US20060180200A1 - Thin-film solar cell - Google Patents

Thin-film solar cell Download PDF

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US20060180200A1
US20060180200A1 US10555792 US55579205A US2006180200A1 US 20060180200 A1 US20060180200 A1 US 20060180200A1 US 10555792 US10555792 US 10555792 US 55579205 A US55579205 A US 55579205A US 2006180200 A1 US2006180200 A1 US 2006180200A1
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layer
buffer
ald
cigs
process
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Charlotte Platzer Bjorkman
John Kessler
lars Stoit
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SOLIBRO RESEARCH AB
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SOLIBRO AB
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264Inorganic materials
    • H01L31/032Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322Inorganic 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/072Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
    • H01L31/0749Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/54Material technologies
    • Y02E10/541CuInSe2 material PV cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/52Manufacturing of products or systems for producing renewable energy
    • Y02P70/521Photovoltaic generators

Abstract

The present invention relates to thin-film solar cells of the CIGS-type. A characteristic feature of the invention is the use of two integrally formed buffer layers, a first ALD Zn(O,S) buffer layer (7) on top of the CIGS-layer (3) and a second ALD ZnO-buffer layer (8) on top of the first (7) buffer layer. Both buffer layers are deposited in the same process step using ALD (atom layer deposition). The invention also relates to a method of producing the cell and a process line for manufacturing of the cell structure.

Description

    TECHNICAL AREA
  • [0001]
    The present invention relates to a thin-film solar cell without cadmium, to a method and production line for manufacturing such cells.
  • BACKGROUND OF THE INVENTION
  • [0002]
    Solar cells provide a means to produce electric power with minimal environmental impact because it is a renewable technology. In order to become a commercial success the solar cells need to be efficient, to have low cost, to be durable, and not add other environmental problems.
  • [0003]
    Today's dominant solar cell technology is based on crystalline silicon. It fulfils many of the requirements mentioned above but can not be produced at such low cost that electricity generation in large scale is cost effective. It also requires relatively large amount of energy in the production, which is an environmental disadvantage.
  • [0004]
    Solar cells based on thin film technologies have been developed. They offer a potential of substantial cost reductions but have, in general, lower conversion efficiencies and less good durability. A very promising thin film solar cell technology is based on the semiconductor Cu(In,Ga)Se2, abbreviated CIGS, which has demonstrated high efficiencies (16,6% in small prototype modules [1]) and durability in operation. It remains to demonstrate low cost in real production.
  • [0005]
    CIGS-solar cells are thin-film solar-cells with a CIGS-layer serving as absorber of sunlight. Electron-hole-pairs are generated therein.
  • [0006]
    A typical CIGS-solar cell is shown in FIG. 1 and comprises a glass substrate 1 with a thickness of 2-3 mm, an Mo-back contact 2 with a thickness of 0,5-1 μm, a CIGS-layer 3 of 1,5-2 μm, a CdS buffer layer 4 with a thickness of 50 nm and a ZnO window layer 5 of 0,5-1 μm. An optional second buffer layer 6 may be present between the CdS buffer layer and the window layer and has a thickness of 50 nm.
  • [0007]
    The CIGS-layer is a Conductive Cu(In,Ga)(Se,S)2 compound. The CdS buffer layer serves as protection of the CIGS-layer. The window layer is a n-type conductive doped zinc oxide layer. With the CIGS-layer it forms a pn-junction and serves as a transparent front contact. The optional second buffer layer comprises non-doped ZnO. Presently its role is not fully understood. Statistically seen, solar cells with this second buffer layer exhibit better properties compared to cells with a single ZnO-layer.
  • [0008]
    The commonly used way of fabricating CIGS solar cell modules include formation of a pn-junction and front contact according to the following: (1) a buffer layer (typically 50 nm of CdS) is deposited by chemical bath deposition (CBD), (2) a high resistivity thin layer of ZnO is deposited on top of the CdS layer by sputtering, (3) the layered structure is patterned by mechanical scribing to open contacts for the serial interconnects, (4) a front contact of a transparent conductive oxide (TCO) is deposited, and (5) an additional patterning step of mechanical patterning as part of the interconnect structure.
  • [0009]
    EP-A2-0 838 863 discloses a thin-film solar cell fabricated on a glass substrate. The solar cell comprises a metallic back electrode, a light-absorbing layer having on its surface a Cu(InGa)(Se)2 layer (CIGS layer), an interfacial layer referred to as a buffer layer, a window layer and an upper electrode. The back electrode is a p-type semiconductor and the window layer is an n-type semiconductor. Between the back and upper electrodes an open circuit voltage in the order of 0,2-0,8 V is obtained when the solar cell is hit by light. Electrical current will be generated in the p-n junction between the p- and n-layers.
  • [0010]
    The buffer layer comprises a group II-VI compound semiconductor containing hydroxyl groups. An exemplary compound is Zn(O,S,OH)2.
  • [0011]
    DE 44 40 878 C2 discloses a thin-film solar cell comprising a glass substrate, a back electrode, a light absorbing layer, a front buffer layer and a window layer. The front buffer layer comprises a mixture of In(OH)3 and In2S3 and is applied in a wet process or a chemical vapour deposition process (CVD) with organo metallic compounds or with atomic layer epitaxy deposition process (ALE). The novel concept here is that the buffer layer does not contain cadmium.
  • [0012]
    To fabricate the solar cell with chemical wet process steps mixed with sputtering makes the solar cell less attractive for large scale production. To fabricate the solar cell wet processes are mixed with the co-vapour deposition process which renders the structure less attractive for large scale production.
  • [0013]
    An example of thin-film solar cells using a first CdZnS buffer layer between a CIGS-layer and a window layer is disclosed in U.S. Pat. No. 5,078,804. A second ZnO buffer layer on top of the first buffer layer and in contact with the window layer is also provided. The first CdZnS buffer layer comprises two layers, a high Zn content CdZnS layer on top of a low Zn content CdZnS layer, both of which are applied using an aqueous solution method. The second ZnO buffer layer also comprises two layers, a low resistivity ZnO layer on top of a high conductivity ZnO layer both of which are applied using sputtering in an argon or oxygen/argon atmosphere.
  • [0014]
    To manufacture the solar cell with chemical wet process steps mixed with sputtering makes the solar cell less attractive for large scale production. The use of toxic cadmium makes the cell less attractive for environmental reasons. Also handling and disposal of the hazardous wastes are costly.
  • [0015]
    U.S. Pat. No. 5,948,176 discloses a solar cell structure comprising a first active CIGS layer on top of a metal back contact. On top of the CIGS layer a buffer layer of n-type conductive doped ZnO layer is deposited by a wet process using a zinc chloride solution as doping source. A second active layer comprising ZnO is deposited on the buffer layer. The second active layer comprises a first high resistive ZnO layer and a second low resistive ZnO layer on top of which a grid of front face electrodes is sputtered.
  • [0016]
    Another example of a cadmium containing solar cell is shown in U.S. Pat. No. 4,611,091.
  • SUMMARY OF THE INVENTION
  • [0017]
    One object of the invention is to reduce the number of process steps for the manufacture of the solar cell, thereby reducing the cost involved in their manufacture.
  • [0018]
    Another object of the invention is to replace the toxic CdS-layer with more environmental-friendly compound.
  • [0019]
    Still another object of the invention is to replace the CdS-layer with a material that absorbs less of the incident light than does a CdS-layer, thereby increasing the amount of light impinging the under-laying CIGS-layer and accordingly increasing the photo current generated by the cell.
  • [0020]
    A further object of the invention is to replace the wet process for manufacture of the CdS-buffer layer with a novel process that allows for integration with the preceding (dry) vacuum deposition of the CIGS-layer and/or integration with the following (dry) sputter deposition of the high resistivity ZnO window layer.
  • [0021]
    These objects are achieved with a thin-film solar cell indicated in the preamble of claim 1, a method of producing an interfacial layer in accordance the preamble of claim 7 and a process line for manufacturing a solar cell structure in accordance with the preamble of claim 14. The characteristic features of the invention are indicated in the characterizing clause of claims 1, 7 and 14 respectively.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [0022]
    FIG. 1 is a simplified sectional view of a known, typical CIGS solar cell structure;
  • [0023]
    FIG. 2 is sectional view of a CIGS solar cell structure with two ALD buffer layers in accordance with the invention;
  • [0024]
    FIG. 3 is a sectional view of a solar cell structure in accordance with the invention wherein the lower of the two ALD buffer layers has a sulphur gradient;
  • [0025]
    FIG. 4 is a schematic side view of a production line for the manufacture of a solar cell in accordance with the invention.
  • [0026]
    FIG. 5 is an alternative embodiment of the production line shown in FIG. 4,
  • [0027]
    FIG. 6 is a diagram showing the efficiency of a CIGS solar cell with two ALD buffer layers in accordance with the invention
  • [0028]
    FIG. 7 is a diagram showing the quantum efficiency of the CIGS solar cell with two ALD buffer layers in accordance with the invention compared to a CIGS solar cell having just one CdS buffer layer;
  • [0029]
    FIG. 8 is a diagram showing the efficiency of CIGS solar cell in accordance with the invention compared to a CIGS solar cell having just one ALD Zn(O,S) buffer layer, and
  • [0030]
    FIG. 9 is a diagram showing the efficiency of CIGS solar cell in accordance with the invention compared to a CIGS solar cell having just one ALD ZnO layer, and to a CIGS solar cell having just one CdS buffer layer.
  • DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • [0031]
    A CIGS-cell in accordance with the present invention is shown in FIG. 2. It comprises the usual glass substrate 1, the back contact layer 2 of molybdenum, the CIGS-layer 3 and the window layer 5. The usual CdS-buffer layer is replaced with two buffer layers, a first buffer layer containing Zn(O,S) deposited on the CIGS-layer and a second buffer layer 8 deposited on the first one and containing ZnO.
  • [0032]
    This is done in one process step in accordance with the invention. At first the Zn(O,S)-layer is deposited by atomic layer deposition (ALD) and immediately following this the ZnO-layer is deposited by A/D in the same process chamber. In effect, it can be considered that the two layers are replaced with one single layer of Zn(O,S), where no sulphur is added during the latter part of the deposition.
  • [0033]
    It is the inventive ALD deposition in the same chamber that makes possible the combination of a Zn(O,S)-layer and a ZnO-layer.
  • [0034]
    The function of the Zn(O,S)-layer is to make the surface of the under-laying active CIGS-layer electronically passive. The CIGS-layer surface contains defects that are active unless the Zn(O,S)-layer is not present. They also have a negative influence on the properties of the under-laying CIGS-layer. The Zn(O,S)-layer will make these defects electronically passive and will to a great extent, if not completely, reduce their influence on the CIGS-layer. At present it is not fully understood what other properties and functions the Zn(O,S)-layer has.
  • [0035]
    The function of the ZnO-layer is to physically protect the under-laying very thin Zn(O,S) layer. The thickness of the Zn(O,S)-layer is less than about 30 nm (=30×10−9 m or 300 Å). Experiments have shown that the thickness of the ZnO-layer does not appear to be critical; its thickness is generally about 50-100 nm.
  • [0036]
    The ZnO- and Zn(O,S)-layers are in this embodiment of the invention two separate, distinct layers. The ZnO-layer is integrally formed with the sulphur containing Zn(O,S)-layer and vice versa. Together the two layers appear as a single unit.
  • [0037]
    In a second embodiment shown in FIG. 3 the sulphur content of the upper part of Zn(O,S)-layer gradually decreases and finally vanishes, indicating the first monolayer of a ZnO-layer of the desired thickness. In other words there is a sulphur gradient over the thickness of the combined ZnO- and Zn(O,S)-layers. In this embodiment there are no distinct layers but the Zn(O,S)-layer transforms into the ZnO-layer, and vice versa Nevertheless, the Zn(O,S)-layer is integral with ZnO-layer.
  • [0038]
    The ALD process for deposition of the Zn(O,S)- and ZnO-layers is in accordance with another aspect of the present invention integrated with a preceding process for deposition of the CIGS-layer. In FIG. 4 a production line in accordance with the invention for manufacturing a solar cell structure of the invention is shown to comprise a conventional CIGS-production line comprising inlet chamber 9, a transport and heating chamber 10, a CIGS-process chamber 11, a transport and cooling chamber 12, and an outlet lock chamber 13. In accordance with the invention the lock chamber is used as ALD process chamber for deposition of the ZnO- and Zn(O,S)-layers. Following the ALD process chamber there is an optional exit lock 14. The exit lock may also be a part of the ALD chamber.
  • [0039]
    Substrates provided with the sputtered back contact Mo-layer are loaded one at a time into the inlet chamber. In the transport chamber they are accelerated and heated to about 500° C. They will thereby arrive in a serial stream, close together, to the CIGS-process chamber where they are deposited in sequence in line. The CIGS-process chamber has sources of Cu, In, Ga and Se for deposition of the CIGS-layer by vapour deposition. After growing the CIGS-layer to the desired thickness the substrates enter the transport and cooling chamber where they are cooled to the desired ALD-process temperature of about 120° C. in vacuum or in an inert environment before they enter the ALD-process chamber. In the ALD process chamber the substrates are processed in parallel as indicated in FIG. 4, or one by one.
  • [0040]
    The ALD process chamber has sources of H2S, diethyl zinc and water. Each source comprises a valve through with the corresponding gaseous compound is injected into the process chamber for a predetermined time. A “pulse” of the corresponding gaseous compound will thus be given.
  • [0041]
    Before the ALD process starts, the ALD process camber is flushed with nitrogen gas so as to purge the reaction chamber.
  • [0042]
    The ALD process starts by injecting a pulse of diethyl zinc. On the surface of the CIGS-layer a monolayer of zinc containing molecules is absorbed. Thermodynamically the process is so controlled that a thin monolayer of Zn molecules will result at the temperature existing; no further mono layers will result even if additional diethyl zinc pulses are given.
  • [0043]
    Next a pulse of H2O or H2S is injected. Following this another pulse of diethyl zinc is injected. Next a pulse of H2O or H2S is given. This will result in the growth of oxygen and sulphur on the monolayer containing zinc molecules. A first monolayer of Zn(O,S) results.
  • [0044]
    These steps are cycled to grow additional Zn(O,S) mono-layers on top of each other until the first Zn(O,S)-layer of the desired thickness is obtained. The mono-layers will grow in a very controlled manner and they grow over edges down into pits and irregularities that may exist in the CIGS-layer.
  • [0045]
    The thickness of the Zn(O,S)-layer is controlled by selecting the number of cycles diethyl zinc pulses alternating with water and H2S.
  • [0046]
    Each second pulse is thus of diethyl zinc and between these pulses of H2O and H2S are injected. Expressed in another way one can say that pulses of diethyl zinc are alternating with pulses of H2O and H2S. The order in which H2O and H2S alternate need not be H2O—H2S —H2O—H2S etc. but may vary. For example one pulse of H2S may be followed of several pulses of H2O in a row. Further, the scheme according to which pulses of H2O and H2S are injected need not be regular, but may vary.
  • [0047]
    Although not described above it should be understood that the ALD process chamber has to be cleaned before a pulse of a new compound is injected. To this end the ALD process chamber is flushed with nitrogen gas.
  • [0048]
    Applicant has found that the first pulses of diethyl zinc may not adhere to the CIGS-layer. For this reason it is important to prevent the substrates from being exposed to the atmosphere during their transport from the CIGS process chamber to the ALD process chamber.
  • [0049]
    It appears to exist an incubation time until the Zn(O,S)-layer starts to grow on the CIGS-layer. It is vital that each pulse of a compound shall cover the entire area of the substrate and be allowed to react with the uppermost monolayer thereon. The reaction will saturate if the pulse is sufficiently long. Therefore the duration of each pulse must be adapted to achieve this. Once a monolayer starts to grow it will grow to the same thickness over the entire surface of the under-laying layer. The reaction is thus self-regulating and the process is cycled until the desired thickness of the Zn(O,S)-layer is achieved.
  • [0050]
    Applicant has found that a solar cell with having a coefficient of efficiency of 16% results if the following scheme is followed: every second pulse is always diethyl zinc; between the zinc pulses a total of five pulses of H2O and H2S are given, four of these being H2O and one being H2S. For example:
    Zn—H2O—Zn—H2O—Zn—H2O—Zn—H2O—Zn—H2S—Zn— etc.
  • [0051]
    With the indicated figures H2S is given in a proportion of 1 to 5 (i.e. 20%) to the total number of water and H2S pulses. A solar cell of almost equal the same coefficient of efficiency is obtained if the proportion of H2S pulses to the total number of H2O and H2S pulses is 1:6 (17%).
  • [0052]
    Solar cells with an efficiency coefficient varying between 13-16% result if the H2S is given in a proportion from 10-100%, preferably in a proportion of 15-25% of the total number of water and H2S pulses. If the ratio of H2S pulses to H2O plus H2S pulses is 10% it is possible to obtain solar cells with a coefficient of efficiency in the order of about 15%. If H2S pulses only are given (corresponding to 100%) the resulting solar cell will have a coefficient of efficiency of 13%.
  • [0053]
    Applicant has thus found that the first buffer layer should comprise Zn(Ox,S1-x), where x varies between 0 and 0,9, preferably between 0,1 and 0,7.
  • [0054]
    Another way of expressing the manner in which the Zn(O,S) buffer layer is grown is to say that pulses of diethyl zinc alternate with pulses of water; some of the latter being replaced with pulses of hydrogen sulphide. Thus, by varying the proportion of H2S pulses the properties of the resulting solar cell is controlled.
  • [0055]
    As indicated above the thickness of the Zn(O,S)-layer is less than about 30 μm. Applicant has found that excellent solar cells are obtained if the thickness is so thin as just 1 nm.
  • [0056]
    When the Zn(O,S)-layer of the predefined thickness has been grown the process is repeated, now without any pulses of H2S, and the process continues to generate ZnO. Giving alternate pulses of diethyl zinc and water a first mono-layers of ZnO is grown on top of the surface of the Zn(O,S)-layer. Continuing to give alternate pulses of diethyl zinc and water additional mono-layers of ZnO will grow on top of each other and the process is cycled until a ZnO-layer of the desired thickness results.
  • [0057]
    Generally speaking the layers will grow at a controlled speed when the above indicated ALD process is followed. The duration of the pulses will depend on the volume of the ALD process chamber.
  • [0058]
    After completion of the ZnO-layer the substrates are transported to the exit lock from which they are delivered to a patterning station which is followed by a station for depositing the front contact and to a station for the additional patterning step as mentioned in the introductory portion of the description.
  • [0059]
    The above described ALD method is well suited for deposition of the combined Zn(O,S) and ZnO sulphur gradient layer shown in FIG. 3. At the end of the process for growing the Zn(O,S)-layer the number of H2S pulses is gradually decreased mono-layer for mono-layer until no H2S pulses is present. Finally diethyl zinc pulses alternating with water pulses only are injected thereby continuing to build ZnO-monolayers on top of each other until the desired thickness of the ZnO-layer is achieved.
  • [0060]
    The process line described above is harmonized in that the vacuum deposition process for growing the CIGS-layer and the ALD processes for growing the two Zn(O,S) and ZnO-layers all are dry processes.
  • FURTHER EMBODIMENTS OF THE INVENTION
  • [0061]
    Instead of diethyl zinc it is possible to use dimethyl zinc or another organo metallic zinc compound. It is also possible to use a organo metallic indium compound.
  • [0062]
    Applicant has found that if the substrates in the ALD chamber have a temperature of about 120° C. the two buffer layers can be grown at this temperature.
  • [0063]
    The Zn(O,S)-layer can be deposited at a temperature of 160° C., and the ZnO-layer at 120° C. Although a temperature of 120° C. of the substrates in the ALD process chamber is preferred, the two buffer layers may be deposited at a temperature as high as about 250° C. and it may also be as low as 100° C. A preferred temperature range is 100-130° C. for the two buffer layers 7, 8.
  • [0064]
    In an alternate embodiment of the process line shown in FIG. 5, there are two separate ALD process chambers 13 and 15 for the deposition of the respective buffer layers 7 and 8. If the two buffer layers are deposited at different temperatures each ALD process chamber is held at the respective temperature. This will increase the throughput since the cooling time of the substrates will be reduced compared to the case in which the substrates are allowed to cool in the same chamber before the ZnO-layer is deposited.
  • [0065]
    Above it has been indicated that the first buffer layer, i.e. the Zn(O,S)-layer, contains zincoxysulfide. During the ALD deposition process a secondary phase may develop, for example zinc hydroxide, and accordingly be present in the buffer layers.
  • [0066]
    According to a further embodiment of the invention the first buffer layer may comprise ALD deposited indiumsulfide In2S3 and the second buffer layer the usual ALD deposited ZnO as described above. The ALD deposited In2S3 is manufactured in the same manner as described above, replacing the diethyl zinc pulses with a organo metallic indium compound such as indium acetyl acetonate, In(acac)3.
  • [0067]
    FIG. 6 is a current density (mA/cm2)-voltage (V) graph of a solar cell provided with a first Zn(O,S)-buffer layer and a second ZnO-buffer layer in accordance with the invention. Characteristic properties of the cell is a open circuit voltage VOC of 684 mV, a fill factor FF of 74%, a short circuit current ISC of 32,0 mA/cm2 and an efficiency of 16, 0%. The solar cell was provided with an anti-reflective coating. These properties demonstrate that the solar cell of the invention has an equal or even superior performance than a common CIGS-cell with a CdS-buffer layer.
  • [0068]
    FIG. 7 is a diagram showing the quantum efficiency QE at different wavelengths for a solar cell provided with a first Zn(O,S)-buffer layer and a second ZnO-buffer layer in accordance with the invention compared with a common CIGS-cell having a CdS-buffer layer. None of the cells had an anti-reflective layer. As appears the solar cell in accordance with the invention has a higher QE in the blue region of the spectrum.
  • [0069]
    FIG. 8 is a graph similar to that of FIG. 6 wherein a solar cell provided with a first Zn(O,S)-buffer layer and a second ZnO-buffer layer in accordance with the invention is compared to a solar cell having only the first Zn(O,S)-buffer layer. As appears from Table 1 below the cell having two buffer layers in accordance with the invention has superior properties
    TABLE 1
    Voc Isc FF Efficiency
    (mV) (mA/cm2) (%) (%)
    U128d2, ALD 538 31.3 69.7 11.7
    Zn(O,S)/ZnO
    U128d1, ALD 389 19.3 24.7 1.9
    Zn(O,S)

    Isc is the short circuit current and FF is the fill factor.
  • [0070]
    FIG. 9 is a graph similar to the graph of FIG. 8 wherein a solar cell provided with a first Zn(O,S)-buffer layer and a second ZnO-buffer layer in accordance with the invention is compared to a common CIGS-cell using a single CdS-buffer layer and to a CIGS-cell with only the second ZnO-buffer layer. As appears from the properties listed in Table 2 below the cell in accordance with the invention has an equal performance with the CIGS-cell using a CdS-buffer layer.
    TABLE 2
    Voc Isc FF Efficiency
    (mV) (mA/cm2) (%) (%)
    ALD ZnO 401 34.4 60.7 8.4
    CdS 566 32.0 74.6 13.5
    ALD 542 34.8 71.5 13.5
    Zn(O,S)/ZnO
  • REFERENCES
  • [0000]
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Claims (15)

  1. 1-15. (canceled)
  2. 16. A thin-film solar cell comprising a thin film of p-type semiconductor Cu(In,Ga)(Se,S)2 light absorbing layer (CIGS-layer) (3) formed on a back electrode layer (2), a thin film of transparent conductive metal oxide formed over the light absorbing layer, having n-type conductivity and serving as a window layer (5) and electrode, and an interfacial layer (6) between the window layer and the CIGS-layer characterized by said interfacial layer comprising a first sulphur containing buffer layer (7) ALD grown on the CIGS-layer, and a second buffer layer (8) integrally formed with the first buffer layer by ALD deposition and comprising ZnO.
  3. 17. A thin-film solar cell in accordance with claim 16 characterized in that the first buffer layer (7) is ALD deposited Zn(Ox,S1-x), where x varies between 0 and 0,9, preferably between 0,1 and 0,7
  4. 18. A thin-film solar cell in accordance with claim 16 characterized in that the first buffer layer (7) is ALD deposited In2S3.
  5. 19. A thin-film solar cell in accordance with claim 17 characterized in that the thickness of the first buffer layer (7) is larger than about 1 nm and less than about 30 nm.
  6. 20. A thin-film solar cell in accordance with claim 16, characterized in that there is a graded transition of the first buffer layer (7) into the second buffer layer (8), the sulphur content of the first buffer layer gradually decreasing in a direction over its thickness.
  7. 21. A method of forming an interfacial layer between a thin film of p-type semiconductor Cu(In,Ga)(Se,S)2 light absorbing layer (CIGS-layer) (3) and a thin film of n-type conductive window layer (5) on a substrate of—a thin film solar cell structure, the method comprising the steps of vacuum deposition of the CIGS layer in a CIGS process chamber vacuum deposition of the CIGS layer in a CIGS process chamber (11), characterized by transporting the substrates with deposited CIGS layer to an ALD process chamber without exposing the substrates to the atmosphere, and transporting the substrates with deposited CIGS layer to an ALD process chamber without exposing the substrates to the atmosphere, and providing said interfacial layer in the ALD process chamber in the ALD process chamber initially by depositing a first sulphur containing buffer layer (6) on the surface of the CIGS-layer using atomic layer deposition (ALD) and finally depositing a second ZnO layer (8) on top of the first buffer layer (7) using atomic layer deposition (ALD).
  8. 22. A method in accordance with claim 21 characterized by forming the first and second buffer layers (7, 8) in one and the same ALD process chamber (13).
  9. 23. A method in accordance with claim 21 characterized by forming the first and second buffer layers in separate, but linked ALD process chambers (13, 15).
  10. 24. A method in accordance with claim 21 characterized by providing the first sulphur containing buffer layer (7) by exposing the absorbing layer (3) in the ALD reaction chamber (13) alternatively to pulses of a organo metallic zinc compound such as for example diethyl zinc or dimethyl zinc to form a zinc containing monolayer or to pulses of water and H2S so as to grow oxygen and sulphur on the zinc atoms in order to form a first monolayer which is adsorbed on top of the light absorbing layer (3), repeating said steps to grow additional sulphur containing monolayers layers on top of each other, and continuing this process until the first sulphur containing buffer layer (7) of a first predefined thickness is obtained.
  11. 25. A method in accordance with claim 24 characterized by providing pulses of H2S in a proportion of 10-100%, preferably in a proportion of 15-25%, and most preferred in a proportion of 10% to the total number water- and H2S pulses.
  12. 26. A method in accordance with claim 24 characterized by providing the second ZnO buffer layer (8) in the same manner as the first buffer (7) layer leaving out the pulses of H2S, by continuing to expose the first buffer layer in the ALD reaction chamber alternatively to gas pulses of an organo metallic zinc compound, such as for example diethyl zinc or dimethyl zinc, and pulses of water until the second ZnO buffer layer of a second predefined thickness is obtained.
  13. 27. A method in accordance with claim 26 characterized by successively decreasing said proportion of sulphur as said additional monolayers are grown so as to obtain a gradual transition of the first buffer layer (7) into the second buffer layer (8).
  14. 28. A process line for manufacturing a solar cell structure comprising a thin film of p-type semiconductor Cu(In,Ga)(Se,S)2 light absorbing layer (CIGS-layer) (3) formed on a back electrode layer (2), a thin film (5) of transparent conductive metal oxide formed over the light absorbing layer, having n-type conductivity and serving as a window layer and electrode, and an interfacial layer (6) between the window layer and the CIGS-layer, said process line comprising a vacuum deposition chamber (11) in which the CIGS layer is vacuum deposited on a substrate characterized by an ALD process chamber (13) for ALD deposition of said interfacial layer by first growing a first sulphur containing buffer layer (7) on the surface of the CIGS-layer using ALD deposition, and finally growing a second buffer layer (8) containing ZnO on top of the first buffer layer using ALD deposition, and a transport chamber (12) arranged between the vacuum deposition chamber and the ALD process chamber for transportation of solar film blanks from the vacuum deposition chamber to the ALD deposition chamber without exposing the blanks to the atmosphere and for cooling the solar film blanks from the CIGS deposition temperature to the ALD deposition temperature.
  15. 29. A process line in accordance with claim 28, characterized by an additional ALD process chamber (15) connected to said one ALD process chamber (13), said first mentioned ALD process chamber (13) being used for the ALD deposition of the first buffer layer (7) and said additional ALD process chamber (15) being used for the ALD deposition of the second buffer layer (8).
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