This invention relates to solar cells, and, more specifically, to multi-bandgap solar photovoltaic (SPV) cells for converting solar energy to electricity.
It is well known that the most efficient conversion of radiant energy to electrical energy with the least thermalization loss in semiconductor materials is accomplished by matching the photon energy of the incident radiation to the amount of energy needed to excite electrons in the semiconductor material to transcend the bandgap from the valence band to the conduction band. However, since solar radiation usually comprises a wide range of wavelengths, use of only one semiconductor material with one band gap to absorb such radiant energy and convert it to electrical energy results in large inefficiencies and energy losses to unwanted heat.
The benefits of using tandem solar cells incorporating both wide bandgap and narrow bandgap materials have been recognized. However, such tandem solar cells have been practically realized only in expensive, Group III-V crystalline materials and in less expensive, but low-efficiency, amorphous silicon (a-Si) thin films. Until this invention, tandem solar cells have not been available in less expensive, but high-efficiency, polycrystalline or amorphous thin film semiconductor materials. Modeling and other work has shown that high efficiency, tandem solar cells could, theoretically, result from certain combinations of polycrystalline thin films, but practical limitations in conventional fabrication techniques have heretofore prevented realization of practical tandem solar cell structures with such materials. For example, modeling work reported recently in Coutts et al., “Modeled performance of polycrystalline thin-film multijunction solar cells”, Progress in Photovoltaics and Applications 10, 2002, pp. 1-9, identified optimum bandgaps for two-junction, tandem thin-film solar cells and showed that a current-matched, 28% efficient tandem solar cell is theoretically possible with a top cell absorber of 1.7 eV and a bottom-cell absorber of 1.1 eV. Coincidentally, these 1.7 eV and 1.1 eV bandgaps for a theoretical 28% efficient tandem solar cell modeled by Coutts, et al., are an ideal match with the CuInSe2 (0.95 eV)-CuGaSe2 (1.7 eV) semiconductor material system. In other words, polycrystalline solar energy absorber materials can be made in this system that have either the desired higher bandgap of 1.7 eV or the desired lower bandgap of 1.1 eV, which the modeling predicts could achieve 28% efficiency, if they could be combined together in a tandem structure. It has also been shown that single-junction, polycrystalline CuInxGa1-xSe2/CdS cells have achieved absorption efficiencies greater than 18%, and that single-junction polycrystalline CuGaSe2/CdS cells have reached efficiencies greater than 9%. See A. Contreras et al., “Progress toward 20% efficiency in Cu(In,Ga)Se2 polycrystalline thin film solar cells”, Progress in Photovoltaics and Applications 7, 1999, pp. 311-316; V. Nadenau et al., Proceedings of the 14 European Photovoltaic Solar Energy Conference, Stephens & Associates, Bedford, U.K., 1997, p. 1250. Therefore, there is a lot of incentive to put these kinds of polycrystalline or even amorphous cells together in tandem solar cells to obtain the solar energy absorption efficiencies, cost effectiveness, and other benefits indicated by the modeling.
Unfortunately, the reality is that fabrication of these as well as many other polycrystalline or amorphous thin film tandem devices is fraught with problems. One of the most pervasive of these problems, which has been considered a “show-stopping” obstacle to further commercial development of such high-efficiency, tandem, polycrystalline or amorphous solar cell devices, is that the high deposition temperatures required to grow good quality polycrystalline, thin film solar energy absorber materials, such as the polycrystalline CuInxGa1-xSe2 and CuGaSe2 materials mentioned above, cause severe degradation or destruction of previously deposited cells. Specifically, in conventional tandem solar cells, a first cell with a first bandgap is grown onto a substrate by depositing a first high temperature, polycrystalline solar energy absorber layer at temperatures above about 500° C. followed by a low-temperature window layer grown at temperatures below about 200° C. to create the p/n junction. In single junction polycrystalline or amorphous cells, such as the polycrystalline CuGaSe2/CdS and Cu(In,Ga)Se2/CdS heterojunction cells discussed above, the polycrystalline CuGaSe2 and Cu(In,Ga)Se2 absorber materials are preferably deposited at high temperatures, e.g., greater than 500° C., followed by a low temperature deposition of the CdS window layer on the CuGaSe2 and Cu(In,Ga)Se2 absorber materials to form the p/n heterojunction, preferably not more than about 200° C. The deposition of the CdS onto the polycrystalline CuGaSe2 and Cu(In,Ga)Se2 absorber materials at the lower temperature, instead of at a higher temperature, prevents the CdS from diffusing into the polycrystalline CuGaSe2 and Cu(In,Ga)Se2 materials, which would destroy the p/n heterojunction. The problem for use of these materials in a tandem cell structure arises in fabrication of the second cell over the first cell. The absorber material of the second cell, e.g., the CuGaSe2 in the system being discussed, also has to be deposited at a high temperature, e.g., 350-700° C., preferably over 500° C., so the substrate and completed first cell have to be raised to that temperature. However, the completed first cell cannot survive in that temperature, because it will cause the CdS window layer of the completed first cell to diffuse into the CuGaSe2 and Cu(In,Ga)Se2 absorber layer of the first cell and destroy the p/n heterojunction. In other words, to avoid diffusion of the window layer into the absorber layer of the first cell and consequent degradation or destruction of the p/n junction of the first cell during deposition of the second cell in a conventional tandem cell construction with polycrystalline absorber materials, the shorting junction, which is usually used between the first and second cells in current matched tandem cells, and the second cell must be deposited at temperature below about 200° C. Thus, the second or top cell used in conventional tandem cells is practically limited to materials that may be deposited at temperatures below about 200° C. so as to not destroy the first cell. Because of this problem, most proposed polycrystalline tandem devices prior to this invention have been either coupled to single-crystal subcells or mechanically stacked to avoid the temperature limitations described above. Similar problems and limitations are encountered in amorphous tandem cells, for example, a-Si tandem cells in which the B-doped P-layers are temperature sensitive.
Accordingly, a general object of this invention is to provide a method for forming a plurality of p/n junctions with polycrystalline or amorphous absorber materials for a multi-bandgap solar cell in which each of the absorber layers of the solar cell can be deposited under high temperature conditions without degrading or destroying previously deposited p/n junctions in the device. A more specific object of the present invention is to provide a method for forming a multi-bandgap tandem solar cell with polycrystalline or amorphous semiconductor absorbers having a top bandgap of about 1.7 eV and a bottom bandgap of about 1.1 eV.
An even more specific object of the present invention is to provide a method of forming a plurality of p/n junctions wherein one p/n junction is comprising polycrystalline or amorphous CuGaSe2 and CdS and a second p/n junction comprising polycrystalline or amorphous Cu(In,Ga)Se2 and CdS.
Another object of the present invention is to provide a multi-bandgap tandem solar cell having a wide bandgap polycrystalline or amorphous absorber and a narrow bandgap polycrystalline or amorphous absorber deposited at high temperatures, and corresponding window layers that are sensitive to the high temperature deposition of the absorber layer.
A more specific object of the present invention is to provide a solar cell with a first p/n junction composed of polycrystalline or amorphous CuGaSe2 and CdS and a second p/n junction composed of polycrystalline or amorphous Cu(In,Ga)Se2 and CdS.
To achieve the foregoing and other objects and in accordance with the purposes of the present invention, as embodied and broadly described herein, the present invention provides a method of forming a plurality of p/n junctions for a multi-bandgap solar cell with a polycrystalline or amorphous first absorber and a polycrystalline or amorphous second absorber deposited onto opposing sides of a transparent substrate at high temperatures followed by lower temperature deposition of first and second window layers onto the respective first and second absorbers to form first and second p/n junctions. Since the higher temperature depositions of the absorber layers for both cells are completed before either of the lower temperature window layers are deposited to complete the p/n junctions, neither of the p/n junctions need be exposed to high temperatures that would compromise its structural integrity by undesirable diffusion. The complementary absorber and window layers of each cell may be sequentially or simultaneously deposited to form the dual p/n junctions. The first and second p/n junctions may be heterojunctions, homojunctions, or combinations thereof. First and second layers of transparent conductors can be deposited onto the opposing sides or surfaces of a transparent substrate prior to deposition of the absorber layers to provide electric contacts or electrodes for the cells. Third and fourth conductors can be deposited onto the first and second windows, respectively, to form the complementary, opposite polarity contacts or electrodes for the cells. Either one or both of the latter electrodes can be transparent conductors, or, alternatively a metal grid may be the third transparent conductor, i.e., on the front cell, and a metal layer may be the fourth transparent conductor, i.e., on the back cell.
Further objects of the invention can be achieved according to this invention by a multi-bandgap solar cell comprising a transparent substrate having first and second surfaces, first and second transparent conductors deposited, respectively, onto the first and second surfaces. A wide bandgap absorber and a narrow bandgap absorber are deposited, respectively, at high temperature(s), onto the first and second transparent conductors, and first and second windows are deposited at lower temperature(s) onto the wide bandgap and narrow bandgap absorbers. The third and fourth transparent conductive media are respectively applied to the first and second windows to form first and second solar cells. A metal grid may be deposited onto the second transparent conductive medium, and a metal layer may be deposited onto the fourth transparent conductive medium.
The accompanying drawings, which are incorporated in and form a part of the specification, illustrate the preferred embodiments of the present invention, and together with the descriptions serve to explain the principles of the invention.
In the Drawings:
A solar cell 5 fabricated and structured in accordance with the present invention is illustrated diagrammatically in
As illustrated in
A significant feature of this invention is the ability to deposit both of the absorber layers 24, 26 of the first and second cells 20, 40, respectively, at high temperatures, e.g., greater than 500° C., prior to depositing either of the window layers 26, 46. Then, after both of the absorber layers 24, 44 are deposited at higher temperature(s), both of the window layers 26, 46, such as CdS, can be deposited on the absorber layers 24, 44, respectively, to form the p/n junctions 25, 45 at low enough temperature(s) to substantially prevent degradation of the p/n junctions from diffusion. Consequently, either one or both of the window layers 26, 46 can be deposited at low temperature(s), such as 200° C. or less. Therefore, this invention provides the advantages of two cells 20, 40, both with absorber layers 24, 44, such as polycrystalline or amorphous CuGaSe2 and Cu(In,Ga)Se2, of the high quality obtainable at high deposition temperatures, but without the p/n junction degradation or destruction that otherwise would accompany raising temperature sensitive p/n junctions to high temperatures. For the particular example multi-junction solar cell 5 shown in
According to this invention, the various layers of the device 5 are deposited and grown outwardly in opposite directions from the substrate 10 in a sequence, so that the high temperature depositions on both sides of the substrate 10 are completed before temperature sensitive layers and materials are deposited on either side of the substrate 10. Therefore, transparent conducting layers 22 and 42 are deposited first onto the respective first and second surfaces 12, 14 of substrate 10. First and second transparent conducting layers 22, 42 may be comprised of a transparent conductive oxide, such as tin oxide or zinc oxide, which can withstand the deposition temperatures required for the absorber and other layers to follow, and preferably with a thickness between 0.5 and 1 microns.
In the example embodiment illustrated in
The first and second window layers 26, 46 for the respective first and second cells 20, 40 are typically thin-film, n-type semiconductors that are deposited onto first and second absorber layers 24 and 44 to form first and second p/n junctions 25 and 45. The resulting p/n junctions may be homojunctions or heterojunctions as desired. An example of a suitable semiconductor materials for first and second window layers 26, 46 include cadmium sulfide, especially when used in combination with the polycrystalline or amorphous CuGaSe2 and polycrystalline or amorphous Cu(In,Ga)Se2 first and second absorber layers 24, 44, discussed above, to form heterojunctions 25, 45. To avoid any confusion, it is probably worth noting that persons skilled in the art understand that p/n junction is a generic term that applies to any junction formed by p-type and n-type semi-conductor materials, regardless of whether they are arranged so that the light is incident first on the p-type material or so that the light is incident first on the n-type material and regardless of whether there is or is not an intrinsic layer between them. The first and second window layers 26, 46 can have any appropriate thickness, for example, between about 0.05 and 3 microns and are usually deposited at lower temperatures, for example, 200° C. or less, to avoid deleterious diffusion into the absorber layers 24, 44.
The third and fourth transparent conducting layers 28, 48 are deposited onto exposed surfaces of the first and second window layers 26, 46, and may also be comprised of a transparent conductive oxide, such as tin oxide or zinc oxide. In one embodiment, first and second transparent conducting layers 22, 42 are tin oxide and third and fourth transparent conductive layers 28, 48 are zinc oxide layers, as shown in
Optionally, a metal current collection grid 30 may be deposited onto third transparent conducting layer 28 to provide one or more terminal electrical connections. A metal layer 50 may be deposited onto fourth transparent conducting layer 48 and may possess reflective properties for reflecting light back into the back and front cells 40, 20, as explained above. Suitable types of metals for the grid 30 and the layer 50 include molybdenum, aluminum, silver, and others.
In operation, incident light passes through metal current collection grid 30 (if present) and into first cell 20. Light having shorter wavelengths (i.e., higher energy) is absorbed by first cell 20 to provide a photovoltage potential across first p/n junction 25. Light having longer wavelengths (i.e., lower energy) passes through first cell 20, through transparent substrate 1 and is absorbed by second cell 40 to provide a photovoltage potential across second p/n junction 45. Light that passes through first and second cells 20, 40 may reflect off metal layer 50 and travel back into the cells 20, 40 for additional absorption.
The solar cell 5 illustrated in
Referring to the tandem solar cell 5 illustrated in
The first and second absorber layers 24, 44 may be sequentially deposited by performing vacuum deposition on one side 12 or 14 of the substrate 10 to deposit one absorber 24 or 44, flipping or rotating the substrate 10, and performing vacuum deposition on the other side 12 or 14 of the substrate 10 to deposit the other absorber 24 or 44. The choice of which absorber layer 24 or 44 to deposit first depends on which absorber 24 or 44 is more tolerant to the deposition conditions of the second-deposited absorber 24 or 44. If both of the first and second absorber layers 24, 44 can be deposited at the same temperature, it is also possible to simultaneously deposit both absorber layers 24, 44.
The resulting composite, including transparent substrate 10, first and second transparent conducting layers 22, 42 and first and second absorber layers 24, 44 may then be removed from the vacuum and placed in a chemical bath at between about 50 and 100° C. to deposit the first and second window layers 26, 46 onto the respective first and second absorber layers 24, 44. Alternatively, first and second window layers 26, 46 may be sequentially or simultaneously deposited by sputtering or evaporation methods. Third and fourth transparent conducting layers 28, 48 are then deposited onto first and second windows 26, 46 by conventional deposition methods such as RF magnetron sputtering at room temperature. Metal grid 30 and metal plate 50 may be deposited onto opposing ends of solar cell 5, if desired.
One characteristic of the present method of manufacturing a tandem solar cell is that the high temperature deposition of both the first and second absorber layers 24, 44 is performed before either of the temperature-sensitive first and second window layers 26, 46 are deposited. If each of the first and second cells 20, 40 are grown sequentially as in conventional methods of manufacturing tandem solar cells, the temperature sensitive window layer and the junction formed during deposition of the first cell 20 may be destroyed by the high-temperature deposition of the absorber layer of the second cell 40 (or vice-versa). Thus, the present method overcomes this problem by either sequentially or simultaneously depositing both absorber layers 24, 44 prior to depositing either one of the window layers 26, 46. Furthermore, this method also reduces product throughput time and energy consumption, resulting in significant cost-savings.
In the multi-junction solar cell device 5 illustrated in
This issue can also be addressed in another manner, as illustrated by the multi-junction solar cell device 5′ in
Solar cells manufactured according to the present method possess several beneficial characteristics. As illustrated in
Furthermore, first and second solar cells 20, 40 produced according to the present method may be easily laser scribed to form a plurality of scribed cells (not shown) in each of cells 20 and 40. The scribed cells within the first and second cells 20, 40 may be electrically connected in series to add voltage between the scribed cells. By depositing complementary layers of each cell as described above, each deposited layer may be scribed prior to deposition of the subsequent layer. This allows for efficient scribing characteristics not necessarily realized by conventional tandem cells.
By laser scribing first and second cells 20 and 40, multiple electrical configurations may also be accomplished. In one embodiment, both cells are optically aligned and share the same area. A four terminal connection to the cells is then current matched. In another embodiment, the first and second cells 20, 40 have different areas which allows almost any voltage output possible in the first and second cells 20, 40. A four terminal connection could draw off of the voltage from the first and second cells, or add the voltages of both cells. These terminal connections may be accomplished without the use of a metal grid.
An embodiment of the tandem solar cell illustrated in
The resulting cell was subjected to several solar cell efficacy tests. X-ray diffraction scans showed the films to be phase pure. Scanning electron microscopy images of CuGaSe2, and Cu(In,Ga)Se2 revealed large-grain dense films with good nucleation to the SnO2 back contacts. Electron probe microanalysis demonstrated suitable film composition given the deposition rates.
The foregoing description and the illustrative embodiments of the present invention have been presented in detail in varying modes, modifications, and alternate embodiments. It should be understood, however, that the foregoing description of the best modes of the present invention is exemplary only, and that numerous other modifications and alternative embodiments and modes of the invention will readily occur to persons skilled in the art. Therefore, the scope of the present invention is to be limited only by the claims below, as properly interpreted by applicable law, and not by the exact constructions, process steps, or parameters shown or described above.
The words “comprise,” “comprises,”, “comprising,”, “include”, “including”, and “includes” when used in this specification or in the following claims are intended to be open-ended, i.e., to specify the presence of stated features or steps, but they do not preclude or exclude the presence or addition of one or more features, steps, or groups thereof, which are not stated or recited. The word “about” when used in relation to bandgap in this specification or in the following means within 0.1 eV. The term “high temperature” when used in this specification or in the following claims means a temperature high enough to cause sufficient diffusion of window layer material into absorber layer material to degrade the performance of the p/n junction in a significant manner, i.e., enough degradation to cause persons skilled in the art to believe it should be avoided or mitigated. The term “low temperature” when used in this specification means less than “high temperature” as defined above. Specific examples of such high temperatures and low temperatures depend on particular materials used, time of exposure, and other factors.
| Number | Date | Country | Kind |
|---|---|---|---|
| PCT/US03/07815 | Mar 2003 | WO | international |
The United States Government has rights in this invention under Contract No. DE-AC36-99G010337 between the United States Department of Energy and the National Renewable Energy Laboratory, a Division of the Midwest Research Institute.