US20060180200A1 - Thin-film solar cell - Google Patents

Thin-film solar cell Download PDF

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US20060180200A1
US20060180200A1 US10/555,792 US55579205A US2006180200A1 US 20060180200 A1 US20060180200 A1 US 20060180200A1 US 55579205 A US55579205 A US 55579205A US 2006180200 A1 US2006180200 A1 US 2006180200A1
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ald
cigs
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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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    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a thin-film solar cell without cadmium, to a method and production line for manufacturing such cells.
  • 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.
  • 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.
  • 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)Se 2 , 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.
  • CIGS-solar cells are thin-film solar-cells with a CIGS-layer serving as absorber of sunlight. Electron-hole-pairs are generated therein.
  • 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 ⁇ m, a CIGS-layer 3 of 1,5-2 ⁇ m, a CdS buffer layer 4 with a thickness of 50 nm and a ZnO window layer 5 of 0,5-1 ⁇ m.
  • 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.
  • 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.
  • 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.
  • CBD chemical bath deposition
  • ZnO high resistivity thin layer of ZnO
  • the layered structure is patterned by mechanical scribing to open contacts for the serial interconnects
  • TCO transparent conductive oxide
  • 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.
  • the buffer layer comprises a group II-VI compound semiconductor containing hydroxyl groups.
  • An exemplary compound is Zn(O,S,OH) 2 .
  • 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 In 2 S 3 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).
  • CVD chemical vapour deposition process
  • ALE atomic layer epitaxy deposition process
  • 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.
  • 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.
  • 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.
  • Another object of the invention is to replace the toxic CdS-layer with more environmental-friendly compound.
  • 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.
  • 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.
  • FIG. 1 is a simplified sectional view of a known, typical CIGS solar cell structure
  • FIG. 2 is sectional view of a CIGS solar cell structure with two ALD buffer layers in accordance with the invention
  • 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;
  • FIG. 4 is a schematic side view of a production line for the manufacture of a solar cell in accordance with the invention.
  • FIG. 5 is an alternative embodiment of the production line shown in FIG. 4 .
  • FIG. 6 is a diagram showing the efficiency of a CIGS solar cell with two ALD buffer layers in accordance with the invention
  • 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;
  • 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
  • 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.
  • 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.
  • 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.
  • ALD atomic layer deposition
  • 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.
  • 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.
  • the function of the ZnO-layer is to physically protect the under-laying very thin Zn(O,S) layer.
  • 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.
  • 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.
  • the Zn(O,S)-layer transforms into the ZnO-layer, and vice versa Nevertheless, the Zn(O,S)-layer is integral with ZnO-layer.
  • 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.
  • 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 .
  • 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.
  • 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.
  • the ALD process chamber has sources of H 2 S, 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.
  • the ALD process camber is flushed with nitrogen gas so as to purge the reaction chamber.
  • 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.
  • the thickness of the Zn(O,S)-layer is controlled by selecting the number of cycles diethyl zinc pulses alternating with water and H 2 S.
  • Each second pulse is thus of diethyl zinc and between these pulses of H 2 O and H 2 S are injected.
  • pulses of diethyl zinc are alternating with pulses of H 2 O and H 2 S.
  • the order in which H 2 O and H 2 S alternate need not be H 2 O—H 2 S —H 2 O—H 2 S etc. but may vary.
  • one pulse of H 2 S may be followed of several pulses of H 2 O in a row.
  • the scheme according to which pulses of H 2 O and H 2 S are injected need not be regular, but may vary.
  • 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.
  • 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.
  • 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.
  • H 2 S is given in a proportion of 1 to 5 (i.e. 20%) to the total number of water and H 2 S pulses.
  • a solar cell of almost equal the same coefficient of efficiency is obtained if the proportion of H 2 S pulses to the total number of H 2 O and H 2 S pulses is 1:6 (17%).
  • Solar cells with an efficiency coefficient varying between 13-16% result if the H 2 S is given in a proportion from 10-100%, preferably in a proportion of 15-25% of the total number of water and H 2 S pulses. If the ratio of H 2 S pulses to H 2 O plus H 2 S pulses is 10% it is possible to obtain solar cells with a coefficient of efficiency in the order of about 15%. If H 2 S pulses only are given (corresponding to 100%) the resulting solar cell will have a coefficient of efficiency of 13%.
  • the first buffer layer should comprise Zn(O x ,S 1-x ), where x varies between 0 and 0,9, preferably between 0,1 and 0,7.
  • the thickness of the Zn(O,S)-layer is less than about 30 ⁇ m. Applicant has found that excellent solar cells are obtained if the thickness is so thin as just 1 nm.
  • 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.
  • the substrates 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.
  • 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 .
  • the number of H 2 S pulses is gradually decreased mono-layer for mono-layer until no H 2 S pulses is present.
  • 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.
  • 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.
  • 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.
  • the two buffer layers can be grown at this temperature.
  • 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 .
  • each ALD process chamber 13 and 15 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.
  • the first buffer layer i.e. the Zn(O,S)-layer
  • a secondary phase may develop, for example zinc hydroxide, and accordingly be present in the buffer layers.
  • the first buffer layer may comprise ALD deposited indiumsulfide In 2 S 3 and the second buffer layer the usual ALD deposited ZnO as described above.
  • the ALD deposited In 2 S 3 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 .
  • FIG. 6 is a current density (mA/cm 2 )-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 V OC of 684 mV, a fill factor FF of 74%, a short circuit current I SC of 32,0 mA/cm 2 and an efficiency of 16, 0%.
  • the solar cell was provided with an anti-reflective coating.
  • 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.
  • 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.
  • 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.
  • 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.
  • Table 2 the cell in accordance with the invention has an equal performance with the CIGS-cell using a CdS-buffer layer.

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WO2009076940A2 (de) * 2007-12-14 2009-06-25 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Verfahren zur herstellung eines eine mindestens zno enthaltende zweifach-pufferschicht aufweisenden heterokontaktes und heterokontakt mit zweifach-pufferschicht
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