1. Field of the Invention
Embodiments of the present invention generally relate to the field of photovoltaic device manufacture and, more specifically, to a method for making crystalline silicon solar cells on low purity substrates.
2. Description of the Related Art
Solar cells are photovoltaic devices that convert sunlight directly into electrical power. The most common solar cell material is crystalline silicon, which is in the form of single or multicrystalline substrates, commonly referred to as wafers. Because the amortized cost of forming crystalline silicon-based solar cells to generate electricity is higher than the cost of generating electricity using traditional methods, there has been an effort to reduce the cost to form solar cells.
The present invention relates to the development of methods to enable the use of low-cost silicon materials for use in solar cells. Generally, in order to obtain good efficiency in crystalline silicon (c-Si) solar cells, high purity polysilicon is used as a starting material. The purity of the silicon is related to the ability of electrons to travel freely and therefore affects efficiency in relation to the conversion of photons in the solar process. Although the level of purity of the silicon required for solar cells is not as great as that necessary for electronic grade silicon used in semiconductor fabrication (close to 99.9999999%, with impurities in the parts per billion range), a high degree of silicon purity (99.9999% or better, with maximum impurity concentration in the parts per million range) is still required.
Typically, high purity polysilicon is obtained by purifying metallurgical grade silicon (MG-Si) using the “Siemens process.” The Siemens process for purifying silicon is commonly used because it removes boron and phosphorus impurities from silicon better than other known methods. In the Siemens process, high-purity silicon rods are exposed to trichlorosilane (or silane) at 1150° C. The trichlorosilane (or silane) gas decomposes and deposits additional silicon onto the rods. Silicon produced from this process is called polycrystalline silicon and typically has impurity levels in the parts per billion range, or 1013 atoms/cm3.
The Siemens process is very expensive and accounts for a major component of the cost of the wafers used to form crystalline silicon solar cells. Upgraded metallurgical grade (UMG) silicon refers to a type of silicon with higher boron or phosphorus impurities but with other harmful impurities such as heavy metals in the parts per million range or better, and is less expensive to manufacture than high purity polysilicon. If UMG silicon, containing higher levels of boron or phosphorus impurities than the silicon produced by the Siemens process, could be used, then less expensive processes could be used to purify the metallurgical grade silicon, thereby lowering the cost of making solar cells.
Therefore, there is a need for a method of making crystalline silicon solar cells on less expensive, low purity UMG substrates.
The present invention generally relates to a method for making crystalline silicon solar cells on low purity substrates.
In one embodiment, a method is provided for forming a crystalline silicon solar cell comprising forming vias of two different diameters through a crystalline silicon substrate from a first surface to a second surface, depositing a first silicon layer on the first surface and on surfaces within the vias, wherein the first silicon layer fills the vias of lesser diameter, depositing a second silicon layer over the first silicon layer, wherein the second silicon layer fills the vias of greater diameter, depositing a third silicon layer over the second silicon layer, and depositing a metallization layer on the second surface of the substrate. In one embodiment, the method further includes depositing a passivation layer on the third silicon layer prior to metallization and forming metal contacts on selected areas of the third silicon layer. In one embodiment, the passivation layer is formed from a compound selected from the group consisting of silicon nitride and silicon oxide. In another embodiment, the crystalline silicon substrate is a p-type silicon substrate, the first silicon layer is a p+-type amorphous silicon layer, the second silicon layer is a p-type amorphous silicon layer, and the third silicon layer is an n+-type amorphous silicon layer. In yet another embodiment, the method further comprises annealing the crystalline silicon substrate, prior to depositing the metallization layer and forming the metal contacts, at a temperature sufficient to cause crystallization of the first, second and third silicon layers and to electrically activate dopants in the layers. In another embodiment, the vias are formed by laser ablation. In one example, the vias of two different diameters comprise a first via having a diameter of about 4 to about 15 microns and a second via having a diameter of about 40 to about 60 microns. In a further embodiment, the second silicon layer is about 20 to 30 microns thick. In another example, the method further comprises removing saw damage from the substrate surfaces and texture etching the crystalline silicon substrate prior to forming the vias. In another embodiment, the crystalline silicon substrate comprises an upgraded metallurgical grade crystalline silicon substrate having a concentration of boron or phosphorus of about 1×1016 atoms/cm3 to about 1×1019 atoms/cm3.
In another embodiment, a method is provided for forming a crystalline silicon solar cell comprising forming vias of two different diameters through a crystalline silicon substrate from a first surface to a second surface, depositing a first silicon layer on the first surface of the crystalline silicon substrate and on surfaces within the vias, wherein the first silicon layer fills vias of lesser diameter, depositing a second silicon layer on the first silicon layer, depositing a third silicon layer on the second silicon layer, wherein the third silicon layer fills vias of greater diameter, depositing a passivation layer on the second surface of the substrate, patterning the passivation layer to expose portions of the first silicon layer and the third silicon layer, and depositing a conductive layer over the patterned passivation layer so that the conductive layer makes contact with the exposed regions of the first silicon layer in the vias of lesser diameter and the third silicon layer in the vias of greater diameter. In another example, the method further comprises annealing the substrate, prior to depositing the passivation layer and depositing the conductive layer, at a temperature sufficient to cause crystallization of the first, second and third silicon layers and to electrically activate dopants in the layers. In one embodiment, the method further comprises depositing a second passivation layer on the third silicon layer after annealing. In another embodiment, the second passivation layer comprises two or more layers. In another embodiment, either of the layers of the second passivation layer is formed from a compound selected from the group consisting of silicon nitride and silicon oxide. In yet another embodiment, the crystalline silicon substrate is a p-type silicon substrate, the first silicon layer is a p+-type amorphous silicon layer, the second silicon layer is a p-type amorphous silicon layer and the third silicon layer is an n+-type amorphous silicon layer. In another embodiment, the crystalline silicon substrate comprises an upgraded metallurgical grade crystalline silicon substrate having a concentration of boron or phosphorus of about 1×1016 atoms/cm3 to about 1×1019 atoms/cm3.
In another embodiment, a method is provided for forming a crystalline silicon solar cell comprising forming vias of two different diameters through a crystalline silicon substrate from a first surface to a second surface, depositing a first silicon layer over the first surface of the crystalline silicon substrate and on surfaces within the vias, wherein the first silicon layer fills vias of lesser diameter, depositing a second silicon layer over the first silicon layer, depositing a third silicon layer over the second silicon layer, wherein vias of greater diameter remain open after deposition of the first, second and third silicon layers, depositing a passivation layer over the second surface of the crystalline silicon substrate, patterning the passivation layer to expose regions of the first silicon layer and the third silicon layer, and depositing a conductive layer over the patterned passivation layer so that the conductive layer contacts the exposed regions of the first silicon layer in the vias of lesser diameter and the third silicon layer in the vias of greater diameter. In one embodiment, the method further comprises depositing a second passivation layer on the third silicon layer prior to deposition of the passivation layer over the second surface. In one embodiment, the second passivation layer comprises two or more layers. In one embodiment, the second passivation layer is formed from a compound selected from the group consisting of silicon nitride and silicon oxide. In another embodiment, the first layer is a p+-type amorphous silicon layer, the second layer is a p-type amorphous silicon layer, and the third layer is a n+-type amorphous silicon layer. In another embodiment, the method further comprises annealing the substrate, prior to depositing the passivation layer and depositing the conductive layer, at a temperature sufficiently low to cause solid phase epitaxial crystallization of the first, second, and third silicon layers and to electrically activate dopants in the layers. In yet another embodiment, the crystalline silicon substrate comprises an upgraded metallurgical grade crystalline silicon substrate having a concentration of boron or phosphorus of about 1×1016 atoms/cm3 to about 1×1019 atoms/cm3.
So that the manner in which the above-recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
Embodiments of the present invention provide a method for making crystalline silicon solar cells on crystalline silicon substrates, such as upgraded metallurgical silicon (UMG) substrates, by depositing amorphous silicon p-type layer(s) and/or amorphous silicon n-type layer(s), on the crystalline silicon substrate with substrate vias, or through holes, of varying diameters formed therein, annealing the stack of amorphous silicon layers to cause solid phase epitaxial conversion, and metalizing the substrate assembly using standard metallization techniques. Additional embodiments of the present invention provide depositing a passivation layer onto the last deposited silicon layer subsequent to the conversion. In one embodiment, a first layer of deposited amorphous silicon fills the substrate vias having a smaller diameter while a second layer of deposited amorphous silicon fills the substrate vias of larger diameter. A sufficient number of larger sized vias are made to obtain sufficient contact area with a reflective metal, such as aluminum, to have good current flow from the solar cell to the backside metal. Also, it is advantageous to increase the contact area, i.e., the number of vias, so as to increase the reflected radiation from metal that increases the charge carrier generation and the collected current. The reflection by the back metal, such as aluminum, can be increased by increasing the number of substrate vias. In another embodiment, the larger diameter substrate vias are made slightly larger so that the second amorphous silicon layer is not able to fill up the substrate vias. In this embodiment, a subsequently deposited third layer of amorphous silicon of a different conductivity than the second silicon layer is able to reach the back surface of the substrate through the larger diameter vias. Therefore, in this configuration, since both the second and third silicon layers are available at the back of the substrate, interdigitated back contact (IBC) metallization techniques can be used to make cell contact, and no metallization is needed on the front. In yet another embodiment, the larger diameter substrate vias are made even larger so that neither the first, second nor third layers of amorphous silicon is able to fill up the substrate vias. This embodiment would also allow for back contact metallization.
In the foregoing embodiments, the second deposited silicon layer (which may be a p-type layer or an n-type layer, depending on the conductivity of the substrate) acts as the active part of the solar cell. Consequently, it is possible to use as the starting substrate upgraded metallurgical (UMG) silicon, which contains higher concentrations of boron or phosphorus that are typically not tolerated by solar cells that use the substrate itself for the photovoltaic activity.
In one embodiment, as shown at step 111, the substrate 200 may undergo saw damage removal and texturing to assist in the coupling of light energy into the solar cell, reduce surface reflectivity, and hence improve efficiency. The saw damage removal may be performed to remove the damage created during the sawing process using techniques known to those skilled in the art, such as caustic etching, other types of chemical etching, lapping, polishing or other similar techniques. In one embodiment, texturing of a single crystalline silicon substrate front surface may be done by chemical etching to create a textured surface with random pyramidal features. Depending on the type of wafer, texturing can also be done by a number of publicly-known alternative methods, including photolithography, acid etching, plasma etching, and mechanical abrasion. Following the texturing, the substrate 200 may be cleaned using a standard pre-diffusion wet cleansing sequence.
At step 112, a plurality of vias of one or more diameters is formed through the substrate 200. In one embodiment, substrate vias of two desired diameters may be formed. In
At step 113, the substrate 200 is placed inside a vacuum deposition chamber. The vacuum deposition chamber may be a stand-alone chamber or part of a multi-chamber processing system. For example, the chamber may be a plasma enhanced chemical vapor deposition (PECVD) chamber. For a detailed illustration and explanation of one embodiment of a PECVD useful for carrying out embodiments of the present invention, reference is made to U.S. Pub. No. 2006/0060138 A1, which is incorporated in its entirety herein. A p-doped amorphous silicon layer with a heavy concentration of boron (p+-type layer 204) (
The desired diameters of the larger substrate via 202 and smaller substrate via 203 will depend upon the step coverage and desired film thicknesses of the deposited p+-type layer 204, p-type layer 205 and n+-type layer 206. In one embodiment, the p+-type layer 204 of amorphous silicon may be deposited at a film thickness from about 3 to 10 microns, the p-type layer 205 of amorphous silicon may be deposited at a film thickness from about 20 to 30 microns, and the n+-type layer 206 of amorphous silicon may be deposited at a film thickness from about 0.3 to 1 micron. In one embodiment, substrate vias of two different desired diameters are formed. In one embodiment, for a deposition process having 70% step coverage, the smaller substrate via 203 can have a desired diameter of approximately 4 to 15 microns, and the larger substrate via 202 can have a desired diameter of approximately 40 to 60 microns, so that the smaller substrate via 203 is filled by the first p+-type layer 204, while the larger substrate via 202 is filled by the second p-type layer 205. It should be noted that the step coverage, and hence the desired substrate via diameter, will vary depending on the deposition process. If the step coverage “s” of the amorphous silicon film is defined as the thickness of film on the vertical edge of the via divided by the thickness deposited on the horizontal top surface of the via, the minimum thickness “t” of the film to be deposited to completely fill a hole of radius “r” is given by t=r/s. Hence, the minimum thickness of the film, or the diameter of the via to be drilled, can be easily calculated.
At step 114, the substrate 200 and the three amorphous silicon layers, p+-type layer 204, p-type layer 205 and n+-type layer 206, may be directionally annealed at a temperature sufficient to crystallize the amorphous silicon layers and to electrically activate the dopants, but not so high as to cause the dopants, such as boron or phosphorus, or unwanted impurities to diffuse out of the substrate 200 beyond the p+-type layer and into the active part of the cell, which is the second, p-type layer 205. In one example, the p+-type layer 204, the p-type layer 205 and the n+-type layer 206 may be converted by solid phase epitaxy. In one embodiment, the conversion of the deposited p+-type layer 204, p-type layer 205 and n+-type layer 206 is accomplished by generating a temperature gradient across the substrate 200 with the deposited amorphous silicon layers thereon. The temperature gradient is provided at a temperature and for a time period sufficient to crystallize the amorphous material, such that, as the layers crystallize, they assume the same grain structure and crystal orientation as that of the underlying substrate 200. Moreover, the temperature gradient is provided at a temperature low enough so that there is no penetration of impurities from the substrate into the active p-type layer.
In one embodiment of step 114, the substrate 200 has heat applied to the back surface 200B thereof, which is on the opposite side of the substrate from the front surface 200A on which the p+-type layer 204, p-type layer 205 and n+-type layer 206 are deposited. The heat may be applied in any manner such that the application of heat is controlled and limited to being supplied to the back surface 200B of the substrate 200. In one embodiment, heat is applied to the back surface 200B of the substrate 200 in a rapid thermal processing (RTP) chamber. Accordingly, heat is applied to the back surface 200B of the substrate 200 at a suitable temperature, such as between about 750° C. and about 1200° C., and over a suitable period of time, such as between about 5 seconds and about 30 minutes, across the silicon substrate to convert the amorphous silicon layers through solid phase epitaxy with little dopant diffusion. The directional heating technique described herein is not limited to rapid thermal processing. Other methods of subjecting a substrate to a temperature gradient may be used as well.
In one embodiment, the heat is applied to the back surface 200B of the substrate 200 at a temperature of about 750° C. to about 1200° C. for a time period of about 5 seconds to about 30 minutes. In one embodiment of the present invention, the heat is applied to the back surface 200B at a temperature of about 1000° C. for a period of about 30 seconds. In one embodiment, the heat is applied to the back surface 200B at a temperature of about 950° C. for a time period of about 120 seconds. In one embodiment, the heat is applied to the back surface 200B at a temperature of about 1000° C. for a time period of about 120 seconds.
The application of the temperature gradient for the short time period causes the amorphous silicon to crystallize starting at the interface with the crystalline silicon substrate 200 and continuing out towards the outer surface of the n+-type layer 206. Thus, directional solid phase crystallization takes place. As this crystallization occurs, the amorphous silicon assumes the same grain structure as that of the underlying crystalline silicon substrate 200. Also, the dopants are electrically activated during this anneal.
In one embodiment, as shown at step 115, after annealing, a passivation layer 207 (
At step 116, the resulting structure is then passed on to a metallization process wherein metal contacts 208 (
In an alternate embodiment, the crystalline silicon substrate may contain an n-type dopant, such as phosphorus. The crystalline silicon substrate may contain a higher level of phosphorus than silicon produced by the Siemens process. In this embodiment, the first layer of deposited amorphous silicon may be n-doped with a high concentration of phosphorus (n+ layer), the second layer of deposited amorphous silicon may be n-doped with a lower concentration of phosphorus (n layer), and the third layer of deposited amorphous silicon may be p-doped with a high concentration of boron (p+ layer). Additionally, the passivation layer(s), metal contacts, and back metal may be formed from materials similar to the ones discussed above.
At step 312, vias are formed through the substrate 400 using, for example, laser ablation or water jet cutting. However, any suitable technique known in the art for forming vias through a silicon wafer may be used to form the perforated substrate 401 (
At step 313, the substrate 400 is placed inside a vacuum deposition chamber. As described above, a p-doped amorphous silicon layer with a heavy concentration of boron (p+-type layer 404) (
In one embodiment, the p+-type layer 404 of amorphous silicon may be deposited at a film thickness from about 3 to 10 microns, the p-type layer 405 of amorphous silicon may be deposited at a film thickness from about 20 to 30 microns, and the n+-type layer 406 of amorphous silicon may be deposited at a film thickness from about 0.3 to 1 microns. In one embodiment, substrate vias of two different desired diameters are formed, larger substrate via 402 and smaller substrate via 403. In one embodiment, for a deposition process having 70% step coverage, the smaller substrate via 403 can have a desired diameter of approximately 4 to 15 microns, and the larger substrate via 402 can have a desired diameter of approximately 40 to 60 microns, so that the smaller substrate via 403 is filled by the p+-type layer 404, while the larger substrate via 402 is finally, or completely, filled by the n+-type layer 406.
At step 314, the substrate 400 and the three layers of amorphous silicon, p+-type layer 404, p-type layer 405 and n+-type layer 406, may be directionally annealed at a temperature sufficient to crystallize the amorphous silicon layers and to electrically activate the dopants, but not so high as to cause the dopants, such as boron or phosphorus, or unwanted impurities to diffuse out of the substrate 400 and beyond the p+-type layer 404, as explained above. In one example, p+-type layer 404, the p-type layer 405 and the n+-type layer 406 may be converted by solid phase epitaxy. In another embodiment, the conversion of the deposited p+-type layer 404, the p-type layer 405 and the n+-type layer 406 can be accomplished by generating a temperature gradient across the substrate 400 with the deposited amorphous silicon layers thereon, as explained above.
At step 315, a passivation layer 407 (
At step 317, the assembly is then passed on to a metallization process wherein a conducting layer 409 (
At step 513, the substrate 600, now perforated, is placed inside a vacuum deposition chamber. As described above, a p-doped amorphous silicon layer (p+-type layer 604) (
In one embodiment, the p+-type layer 604 of amorphous silicon may be deposited at a film thickness from about 3 to 10 microns, the p-type layer 605 of amorphous silicon may be deposited at a film thickness from about 20 to 30 microns, and the n+-type layer 606 of amorphous silicon may be deposited at a film thickness from about 0.3 to 1 micron. In one embodiment, substrate vias of two different desired diameters are formed, larger substrate via 602 and smaller substrate via 603. In one embodiment, for a deposition process having 70% step coverage, the smaller substrate via 603 can have a desired diameter of approximately 4 to 15 microns, and the larger substrate via 602 can have a desired diameter of approximately 40 to 60 microns so that the smaller substrate via 603 is filled by the p+-type layer 604, while the larger substrate via 602 is not filled by any of the three amorphous silicon layers.
At step 514, the substrate 600 and the three layers of amorphous silicon, p+-type layer 604, p-type layer 605, and n+-type layer 606, are annealed at a temperature sufficiently high to convert the amorphous silicon layers by solid phase epitaxy with little dopant diffusion and to electrically activate the dopants, but not so high as to cause the dopants, such as boron or phosphorus, or unwanted impurities to diffuse out of the substrate 600 beyond the p+-type layer 604, such as by the methods described above. In one example, the p+-type layer 604, the p-type layer 605 and the n+-type layer 606 may be converted by solid phase epitaxy. In another embodiment, the conversion of the p+-type layer 604, the p-type layer 605 and the n+-type layer 606 can be accomplished by generating a temperature gradient across the substrate 600 with the deposited amorphous silicon layers thereon, as explained above.
At step 515, a passivation layer 607 (
At step 518, the assembly is then passed on to a metallization process wherein a conducting layer 609 (
Although the invention has been described in accordance with certain embodiments and examples, the invention is not meant to be limited thereto. For instance, it should be noted that the desired substrate via diameters will depend on the step coverage and thicknesses of the layers of amorphous silicon deposited on the c-Si substrate. Also, the PECVD process described herein can be carried out using other chemical vapor deposition (CVD) chambers, adjusting the gas flows, pressure, plasma density, and the temperature so as to obtain high quality amorphous films at practical deposition rates. Additionally, embodiments of the present invention may be carried out via hot wire chemical vapor deposition (HWCVD), low pressure chemical vapor deposition (LPCVD), or physical vapor deposition (PVD). Furthermore, embodiments of the invention include scaling up or scaling down any of the process parameters or variables as described herein according to the number of substrates being utilized, chamber conditions, chamber sizes, and the like.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
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