this method is not very suitable for mass production.
The object of the present invention is to provide a method which overcomes the aforesaid drawbacks, and wherein the choice of substrate is not critical. In addition to that it is desirable to deposit the layer of copper-indium-sulphur or a related compound as referred to in the introduction in a reproducible, possibly continuous process, wherein any impurities in the starting material do not affect the composition of the layer of copper-indium-sulphur or a related compound as referred to in the introduction, which is to be applied by deposition. The method as referred to in the introduction is according to the present invention characterized in that as the substrate a material which is flexible at ambient temperature and one or more targets selected from the group consisting of Cu, In, S and Ga and/or alloys thereof are used, wherein steps i) - iv) are carried out in a continuous process, wherein a strip of the substrate present on a roll is led into said deposition chamber, the strip is provided with the layer of target material in said deposition chamber, after which the substrate strip
provided with the layer of target material is removed from the depositon chamber.
The deposition of layers on a substrate material by means of a laser is known per se from International patent application 0-93/12537. Accordingto the method described in said international patent application, however, asolarcell is fabricatedwherein the characteristic layers are built up of amorphous germanium or amorphous silicon. A layered structure of solar cells as referred to therein is essentially different from the layered structure for the solar cells obtained by using the method according to the present invention, which solar cells comprise a layer of copper-indium-sulphur or a related compound. Surprisingly, the energy efficiency of a solar cell consisting of a layer of copper-indium-sulphur or a related compound is higher than that of a solar cell which is built up of amorphous germanium or amorphous silicon. Said international patent application moreover does not provide any indication that copper-indium- sulphur or a related compound can be applied to a substrate, in particular a substrate which is flexible at ambient temperature, in a continuous process by means of laser deposition.
In a preferred embodiment of the method of manufacturing solar cells according to the present invention, a Cu-In-S alloy is used as the target in step ii). When such an alloy is used, it is possible to transfer this alloy quantitatively to the substrate in substantially the same composition by means of the pulsed laser. Thus it is possible, by selecting a special target, to reproducibly transfer a desired composition of copper-indium-sulphur or a related compound to the substrate.
In another embodiment of the method according to the present invention, it is preferred to use targets of the individual elements selected from the group consisting of Cu, In, S and Ga, for example Cu, In and S, as individual elements rather than as an alloy of Cu, In and S in step ii), and subsequently deposit a layer of target material on the substrate by means of a pulsed laser. After the substrate has been provided with the individual elements, the aggregate is heated in step v) to the temperature at which an alloy is formed. Said temperature level depends on the elements deposited by means of the pulsed laser and on the alloy to be formed with said elements, and it can be determined in a simple manner by a person skilled in the art by carrying out routine experiments. It should be noted, however, that the temperature which is used in step v) must not lead to decomposition or disturbance of the
substrate. The preferred embodiment discussed above is not limited to the individual application of the elements selected from the group consisting of Cu, In, S and Ga. but it is for example also possible, in the embodiment wherein a CuInS2 layer on the substrate is desired, to irradiate an alloy of Cu and In as a first target, and to irradiate S as a second target, after which the aggregate is heated in step v) for the purpose of forming the intended CuInS2 layer on the substrate.
Experiments have shown that the layer of CuInS2 or a related compound which has been deposited by means of pulsed laser deposition may exhibit so-called micro interspaces, which leads to a reduced light trans ittance and a shorter life, which is undesirable in practice. The presence of such defects can be reduced in that the target also contains impurities such as boron, phosphor or carbon besides the desired elements. The irradiation of the target by means of the pulsed laser is preferably carried out in a hydrogen-containing atmosphere. The laser beam functions to photodissociate H2, as a result of which free radicals and other activated species are formed for the deposition. Furthermore it is desirable to generate a sub-atmospheric pressure in the deposition chamber in order to minimize contamination.
With the method according to the present invention, a material which is flexible at ambient temperature, in particular a thermoplastic plastic material, in particular polyimide. polyethylene terephthalate or PEN, is used as the substrate. Polymers of this kind are readily available on an industrial scale and they bond excellently to the layers to be applied. The use of a flexible substrate provides a very wide range of applications of the solar cells obtained with the present method. The flexible substrate material can be used on all kinds of surfaces, irrespective of their shapes and dimensions. In addition, the substrate material can be simply processed into substrate materials of smaller dimensions, so that there are no limitations to their use for generating electricity. It is also possible, however, to use a metal as the substrate, whereby the thickness of the metal is such that the substrate will be flexible at ambient temperature. A preferred material is steel, whereby a thickness of less than 3 mm is required. Another preferred substrate is copper, which conducts electricity very well, whereby the thickness of the copper must be less than 3 mm in order to ensure the flexibility
thereof. The substrate generally comprises a layer of Mo which is applied thereto, which may or may not be done by means of laser deposition.
Experiments have shown that an improved bond between the substrate and the layer of target material deposited thereon is obtained if the substrate is heated before step iv) is carried out. The temperature of the substrate is not critical, but it must be selected so that the substrate is not adversely affected, for example as a result of decomposition or cracking.
The output of the laser is adjusted so that the desired energy density on the target surface is obtained, preferably approximately 3 - 6 joule/cm2. The energy density must not be too low, because evaporation must take place from the target surface in order to obtain a desired thickness of the layer of target material on the substrate. On the other hand, the energy density must not be too high either, because this would cause the target material to deposit on the substrate in the form of large particles, which would result in a very rough microstructure on the substrate, which leads to poor electric conductivity.
In a preferred embodiment of the method of manufacturing solar cells according to the present invention, it is preferred to use a laser pulse frequency of about 12 - 50 Hz. If the laser pulse frequency is too low, the build-up of the layer of target material on the substrate will take place slowly. If on the other hand the laser pulse frequency is too high, this will have a negative influence on the evaporation process which takes place on the irradiated target, which will result in an irregular structure of the layer which is being formed on the substrate.
Steps i) - iv). and possibly step v), are carried out in a continuous process, wherein a strip of a substrate present on a roll is led into the deposition chamber. The strip is then provided with the layer of target material in a continuous process, after which the substrate strip provided with the layer of target material is removed from the deposition chamber, and. in the embodiment which comprises step v), is furthermore heated and possibly wound into a roll again. Preferably, the substrate strip provided with the layer of target material is provided with a so-called window layer, viz. a transparent layer of electrically conductive oxide, preferably ZnO. Other preferred oxides are indium tin oxide (ITO). gallium indium oxide (Galn03), Ti02 and TaOx. When indium tin oxide, for example, is to be applied by means of laser deposition, it is desirable to use a sintered mixture of ln203 and Sn02 as the target. Gallium
indium oxide exhibits a better transmittance over the entire wave length spectrum than indium tin oxide, so that the former is preferred.
In certain embodiments it is preferred to use zinc oxide doped with an element from the group III B (Ga, Al , B or In) of the Periodic System as the electrically conductive oxide. In particular aluminium doped zinc oxide exhibits great thermal stability, and the average transmittance in the visible part of the spectrum is higher than 90$. A suitable target is ZnO doped with 2 % by weight of A1203. If smooth surfaces are required, it is preferred to use gallium doped zinc oxide, whereby the average transmittance in the visible spectrum is 82$, however. A suitable target is ZnO doped with 7 % by weight of Ga203.
The deposition of such an oxide layer preferably takes place by irradiation of an oxide target with a pulsed laser. After the layer of CuInS2 or a related compound as referred to in the introduction has been deposited, a buffer layer of CdS is usually applied, after which the transparent layer of electrically conductive oxide, in particular ZnO is applied. The deposition of such a buffer layer preferably takes place by means of a pulsed laser. In certain embodiments it is desirable to use CuS as the buffer layer. A CuS buffer layer provides a better bond to a Cu-containing layer of CuInS2 deposited by laser deposition or to a layer of a related compound than does a CdS buffer layer. After the layer of an electrically conductive oxide has been deposited, an anti-reflective upper layer, in particular a layer of MgF2. may be applied on top of said layer, preferably by means of a pulsed laser. Other materials which can be suitably used for the anti -reflective layer are Ti02 and silicium nitrides.
Claims
1. A method of manufacturing solar cells, more in particular thin film solar cells, comprising a substrate on which a structure consisting of one ore more layers is provided, which method comprises the steps of: i) placing the substrate into a deposition chamber; ii) placing one or more targets into said deposition chamber for the purpose of depositing on the substrate a layer consisting of a compound of several elements, namely copper-indium-sulphur (CuInS2) or a related compound wherein indium (In) can be replaced entirely or partially for gallium (Ga); iii) generating a sub-atmospheric pressure in said deposition chamber; and iv) irradiating said target(s), using a pulsed laser, in order to form a layer of target material on said substrate, characterized in that as the substrate a material which is flexible at ambient temperature and one or more targets selected from the group consisting of Cu, In. S and Ga and/or alloys thereof are used, wherein steps i) - iv) are carried out in a continuous process, wherein a strip of the substrate present on a roll is led into said deposition chamber, the strip is provided with the layer of target material in said deposition chamber, after which the substrate strip provided with the layer of target material is removed from the deposition chamber.
2. A method of manufacturing solar cells according to claim
1, characterized in that a Cu-In-S alloy is used as a target in step ii).
3. A method according to claim 1. characterized in that targets of the individual elements selected from the group consisting of Cu, In, S and Ga are used in step ii), after which the substrate obtained in step iv) is heated in step v) so as to form the layer of CuInS2or said related compound.
4. A method according to claim 3, characterized in that step v) is carried out in a continuous process.
5. A method of manufacturing solar cells according to claims 1 - 4, characterized in that said target furthermore contains impurities such as boron, phosphor or carbon.
6. A method of manufacturing solar cells according to claims 1 - 5, characterized in that step iv) is carried out in an H2- atmosphere
7. A method of manufacturing solar cells according to claims 1 - 6, characterized in that said substrate is a thermoplastic plastic material.
8. A method of manufacturing solar cells according to claim 7. characterized in that polyimide is used.
9. A method of manufacturing solar cells according to claim 7. characterized in that polyethylene terephthalate (PET) is used.
10. A method of manufacturing solar cells according to claim 7, characterized in that PEN is used.
11. A method of manufacturing solar cells according to claims 1 - 6. characterized in that the substrate which is used is a metal having a thickness so that the substrate will be flexible at ambient temperature.
12. A method of manufacturing solar cells according to claim 11, characterized in that copper having a thickness of less than 3 mm is used.
13. A method of manufacturing solar cells according to claim
11, characterized in that strip steel having a thickness of less than 3 mm is used.
14. A method of manufacturing solar cells according to claims 1-13, characterized in that said substrate is heated before step iv) is carried out.
15. A method of manufacturing solar cells according to claim 14, characterized in that said substrate is heated to maximally 150 °C.
16. A method of manufacturing solar cells according to claims 1- 15, characterized in that step iv) is carried out with a laser output of about 3 - 6 joule/cm2.
17. A method of manufacturing solar cells according to claims 1 - 16. characterized in that step iv) is carried out at a laser pulse frequency of about 12 - 50 Hz.
18. A method of manufacturing solar cells according to claims 1 - 17, characterized in that a transparant layer of an electrically conductive oxide, which may be provided with a buffer layer, is applied to the substrate strip comprising a layer of target material after said strip has been removed from the deposition chamber.
19. A method of manufacturing solar eel1s according to claim 18. characterized in that said transparent layer of an oxide is applied by irradiation of an oxide target by means of a pulsed laser.
20. A method of manufacturing solar cells according to claim 19, characterized in that ZnO is used as said oxide.
21. A method of manufacturing solar cells according to claim
20. characterized in that zinc oxide doped with one or more group IIIB elements is used.
22. A method of manufacturing solar cells according to claim 21. characterized in that aluminium doped zinc oxide is used.
23. A method of manufacturing solar cells according to claim
21, characterized in that gallium doped zinc oxide is used.
24. A method of manufacturing solar cells according to claims 18 - 23, characterized in that CuS is used as said buffer layer.
25. A method of manufacturing solar cells according to claims 18- 23. characterized in that CdS is used as said buffer layer.
26. A solar cell obtained by carrying out the method as defined in any one of the claims 1 - 25.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU88894/98A AU8889498A (en) | 1997-08-22 | 1998-08-19 | A method of manufacturing solar cells, particularly thin film solar cells, and solar cells obtained by using such method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1006827 | 1997-08-22 | ||
| NL1006827A NL1006827C2 (en) | 1997-08-22 | 1997-08-22 | A method of manufacturing solar cells, more particularly thin film solar cells and solar cells obtained by such a method. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1999010932A1 true WO1999010932A1 (en) | 1999-03-04 |
Family
ID=19765533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/NL1998/000468 WO1999010932A1 (en) | 1997-08-22 | 1998-08-19 | A method of manufacturing solar cells, particularly thin film solar cells, and solar cells obtained by using such a method |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU8889498A (en) |
| NL (1) | NL1006827C2 (en) |
| WO (1) | WO1999010932A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6566628B2 (en) * | 1999-04-07 | 2003-05-20 | Siemens And Shell Solar Gmbh | Method and device for thin-film ablation of a substrate |
| WO2007096486A1 (en) * | 2006-02-23 | 2007-08-30 | Picodeon Ltd Oy | Solar cell and an arrangement and a method for producing a solar cell |
| CN102796988A (en) * | 2012-08-24 | 2012-11-28 | 广州金升阳科技有限公司 | Method for preparing highly ordered CuInS2 epitaxial film by using a sputtering method |
| CN103233202A (en) * | 2013-02-19 | 2013-08-07 | 广州金升阳科技有限公司 | Method for preparing CuInS2 nanorods by pulsed laser deposition |
| US20140102891A1 (en) * | 2002-09-30 | 2014-04-17 | Miasole | Manufacturing Apparatus and Method for Large-Scale Production of Thin-Film Solar Cells |
-
1997
- 1997-08-22 NL NL1006827A patent/NL1006827C2/en not_active IP Right Cessation
-
1998
- 1998-08-19 WO PCT/NL1998/000468 patent/WO1999010932A1/en active Application Filing
- 1998-08-19 AU AU88894/98A patent/AU8889498A/en not_active Abandoned
Non-Patent Citations (6)
| Title |
|---|
| BODNAR I V ET AL: "PREPARATION AND PROPERTIES OF LASER-EVAPORATED CUGA0.1IN0.9SE2 THIN FILMS", THIN SOLID FILMS, vol. 207, no. 1 / 02, 30 January 1992 (1992-01-30), pages 54 - 56, XP000355354 * |
| E.P. ZARETSKAYA ET AL.: "Photoelectric properties of laser-deposited p-CuInSe2 layers and structures based on them", JOURNAL OF APPLIED SPECTROSCOPY, vol. 60, no. 3-4, July 1994 (1994-07-01) - August 1994 (1994-08-01), pages 265 - 268, XP002063120 * |
| H. DITTRICH ET AL.: "CuInSe2 thin film solar cells by pulsed laser deposition", 23RD IEEE PHOTOVOLTAIC SPECIALISTS CONFERENCE, 10 May 1993 (1993-05-10) - 14 May 1993 (1993-05-14), LOUISVILLE, USA, pages 617 - 620, XP002063121 * |
| J. LEVOSKA ET AL.: "Laser ablation deposition of CuInSe2 thin films on silicon and fused silica", 9TH INTERNATIONAL CONFERENCE ON TERNARY AND MULTINARY COMPOUNDS. JAPANESE JOURNAL OF APPLIED PHYSICS SUPPLEMENTS, vol. 32 Suppl. 32-3, 8 August 1993 (1993-08-08) - 12 August 1993 (1993-08-12), YOKOHAMA, JP, pages 43 - 44, XP002063119 * |
| KINDYAK V V ET AL: "OPTICAL TRANSITIONS IN LASER-EVAPORATED THIN CUINSE2 FILMS", THIN SOLID FILMS, vol. 240, no. 1/02, 15 March 1994 (1994-03-15), pages 114/115, XP000434050 * |
| R.SCHÄFFLER ET AL.: "Pulsed laser deposition and characterization of CuInSe2 thin films for solar cell applications", MATERIAL SCIENCE FORUM. FIRST INTERNATIONAL SYMPOSIUM ON SEMICONDUCTOR PROCESSING AND CHARACTERIZATION WITH LASERS, vol. 173-174, 18 April 1994 (1994-04-18) - 20 April 1994 (1994-04-20), STUTTGART, DE, pages 135 - 140, XP002063122 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6566628B2 (en) * | 1999-04-07 | 2003-05-20 | Siemens And Shell Solar Gmbh | Method and device for thin-film ablation of a substrate |
| US20140102891A1 (en) * | 2002-09-30 | 2014-04-17 | Miasole | Manufacturing Apparatus and Method for Large-Scale Production of Thin-Film Solar Cells |
| WO2007096486A1 (en) * | 2006-02-23 | 2007-08-30 | Picodeon Ltd Oy | Solar cell and an arrangement and a method for producing a solar cell |
| CN102796988A (en) * | 2012-08-24 | 2012-11-28 | 广州金升阳科技有限公司 | Method for preparing highly ordered CuInS2 epitaxial film by using a sputtering method |
| CN102796988B (en) * | 2012-08-24 | 2014-09-03 | 广州金升阳科技有限公司 | Method for preparing highly ordered CuInS2 epitaxial film by using a sputtering method |
| CN103233202A (en) * | 2013-02-19 | 2013-08-07 | 广州金升阳科技有限公司 | Method for preparing CuInS2 nanorods by pulsed laser deposition |
| CN103233202B (en) * | 2013-02-19 | 2015-10-28 | 广州金升阳科技有限公司 | One utilizes pulsed laser deposition to prepare CuInS 2the method of nanometer rod |
Also Published As
| Publication number | Publication date |
|---|---|
| NL1006827C2 (en) | 1999-02-23 |
| AU8889498A (en) | 1999-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4739750B2 (en) | Method for producing thin-film semiconductors for photovoltaic applications based on I-III-VI2 compounds | |
| Moholkar et al. | Development of CZTS thin films solar cells by pulsed laser deposition: influence of pulse repetition rate | |
| EP2230693B1 (en) | Formation of solar cells on foil substrates | |
| JP4994032B2 (en) | IB-IIIA-VIA group quaternary alloy or method for producing a semiconductor thin film made of an alloy of five or more alloys | |
| EP0881695B1 (en) | A method of making group IB-IIIA-VIA compound semiconductor films and method of fabricating a photovoltaic device | |
| EP2197038A1 (en) | Substrate for solar cell and solar cell | |
| KR20070064345A (en) | Formation of solar cells on foil substrates | |
| TW201138144A (en) | Method of manufacturing solar cell | |
| TW201329009A (en) | Controlling alkali in CIGS thin films via glass and application of voltage | |
| JP2011513595A (en) | Method for depositing a film on a substrate | |
| KR101747395B1 (en) | Molybdenum substrates for cigs photovoltaic devices | |
| US20130109124A1 (en) | Methods of making a transparent layer and a photovoltaic device | |
| TWI558830B (en) | Method of making a transparent conductive oxide layer | |
| JPH11340482A (en) | Compound semiconductor film and manufacture of relative electronic device | |
| US8779283B2 (en) | Absorber layer for thin film photovoltaics and a solar cell made therefrom | |
| CN102782860A (en) | Photovoltaic cell having a novel TCO layer built therein | |
| WO1999010932A1 (en) | A method of manufacturing solar cells, particularly thin film solar cells, and solar cells obtained by using such a method | |
| AU2011202985A1 (en) | Transparent electrically conductive layer and method for forming same | |
| JPH07258881A (en) | Production of cuinse2 film | |
| CN101807620B (en) | Absorbed layer for thin film photovoltaic and solar cell made therefrom | |
| Lee et al. | Optical and morphological properties of Ge-incorporated polycrystalline Sb2Se3 thin-film for photovoltaic applications | |
| EP2221876A1 (en) | Absorber layer for thin film photovoltaic cells and a solar cell made therefrom | |
| Ho | Synthesis of Thin Films on Flexible Substrates: A Review | |
| AU2009200640B2 (en) | Absorber layer for thin film photovoltaics and a solar cell made therefrom | |
| Tuerxunjiang et al. | Thin-Film Solar Cells with 19% Efficiency by Thermal Evaporation of CdSe and CdTe |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AT AU AZ BA BB BG BR BY CA CH CN CU CZ CZ DE DE DK DK EE EE ES FI FI GB GE GH GM HR HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SK SL TJ TM TR TT UA UG US UZ VN YU ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| NENP | Non-entry into the national phase |
Ref country code: KR |
|
| REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
| 122 | Ep: pct application non-entry in european phase | ||
| NENP | Non-entry into the national phase |
Ref country code: CA |