The present invention relates to photovoltaic devices, and in particular, a photovoltaic device structure with improved photovoltaic properties and a simplified method of manufacture.
Conventional methods for manufacturing photovoltaic materials typically requires some additives to a semiconductor. Such additives, including gallium arsenide (GaAs), can be highly toxic and carcinogenic, and their use in the manufacturing process of photovoltaic materials can increase the risk of negative health and environmental effects. It is highly desirable to have a manufacturing process of photovoltaic material with reduced use of additives.
The conventional methods for manufacturing photovoltaic materials also require a multi-step process, or different processes, with each step possibly taking place at a different apparatus and at different times, and requiring its own management and resources. For instance, different doping processes are applied to manufacture different semiconductor wafers, and the wafers of different types are sealed together in a particular way to form a photovoltaic material. The purpose for the doping processes and assembly of the wafers is to create p-n junctions, or p-i-n junctions, in between wafers to achieve an overall photovoltaic effect in the assembled material. Each of such manufacturing stages incurs a cost. It is highly desirable to have a manufacturing process for photovoltaic material that reduces the number of necessary processes or steps to reduce costs.
The approaches described in this section are approaches that could be pursued, but not necessarily approaches that have been previously conceived or pursued. Therefore, unless otherwise indicated, it should not be assumed that any of the approaches described in this section qualify as prior art merely by virtue of their inclusion in this section.
Preferred embodiments of the invention provide a novel method of manufacturing a new material with photovoltaic properties. Embodiments include processes for manufacturing using a heating process to create one or more photovoltaic structures on a semiconductor wafer, and provide the advantage of low manufacturing cost. Embodiments further include processes for reducing the resistivity of a surface opposite a high-resistivity surface on the semiconductor wafer.
Preferred embodiments of the present invention are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which like reference numerals refer to similar elements and in which:
In the following description numerous specific details have been set forth to provide a more thorough understanding of embodiments of the present invention. It will be appreciated however, by one skilled in the art, that embodiments of the invention may be practiced without such specific details or with different implementations for such details. Additionally some well known structures have not been shown in detail to avoid unnecessarily obscuring the present invention.
According to embodiments of the invention, a semiconductor wafer having a dopant element in the wafer, is treated in a heating process to manufacture a material with photovoltaic properties. The heating process induces diffusion of the dopant element in the wafer, causing a change in the semiconductor resistivity. By controlling the mechanics of this heating process, such as heating speed, temperature, time, and cooling speed, among other parameters further described below, a photovoltaic structure forms at the surface of the semiconductor wafer.
In accordance with preferred embodiments of the invention,
According to some embodiments of the invention, semiconductor wafer 10 comprises a doped single-crystal silicon wafer, such as an n-type silicon wafer. The silicon wafer has a thickness of above 10 μm. In a preferred embodiment, the silicon wafer has a thickness of 200 μm. In some embodiments, semiconductor wafer 10 comprises any one of Silicon (Si), Germanium (Ge), or any other group IV semiconductor. In some embodiments, semiconductor wafer 10 has a resistivity of 1 to 5 Ω·cm in the (100) face of crystal orientation.
The dopant element comprises any one of Phosphorus (P), Nitrogen (N), Antimony (Sb), Arsenic (As) or any other element of group V. In one example, the phosphorus content in the silicon wafer is above 0.01 ppb. In some embodiments, the phosphorus content is the minimum amount of dopant present in n-type silicon wafers as a result of standard n-type silicon wafer fabrication. For a higher concentration, phosphorus is added by methods such as ion implantation and chemical diffusion.
According to embodiments of the invention, wafer heating is performed in diverse methods, including but not limited to infrared heating, laser heating, and hot-wall furnace heating. In some embodiments, heating methods for treating semiconductor wafer 10 affect photovoltaic performance of the photovoltaic cell constructed from treated semiconductor wafer 10. In some embodiments, the cooling rate after the heating stage is a crucial factor to photovoltaic cell fabrication, whereas the heating rate is a less crucial factor to photovoltaic cell fabrication.
In a preferred embodiment, maximum photovoltaic cell performance is obtained at heating temperatures above 1500 K, at heating times above 5 minutes, at approximately 1×10−3 Pa. Table 1 provides a summary of parameters used in heating semiconductor wafer 10 according to embodiments of the invention.
After the heating process is completed, semiconductor wafer 10 transforms into a photovoltaic semiconductor material 11 that includes the layered structures as illustrated in the diagram in
According to some embodiments of the invention, after the heating process, which creates photovoltaic structures 16 and 20 when both surfaces are subjected to the conditions of Table 1, the bottom surface of photovoltaic semiconductor wafer 11 is treated to reduce its resistivity before fabricating the material into a photovoltaic cell. Treatments include but are not limited to one or more of physical removal of the bottom surface layer, formation of silicide at the bottom surface, and ion implantation into the bottom surface layer. Such lowering of resistivity at a bottom surface produces a greater output from a photovoltaic cell fabricated from the photovoltaic semiconductor wafer 11.
In some embodiments, a high-resistivity layer is physically removed by removal of some or all of photovoltaic structure 20.
In some embodiments, physical polishing is achieved by polishing with an abrasive grain that can polish a silicon substrate, such as a diamond paste, alumina, or silicon carbide. As the heat processing conditions may affect the depth of the bottom high resistivity layer, the thickness of the removed layer varies. In some embodiments, the bottom surface is polished to a depth of 10 μm. In some embodiments, photovoltaic semiconductor wafer 11 is polished using chemical mechanical planarization (CMP) techniques. In some embodiments, a combination of physical polishing and CMP is used to remove material from the bottom surface of photovoltaic semiconductor wafer 11.
In some embodiments, the high-resistivity bottom surface of semiconductor 10 is removed by laser ablation using high-output beams including but not limited to YAG laser, excimer laser, argon ion laser, solid green laser, or electron beam laser, or by performing line scanning on the rear surface. In some embodiments, the ablation is provided only for the center of the substrate to prevent failure or surface leakage of the semiconductor substrate caused by fragments created during the laser ablation that have scattered onto the photovoltaic power generation layer or onto the transparent conductive film on the top surface. In some embodiments, a protective film such as polymide film is formed on the bottom surface before laser ablation, and removed by peeling and cleaning after laser ablation, to minimize scattered fragments.
In some embodiments, chemical etching is used to remove the bottom high-resistivity surface layer from photovoltaic semiconductor wafer 11. A protective film for silicon, such as a SiN film, is formed at the top surface to mask the top surface from contact with an etching chemical. The bottom side of photovoltaic semiconductor wafer 11 is dipped into the etching chemical for etching the bottom surface to a depth of approximately 10 μm. Examples of etching chemicals used include but are not limited to KOH, NaOH, mixed solution of nitric acid and hydrofluoric acid, or an etching solution in which these materials are diluted with acetic acid and water. Alternatively, dry etching may be used. After the removal of the bottom surface by etching, the protective film is removed to expose the top surface of photovoltaic semiconductor wafer 11. For example, phosphoric acid is used to remove the SiN film.
In some embodiments, treatments of the bottom surface for lowering the resistivity of the bottom surface includes formation of silicide on the rear surface of photovoltaic semiconductor wafer 11 after the heating process.
In some embodiments, once the metal material is formed, heat is applied to the surface to form silicide. Heating temperatures vary depending on the material used. For example, the formation of Co onto a surface of silicon requires heat processing of 620K or higher to form silicide.
The thickness of silicide necessary to lower the resistivity of the high-resistivity layer at bottom surface depends on the thickness of the high-resistivity layer. An example range of silicide formation for layer 26 is between approximately 20 nm to 10 μm.
In some embodiments, treatments of the bottom surface for lowering the resistivity of the bottom surface includes ion implantation at the bottom surface to convert a portion of the material into an n++-type semiconductor.
In some embodiments, a preventative process may be performed on semiconductor 10 before the heating process reduces the resistivity of the bottom surface by preventing the formation of at least one high-resistivity layer, for example, in photovoltaic structure 20. Preventative processes performed before heating include but are not limited to using a particular type of semiconductor wafer, such as an n-on-n++ silicon substrate, that prevents formation a bottom high-resistivity layer upon heating; forming a protective film to prevent a bottom surface from forming into a high-resistivity layer upon heating; and preventing one surface from being heated to a sufficient temperature by concentrating heating to one surface or by placing semiconductor 10 on a heat reservoir to shield against the heat source.
In some embodiments, as shown in the top view 800 of
In some embodiments using SiC as isolation layer 36, the layer is not removed before forming the photovoltaic material into a photovoltaic cell because it does not negatively affect photovoltaic performance. For example, when a bottom electrode is placed on isolation layer 36 made from SiC, isolation layer 36 forms a buffer to create ohmic contact between semiconductor bulk 18 and a bottom electrode. Details of the method for using SiC to create ohmic contact between semiconductor bulk 18 and a bottom electrode is further described in copending U.S. patent application Ser. No. 13/______, filed ______, which claims priority to U.S. Provisional Application No. 61/655,449, filed Jun. 4, 2012 (Attorney Docket No. 44671-035 (P4)).
In some embodiments, as shown in
According to some embodiments, using the heating process as shown in
A reduction in top surface resistivity in wafer structure 22 is desirable to optimize photovoltaic performance. In one embodiment, cell efficiency is high when the junction between the photovoltaic structure 16 and semiconductor bulk 18 is positioned relatively close to the wafer surface, or within 0.5 and 1.5 microns. When the junction is too deep into the bulk, or above 2 microns, cell efficiency starts to degrade due to the decreased penetration of light into the wafer. Treatment temperature, time, and treatment pressure are adjustable for achieving a desired position of the junction.
The completed cell 44 includes bottom electrode 48. In some embodiments, an aluminum layer is preferred for bottom electrode 48. Thickness of the bottom electrode may vary between 1 and 800 microns, typically about 400 microns. A bottom aluminum electrode may be fabricated by physical vapor deposition (sputtering), screen printing, ink-jet printing or other standard printing or metal deposition techniques. Bottom electrode 48 may be placed directly over the bottom surface of photovoltaic material 42 or over a buffer in between, as previously described above with reference to related U.S. patent application Ser. No. 13/______.
In some embodiments, a photovoltaic material formed using the heating process described above with reference to
The steps in a process 1200 according to some embodiments of the invention for creating a photovoltaic material and cell is described with reference to a flowchart in
At step 1204, wafer heating is performed. Heat sources are applied to the top and the bottom of the wafer under the conditions described in Table 1 above. At step 1206, process for lowering the resistivity of the bottom layer is performed. Processes for lowering resistivity of the bottom layer include but are not limited to physical removal of the bottom surface layer, formation of silicide at the bottom surface, and ion implantation into the bottom surface layer to convert a portion of the material into an n++-type semiconductor. In some embodiments, step 1206 is performed prior to step 1204. Processes for lowering resistivity of the bottom layer prior to a heating step include but are not limited to using a particular type of semiconductor wafer, such as an n-on-n++ silicon substrate, that prevents formation a bottom high-resistivity layer upon heating; forming a protective film to prevent a bottom surface from forming into a high-resistivity layer upon heating; and preventing one surface from being heated to a sufficient temperature by concentrating heating to one surface or by placing semiconductor on a heat reservoir to shield against the heat source.
At step 1208, wafer cleaning is optionally performed if necessary. At step 1210, a top electrode is placed over the photovoltaic structure 16 of the wafer. In preferred embodiments, any transparent conductive oxides (TCO), such as indium-tin-oxide (ITO), ZnO, NiO, or any other type of transparent electrodes can be used as a top electrode. Semi transparent or translucent electrodes can also be used depending on the efficiency goals and desired cost of the photovoltaic cell.
At step 1212, an optional anti-reflecting coating may be placed on the top surface (on top of TCO layer) in order to improve light absorption and therefore cell performance.
At step 1214, placement of bottom electrode occurs. In some embodiments, an aluminum layer is preferred for the bottom electrode. Thickness of the bottom electrode may vary between 1 and 800 microns, typically about 400 microns. A bottom aluminum electrode may be fabricated by physical vapor deposition (sputtering), screen printing, ink-jet printing or other standard printing or metal deposition techniques. At step 1216, cell testing is optionally performed to verify the photovoltaic device and to test performance.
In one embodiment, measurement of an open circuit voltage (VOC) is used to test the performance of the cell.
Other features, aspects and objects of the invention can be obtained from a review of the figures and the claims. It is to be understood that other embodiments of the invention can be developed and fall within the spirit and scope of the invention and claims.
The foregoing description of preferred embodiments of the present invention has been provided for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Various additions, deletions and modifications are contemplated as being within its scope. The scope of the invention is, therefore, indicated by the appended claims rather than the foregoing description. Further, all changes which may fall within the meaning and range of equivalency of the claims and elements and features thereof are to be embraced within their scope.
This application claims the benefit of U.S. Provisional Application No. 61/761,342, filed Feb. 6, 2013 (Attorney Docket No. 44671-047 (P7)); U.S. Provisional Application No. 61/619,410, filed Apr. 2, 2012 (Attorney Docket No. 44671-033 (P2)); U.S. Provisional Application No. 61/722,693, filed Nov. 5, 2012 (Attorney Docket No. 44671-034 (P3)); U.S. Provisional Application No. 61/655,449, filed Jun. 4, 2012 (Attorney Docket No. 44671-035 (P4)); U.S. Provisional Application No. 61/738,375, filed Dec. 17, 2012 (Attorney Docket No. 44671-038 (P5)); U.S. Provisional Application No. 61/715,283, filed Oct. 17, 2012 (Attorney Docket No. 44671-041 (P12)); U.S. Provisional Application No. 61/715,286, filed Oct. 18, 2012 (Attorney Docket No. 44671-043 (P13)), and U.S. Provisional Application No. 61/715,287, filed Oct. 18, 2012 (Attorney Docket No. 44671-044 (P14)), the entireties of which are incorporated by reference as if fully set forth herein. This application is related to copending U.S. application Ser. No. 13/______, “Single-Piece Photovoltaic Structure,” (Attorney Docket No. 44671-033-002 (P2)), filed on even date herewith and is incorporated by reference as if fully set forth herein.
Number | Date | Country | |
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61722693 | Nov 2012 | US | |
61655449 | Jun 2012 | US | |
61619410 | Apr 2012 | US | |
61715280 | Oct 2012 | US | |
61761342 | Feb 2013 | US | |
61738375 | Dec 2012 | US | |
61715283 | Oct 2012 | US | |
61715286 | Oct 2012 | US | |
61715287 | Oct 2012 | US |