EP2462626A2 - Cellules photovoltaïques à couches minces à revêtement protecteur - Google Patents
Cellules photovoltaïques à couches minces à revêtement protecteurInfo
- Publication number
- EP2462626A2 EP2462626A2 EP10807129A EP10807129A EP2462626A2 EP 2462626 A2 EP2462626 A2 EP 2462626A2 EP 10807129 A EP10807129 A EP 10807129A EP 10807129 A EP10807129 A EP 10807129A EP 2462626 A2 EP2462626 A2 EP 2462626A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- photovoltaic cell
- layer
- recited
- thin
- substrate
- 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.)
- Withdrawn
Links
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- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 6
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- 238000000231 atomic layer deposition Methods 0.000 abstract description 52
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 238000000151 deposition Methods 0.000 description 10
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- 230000008021 deposition Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
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- 229920000307 polymer substrate Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910000676 Si alloy Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 230000003287 optical effect Effects 0.000 description 3
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- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- -1 CuInSe2 Chemical class 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- 239000004642 Polyimide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920006356 Teflon™ FEP Polymers 0.000 description 1
- 229910003107 Zn2SnO4 Inorganic materials 0.000 description 1
- IQTMWNQRJYAGDL-UHFFFAOYSA-N [SeH2]=[Se] Chemical compound [SeH2]=[Se] IQTMWNQRJYAGDL-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000003877 atomic layer epitaxy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
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- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
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- 229920006254 polymer film Polymers 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
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- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for 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
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/10—Photovoltaic [PV]
-
- 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
Definitions
- This invention provides a thin-film photovoltaic cell in which one or more layers are coated by atomic layer deposition with a barrier layer of an inorganic oxide to prevent attack by moisture and/or atmospheric gases of the water-sensitive and/or oxygen-sensitive layers of the cell.
- PV cells Photovoltaic (PV) cells that convert solar radiation or light to electricity need to operate year round in outdoor conditions that are often harsh. To insure a lifetime of 25 years or more, solar cells need robust packaging. For integrating solar cells into buildings as a roof-top
- PV cells be a flexible product in roll form.
- Thin-film PV cells can be fabricated as a roll product on metal foil or plastic substrates.
- the top or front sheet for flexible PV cells, through which solar radiation is collected, must be optically transparent, weather- resistant and soil-proof, with low permeability to moisture and other atmospheric gases.
- Thin-film PV cells can be based on inorganic materials such as amorphous silicon (a-Si), cadmium telluride (CdTe) or copper indium (gallium) di-selenide (CIS/CIGS), or on emerging technologies based on dye-sensitized, organic, and nano-matehals.
- Moisture-sensitivity is an issue for all thin-film PV technologies, but is particularly acute for CIGS.
- a barrier must provide a water vapor transmission rate of less than 5x10 "4 g-H 2 O/nn 2 /clay. Despite this stringent requirement, CIGS PV cells are attractive because of their high efficiency (-20% for small laboratory- size cells).
- FIG. 1 A typical packaging scheme for thin-film PV cells on flexible substrates is illustrated in Figure 1.
- the structure is comprised of a substrate 12, which may be metal foil or polymer on which the PV cell 10 is fabricated, an encapsulant material 14, and a transparent front sheet 16. Without a moisture barrier, this structure will have a limited lifetime, typically less than 1 year for moisture-sensitive thin-film PV cells.
- the front sheet provides some moisture barrier properties, and there may also be an intervening polymer sheet 18, which may comprise one or more layers (e.g., 18a and 18b) of polymers (e.g., polyesters, fluoropolymers).
- the intrinsic permeability of polymers is, in general, too high to achieve the level of protection needed for CIGS PV cells.
- AI2O3 films via ALD processes has been disclosed for encapsulating organic light-emitting diode (OLEDs), creating potential barrier films for such devices.
- OLEDs organic light-emitting diode
- Water and ozone have each been used as the oxidizer in ALD processes.
- Encapsulation of pentacene/C ⁇ o heterojunction organic solar cells in a superstrate configuration with a layer Of AI 2 O 3 deposited by ALD has also been disclosed. In such devices, light is collected through the glass substrate.
- the present invention provides, in different embodiments, a photovoltaic cell device and a process for the manufacture thereof.
- a thin-film photovoltaic cell device comprising a substrate, a photovoltaic cell attached to the substrate, and at least one gas permeation barrier layer formed by an ALD process employing a water vapor precursor and a trimethyl aluminum reactant.
- the photovoltaic cell comprises a Cu(In, Ga)S ⁇ 2 absorber layer and a CdS window layer, and optional additional layers.
- a process for constructing a photovoltaic cell device that comprises: (i) providing a substrate; (ii) forming on the substrate a photovoltaic cell comprising a Cu(In, Ga)S ⁇ 2 absorber layer and a CdS window layer; and (iii) coating the photovoltaic cell with a gas permeation barrier layer formed by an ALD process employing a water vapor precursor and a thmethyl aluminum reactant.
- the ALD process of the invention is carried out in a reactor incorporating a vacuum chamber and comprises in sequence the steps of: (i) admitting a vapor of a precursor into the chamber; (ii) purging the vapor of the precursor from the chamber to leave a thin adsorbed layer of the precursor; (iii) introducing a reactant to the chamber under thermal conditions that promote a reaction with the precursor to form a sublayer of material of a desired gas permeation barrier layer; (iv) purging the chamber of the reactant and reaction products produced by the reaction; and (v) repeating the foregoing steps for a number of times sufficient to form a gas permeation barrier layer having a preselected thickness.
- Figure 1 illustrates a PV device of the prior art, comprising a metal foil or polymer substrate on which the PV cell is fabricated, an encapsulant material, and a transparent front sheet;
- Figure 2 illustrates a configuration of an embodiment of an ALD coated PV cell of this invention
- Figure 3 illustrates a configuration of another embodiment of an ALD coated PV cell of this invention
- Figures 4A-4D show certain configurations for chalcopyhte and CdTe solar cells
- Figure 5 illustrates a configuration for amorphous or nanocrystalline thin film silicon solar cells
- Figure 6 illustrates a top view schematic representation of the cell of the Example.
- Figure 7 is a graph of open-circuit voltage V oc vs time, showing the stability of the coated and encapsulated CIGS PV cell of the Example at 85 0 C and 85% relative humidity.
- Atomic layer deposition is a film growth method that produces films that potentially satisfy many of the criteria for low
- a description of the atomic layer deposition process can be found in "Atomic Layer Epitaxy," by Tuomo Suntola in Thin Solid Films, vol. 216 (1992) pp. 84-89.
- the ALD process permits deposition of a material layer-by-layer.
- the process is accomplished in a chamber using a two-stage reaction, and is carried out repetitively to build up layers forming a coating of the requisite thickness.
- a vapor of film precursor is introduced into the chamber. Without being bound by any theory, it is believed that a thin layer of the precursor, usually essentially a monolayer, is adsorbed on a substrate or device in the chamber.
- the term "adsorbed layer” is understood to mean a layer whose atoms are weakly bound to the surface of a substrate. Thereafter, the vapor is purged from the chamber, e.g. by evacuating the chamber or by flowing an inert purging gas, to remove any excess or un- adsorbed vapor. A reactant is then introduced into the chamber under thermal conditions that promote reaction with the adsorbed precursor to form a sublayer of the desired barrier material. The volatile reaction products and excess precursors are then pumped from the chamber.
- Additional sublayers of material are be formed by repeating the foregoing steps for a number of times sufficient to form a layer having a preselected thickness.
- Common CVD and PVD deposition methods entail initiation and film growth at discrete nucleation sites.
- the PVD method is particularly prone to creation of columnar microstructures having boundaries along which gas permeation can be facile.
- ALD can produce very thin films with extremely low gas permeability, making such films attractive as barrier layers for protecting sensitive electronic devices such as PV cells.
- ALD is a particularly attractive method for protecting moisture and/or oxygen-sensitive devices because it forms a highly conformal coating. This allows devices with complex topographies to be fully coated and protected.
- PV cells comprising one or more layers that are coated with a barrier layer formed by ALD to prevent the passage of atmospheric gases.
- a representative embodiment of such a PV cell device is shown generally at 20 in Figure 2.
- a photovoltaic cell 22 is constructed atop a flexible substrate 24, which may be made of metal or polymer.
- a protective layer 26 is applied on cell 22 using an ALD deposition process. Layer 26 is impermeable, which is to say that it reduces the permeation of atmospheric gases, including oxygen and water vapor, which are known to degrade the performance of typical PV devices, by at least a factor of 10 5 . Further protection for both ALD layer 26 and the PV cell 22 is afforded by a weather-proof top layer 28.
- Materials formed by ALD and suitable for barriers include oxides and nitrides of Groups IVB, VB, VIB, IMA, and IVA of the Periodic Table and combinations thereof. Of particular interest in this group are Si ⁇ 2 AI2O3, and Si3l ⁇ l4.
- One advantage of the oxides in this group is optical transparency which is attractive for optoelectronic devices, including photovoltaic cells, in which visible light must either exit or enter the device. It is to be understood that the term "visible light” as used herein includes electromagnetic radiation having a wavelength that falls in the infrared and ultraviolet spectral regions, as well as wavelengths generally perceptible to the human eye, all being within the operational limits of typical
- the nitrides of Si and Al are also transparent in the visible spectrum.
- the precursors and reactants used in the ALD process to form barrier materials usefully employed in the present devices can be selected from substances known to those skilled in the art and tabulated in published references such as M. Leskela and M. Ritala, "ALD precursor chemistry: Evolution and future challenges," in Journal de Physique IV, vol. 9, pp 837-852 (1999) and references therein. Water vapor or ozone is beneficially used as the precursor.
- the ALD process can be described by the overall reaction:
- reaction proceeds in two half-reactions at the surface that may be represented as:
- the ALD process may be carried out with other precursors and reactants.
- the present ALD barrier synthesis may be carried out with the PV cell held at a temperature within a range of about 50 0 C to 250 0 C. Too high temperature (>250 0 C) is found to be incompatible with processing of temperature-sensitive polymer substrates, either because of chemical degradation of the polymer(s) or disruption of the ALD coating due to large dimensional changes of the substrate. The reaction kinetics generally are found to be too slow below 50 0 C.
- a thickness range found to be suitable for barrier films is 2 nm to 100 nm. A more preferred range is 2 nm to 50 nm. Thinner layers will be more tolerant to flexing without causing the film to crack. This is important for polymer substrates where flexibility is a desired property. Film cracking will compromise barrier properties. Thin barrier films also increase transparency. There may be a minimum thickness corresponding to continuous film coverage, for which substantially all of the imperfections of the substrate are covered by the barrier film. For a nearly defect-free substrate, the threshold thickness for acceptable barrier properties is estimated to be at least 2 nm, but may be as thick as 10 nm. It has been found that a 25 nm thick ALD barrier layer is typically sufficient to reduce oxygen transport through a polymer film to a level below a measurement sensitivity of 0.0005 g-H 2 O/m 2 /day.
- the present PV cell device may include an adhesion layer interposed between the semiconductors of the photovoltaic cell and a protective ALD gas permeation barrier layer.
- the thickness of the adhesion layer is in the range of 1 nm to 100 nm.
- the material for the adhesion layer is selected from the same group as that of the barrier material.
- Aluminum oxide and silicon oxide are preferred for the adhesion layer, which may also be deposited by ALD, although other methods such as chemical and physical vapor deposition or other deposition methods known in the art may also be suitable.
- FIG. 3 Another embodiment of a thin-film PV cell device is depicted generally at 30 in Figure 3.
- a CIGS PV cell 32 is formed on a glass substrate 34 and is protected by an ALD moisture barrier coating 26.
- Cell 32 and coating 26 are encapsulated by an epoxy coating 36, which in turn is covered by a top layer 38, which may be a TEFLON® FEP 260C fluoropolymer.
- each cell device comprises a substrate, a transparent conductive oxide (TCO) layer forming a front contact (f-contact), one or more absorber layers, and a layer for a back contact (b-contact). Electric power is extracted in a conventional manner from the PV cell through connections to the f- and b-contacts, as shown by "+" and "-" indicators.
- Some cell device embodiments further comprise one or more layers selected from window layers, buffer layers, and interconnect layers, and combinations thereof.
- the substrate consists essentially of metal, polymer, or glass. Thin metal and polymer substrates have the advantage of being flexible; glass and some polymers have the advantage of being
- Suitable polymers include polyesters (e.g., PET, PEN), polyamides, polyacrylates and polyimides.
- an ALD layer can be coated on one or both sides of the substrate.
- the substrate may also include other functional coatings used to enhance the PV device's optical, electrical, or mechanical properties.
- the TCO layer typically comprises mixtures or doped oxides of In 2 O 3 , SnO 2 , ZnO, CdO, and Ga 2 O 3 , and provides a conductive pathway through which current generated by substantially the full active area of the PV cell can flow.
- Common examples in PV cells include ITO (In 2 O 3 doped with about 9 atomic % Sn) and AZO (ZnO doped with 3-5 atomic % Al).
- the absorber layer absorbs light from the incident light spectrum (400 - 1200 nm).
- Suitable absorber materials include ternary
- chalchopyrite compounds such as CuInSe 2 , CuInS 2 , CuGaSe 2 , CuInS 2 , CuGaS 2 , CuAISe 2 , CuAIS 2 , CuAITe 2 , CuGaTe 2 and combinations thereof, and CdTe and related compounds.
- the window layer is a thin semiconductor film (an n-type if the absorber is a p-type, or a p-type if the absorber is an n-type) that forms a heterojunction with the absorber layer, by which electric charges are separated by the built-in electric field at the junction.
- Suitable materials for the window layer include CdS, ZnS, ZnSe, In 2 S 3 , (Zn 1 Cd)S, and Zn(O 1 S) for a chalcopyrite absorber, and ITO, CdS and ZnO for a CdTe absorber.
- the foregoing p-n semiconductor junction structure includes an intervening i-type semiconductor, forming a p-i-n configuration.
- the layer for b-contact is typically either a TCO layer or a metal.
- the buffer layer is typically consists essentially of a transparent, electrically insulating dielectric. Suitable materials include ZnO, Ga 2 O 3 , SnO 2 , and Zn 2 SnO 4 , and mixtures thereof.
- the top of the PV cell device is configured to accept light incident in the direction indicated by the arrow onto a transparent substrate 42, which thus may be termed a superstrate because of its top location.
- TCO layer 44 provides the positive f-contact.
- a window 46 lies between TCO 44 and absorber 48.
- a metal layer 50 provides the negative b-contact, on which an ALD barrier is coated to protect the PV cell against harmful moisture and gas permeation.
- an ALD barrier is coated on the metalized TCO and/or the buffer layer.
- an ALD layer can itself be used for the buffer layer.
- top TCO layer 44 with electrodes 58 (typically formed by screen printing and firing a metal-powder paste).
- the active semiconductor window 46 and absorber layer 48 are separated from TCO 44 by buffer layer 52.
- a bottom TCO layer 54 provides the b-contact and is formed atop substrate 56.
- ALD barrier layers are also beneficial in tandem configurations, which use multiple absorbers in a stacked configuration, generally to improve conversion efficiency of the device over the entire incident spectrum.
- An ALD barrier layer can again be coated on the metalized TCO and/or buffer-window layers.
- the Figure 4D tandem configuration is constructed on substrate 56 and includes first absorber 64 and second absorber 72 in conjunction with respective buffer-window layers 62 and 70. The two absorber/buffer-window layers provide sensitivity over different spectral ranges. Light is incident through first TCO layer 44
- first absorber 64 (functioning as front contact) and first impinges on first absorber 64. Light that is not absorbed continues to propagate and reaches second absorber 72. A series electrical connection is provided by interconnect layer 66 connecting absorber 64 to second TCO layer 68. The back side of second absorber 72 is connected to metal layer 50, which provides the back contact.
- ALD layers can also be used to protect amorphous or
- nanocrystalline thin film silicon (a-Si, nc-Si) solar cells illustrates one form of a single junction solar cell, but double and triple junction cells are also known.
- One or more ALD layers are beneficially employed in each.
- Amorphous or nanocrystalline Si used in PV applications is usually an alloy with hydrogen, denoted as a-Si:H or nc-Si:H.
- Doping to produce n-type or p-type can be accomplished using the same dopants commonly used for crystalline Si.
- Suitable p-type dopants include Group III elements (e.g., B).
- Suitable n-type dopants include Group V elements (e.g., P). Alloying with Ge or C can also be used to change the optical absorption characteristics and other electrical parameters.
- Thin film a-Si and nc-Si silicon solar cells typically comprise a sequence of layers including a TCO layer 44, a p-i-n semiconductor structure 80 with a p-type Si alloy layer 82, an i-Si alloy layer 84, and an n- type Si alloy layer 86, a buffer layer 88, and a metal layer 90 for the b- contact, all formed on substrate 92.
- the same substrates and TCO materials used in the Figure 4 configurations are suitable. Tandem cells with higher efficiency are produced by repeating the layers of
- semiconductor structure 80 of the basic cell one or more times and optimizing the absorption of the stack.
- an ALD barrier layer on the metalized TCO layer can prevent moisture ingress into the PV cell.
- an ALD barrier layer can be coated on the metalized TCO and/or buffer layers.
- an ALD layer can be used for one or all of the buffer layers.
- the ALD coating can also protect the edges of the layers of the PV cell.
- ALD Barrier Deposited Directly on a CIGS Photovoltaic Cell ALD Barrier Deposited Directly on a CIGS Photovoltaic Cell.
- a photovoltaic (PV) cell device was fabricated on a 2 inch x 2 inch glass substrate using methods well-known in the art of CIGS cell fabrication.
- a top view schematic representation of the cell device 100 before the ALD deposition is shown in Figure 6.
- the sequence of layers included a molybdenum metal layer on the glass substrate 102; an absorber layer of Cu(In, Ga)S ⁇ 2 (CIGS), a thin window layer of CdS, a thin insulating buffer layer of ZnO, a transparent conducting oxide layer (TCO) of indium-tin oxide (ITO) 104, and a metal grid electrode of a Ni/AI alloy 106.
- the cell size (1 cm 2 ) was defined by the ITO layer 104 which was deposited through a 1 cm x 1 cm shadow mask.
- a 1 -2 mm wide portion 108 of the Ni/AI top electrode 106 was masked near the edge of the glass for subsequent electrical contact, and the masked CIGS PV cell was placed in a reactor (Cambridge Nanotech Savannah 200) for carrying out the ALD process.
- the reactor was continuously purged with nitrogen gas at 20 seem and pumped with a small mechanical pump to a background pressure (no reactant or precursor) of about 0.3 Torr. Nitrogen gas was used both as a carrier for the reactants and as a purging gas.
- the reactant trimethyl aluminum vapor and precursor water vapor were introduced sequentially into the reactor.
- the CIGS PV cell was dosed with water vapor carried by nitrogen gas for 15 milliseconds, followed by purging of the reactor with flowing nitrogen for 30 seconds.
- the PV cell was then dosed for 15 milliseconds with trimethyl aluminum vapor carried by nitrogen gas, followed by a 15 second purge of flowing nitrogen.
- This reaction sequence produced a layer of AI2O3 on the PV cell.
- This deposition step was repeated sequentially for 500 times
- the thickness Of AI 2 O 3 formed was determined optically on a Si witness slide to be about 55 nm, corresponding to an ALD deposition rate of about 0.11 nm per cycle.
- Teflon® FEP 200C (0.002 inches thick) was attached to the photovoltaic cell with a uv-curable epoxy encapsulant, leaving a space at the edges of the cell for attaching electrical leads.
- the Teflon FEP® acts as a weathering layer that prevents condensation of water vapor on the ALD AI 2 O 3 barrier and cell, adding further protection against degradation of the PV cell during end use.
- the encapsulated PV cell was placed in an environmental chamber and aged at 85 0 C and 85% relative humidity (RH), while simultaneously being exposed to constant illumination at 1000 VWm 2 from a solar simulator. During this test, the open circuit voltage was monitored as a function of time, yielding the results depicted in the graph of Figure 7.
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Abstract
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US23149309P | 2009-08-05 | 2009-08-05 | |
PCT/US2010/044483 WO2011017479A2 (fr) | 2009-08-05 | 2010-08-05 | Cellules photovoltaïques à couches minces à revêtement protecteur |
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JP (1) | JP2013501382A (fr) |
KR (1) | KR20120055588A (fr) |
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KR20140047113A (ko) * | 2011-08-10 | 2014-04-21 | 쌩-고벵 글래스 프랑스 | 전력 손실이 감소된 태양광 모듈 및 그의 제조 방법 |
KR101892433B1 (ko) * | 2012-12-31 | 2018-08-30 | 생-고뱅 퍼포먼스 플라스틱스 코포레이션 | 유연성 기재 상의 박막 규소질화물 장벽 층들 |
CN105229801B (zh) | 2013-02-07 | 2017-03-15 | 第一太阳能有限公司 | 窗口层上具有保护层的光伏器件及其制造方法 |
CN105161623B (zh) * | 2015-08-07 | 2018-06-08 | 常州大学 | 一种钙钛矿太阳能电池及其制备方法 |
KR20200037825A (ko) * | 2017-07-27 | 2020-04-09 | 에바텍 아크티엔게젤샤프트 | 투과 장벽 |
KR101886832B1 (ko) * | 2017-11-20 | 2018-08-08 | 충남대학교산학협력단 | 전하 선택 접합 실리콘 태양 전지 제조 방법 |
CN112526663A (zh) * | 2020-11-04 | 2021-03-19 | 浙江大学 | 一种基于原子层沉积的吸收膜及其制作方法 |
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US20090159119A1 (en) * | 2007-03-28 | 2009-06-25 | Basol Bulent M | Technique and apparatus for manufacturing flexible and moisture resistive photovoltaic modules |
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US7115304B2 (en) * | 2004-02-19 | 2006-10-03 | Nanosolar, Inc. | High throughput surface treatment on coiled flexible substrates |
JP2006140414A (ja) * | 2004-11-15 | 2006-06-01 | Matsushita Electric Ind Co Ltd | 太陽電池用基板及びこれを用いた太陽電池 |
US20070295386A1 (en) | 2006-05-05 | 2007-12-27 | Nanosolar, Inc. | Individually encapsulated solar cells and solar cell strings having a hybrid organic/inorganic protective layer |
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US7959742B2 (en) | 2007-07-11 | 2011-06-14 | Whirlpool Corporation | Outer support body for a drawer-type dishwasher |
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- 2010-08-05 KR KR1020127005664A patent/KR20120055588A/ko not_active Application Discontinuation
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US20090159119A1 (en) * | 2007-03-28 | 2009-06-25 | Basol Bulent M | Technique and apparatus for manufacturing flexible and moisture resistive photovoltaic modules |
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EP2462626A4 (fr) | 2013-10-16 |
WO2011017479A3 (fr) | 2011-06-16 |
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