1. Field of the Invention
The present invention relates generally to photovoltaic devices and, more specifically, to deposition of photovoltaic material on an interfacial wetting layer.
2. Description of the Prior Art
Cu(In-xGax)Se2, (0≦x≦1) (CIGS) has been established as a promising material for thin film photovoltaics, with record laboratory power conversion efficiencies of ˜20%. (I. Repins et al., “19.9%-efficient ZnO/CdS/CuInGaSe2 solar cell with 81.2% fill factor,” Progress in Photovoltaics: Research and Applications, 16, 235-239 (2008)). Thin films of CIGS are typically deposited using one of several methods. Thermal co-evaporation has demonstrated the highest efficiencies in the laboratory, but sputtering precursors followed by selenization has found adoption in industry. (N. G. Dhere, “Toward GW/year of CIGS production within the next decade,” Solar Energy Materials and Solar Cells, 91, 1376-1382 (2007)). It is also possible to directly sputter the quaternary compound without post-selenization. (J. A. Frantz et al., “Cu(In,Ga)Se2 thin films and devices sputtered from a single target without additional selenization,” Thin Solid Films, 519, 7763-7765 (2011)).
Extensive research has been performed to determine the optimum growth conditions of CIGS that result in a desirable film morphology. The highest efficiency laboratory devices utilize the so-called “three-stage” process where three different compositions are co-evaporated in succession on top of a molybdenum electrical contact. Upon annealing a dense, large-grained structure emerges in the completed film. While this is practical at the laboratory scale for co-evaporation, sputtering, particularly single-target quaternary sputtering, does not natively form this desirable microstructure without extensive post processing and annealing.
The present invention pertains to the use of thin interfacial films to wet and improve the film quality of subsequently deposited photovoltaic thin films, such as Cu(In1-xGax)Se2, (0≦x−1) (CIGS). The present invention provides a method for forming a photovoltaic device by depositing at least one wetting layer onto a substrate where the wetting layer is <100 nm and sputtering a photovoltaic material onto the wetting layer where the wetting layer interacts with the photovoltaic material. Also disclosed is the related photovoltaic device made by this method.
The present system has advantages over other CIGS thin films and methods of making the CIGS thin films. The present invention can eliminate the need for post-deposition selenization and/or annealing because the desired morphology can be influenced by the interfacial layer. As a result of the elimination of post-deposition selenization and/or annealing, the present invention makes it possible to deposit on substrates that cannot tolerate high temperatures, such as plastics. Also, the present invention can make lower-cost deposition methods, such as quaternary sputtering, competitive with state-of-the-art co-evaporation. Moreover, the wetting layer of the present invention can be deposited on flexible or rigid substrates selected from several materials including plastics, metals, ceramics, and glasses. Additionally, the present invention enables deposition of CIGS and its variations including addition/substitution of S, Te, Al, Ag, and others. Furthermore, the proposed invention could enable higher efficiencies than those obtained by evaporation techniques, i.e. >21%.
These and other features and advantages of the invention, as well as the invention itself, will become better understood by reference to the following detailed description, appended claims, and accompanying drawings.
The present invention provides a method for inducing a desirable morphology in photovoltaic thin films by first depositing an interfacial wetting layer, such as In2Se3, before deposition of a photovoltaic material, such as a CIGS material. Without a wetting layer, CIGS exhibits a strong preference for island growth on molybdenum, the industry standard back electrical contact. (T. Schlenker et al., “Initial growth behavior of Cu(In,Ga)Se2 on molybdenum substrates,” Journal of Crystal Growth, 259, 47-51 (2003)). This island growth leads to smaller grains and poor electrical transport and optical performance near the Mo interface, compromising the performance of the PV device. However, with a wetting layer that has a more favorable interaction energy with CIGS, island growth can be suppressed to allow for larger grains and a more preferable morphology to grow without additional processing and expense, leading to superior device performance.
Several materials may be used for the wetting layer. In2Se3, CuSe2, Cu2Se, Ga2Se3, or any combination thereof. Ternary compounds such as CuInSe2, CuGaSe2, InxGa2-xSe3, (0≦x≦2), or any combination thereof can be used. Multiple layers, such as a stack of In2Se3, Ga2Se3, CuSe2, Cu2Se or any combination thereof can be used. Sulfide analogues, such as In2S3, Ga2S3, CuS2, Cu2S or any combination thereof can be used along with their ternary compounds, such as CuInS2, CuGaS2, InxGa2-xS3, (0≦x≦2), or any combination thereof. Sulfide-selenide compounds, such as In2Se3-xSx, (0≦x≦3), CuSe2-xSx, (0≦x≦2), Cu2Se1-xSx, (0≦x≦1) and Ga2Se3-xSx, (0≦x≦3) and related compounds, including InxGa2-xS3-ySy, (0≦x≦2, 0≦y≦3) and other similar compounds may also be used along with any combination thereof. Other materials that favorably interact with the photovoltaic material may also be used.
The composition of the interfacial layer can be varied to modify its interaction with both CIGS and molybdenum (or another electrode material). This could result in, for example, control of the subsequent CIGS morphology without changes in deposition conditions. Additionally, multiple materials could be used to form a stack of interfacial layers, or a single (or multiple) layer structure consisting of a composite material, such as a ternary compound (i.e. InxGa2-xSe3, (0≦x≦2)). The present invention is also compatible with the sulfide-selenide analogue of CIGS, Cu(In1-xGax)S2-ySey, (0≦x≦1, 0≦y≦2).
The wetting layer should be less than or equal to 100 nm. In a preferred embodiment, the wetting layer was between 10 and 20 nm. The thickness of the photovoltaic material, e.g. CIGS, is typically between 1-2 μm.
In one embodiment of the invention, the photovoltaic material is deposited by sputtering. Unlike other sputtering techniques, the present invention does not require further selenization treatment after sputtering.
A sputtering target of In2Se3 can be fabricated in-house by material synthesis and machining or commercially purchased. Deposition was carried out onto a molybdenum-coated soda lime glass substrate, where the molybdenum served as the bottom electrode (anode) of the photovoltaic device. In2Se3 was deposited onto the substrate using RF magnetron sputtering in a sputter-up geometry in an Ar atmosphere at a pressure of 1-5 mT with an energy density on the order of 0.5-2 W/cm2 with the substrate held at room temperature. The nominal thickness of the deposited In2Se3 layer was 10-20 nm. The substrate was rotated at ˜10 rpm during deposition.
Subsequently, quaternary CIGS was sputtered onto the In2Se3 layer from a single target in a similar geometry with an energy density of ˜4 W/cm2 and a chamber pressure of 1-5 mT in an Ar atmosphere. The total CIGS thickness was 1-2 μm. The substrate temperature was approximately 550° C.
The above descriptions are those of the preferred embodiments of the invention. Various modifications and variations are possible in light of the above teachings without departing from the spirit and broader aspects of the invention. It is therefore to be understood that the claimed invention may be practiced otherwise than as specifically described. Any references to claim elements in the singular, for example, using the articles “a,” “an,” “the,” or “said,” is not to be construed as limiting the element to the singular.
This Application claims priority from U.S. Provisional Application No. 61/700,901 filed on Sep. 14, 2012 by Jason D. Myers et al., entitled “Controlled Growth of Copper Indium Gallium Diselenide Thin Films Using Interfacial Wetting Layers.” The entire contents of the provisional application and all references cited throughout this application and the provisional application are incorporated herein by reference.
Number | Date | Country | |
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61700901 | Sep 2012 | US |