Patent Grant
10087080
The invention relates to a crystalline silicon ingot and a fabricating method thereof, and particularly to a crystalline silicon ingot having a low bulk defect density and small-sized silicon grains at the bottom thereof by using a nucleation promotion layer and a fabricating method thereof.
Most of the solar cells produce a photovoltaic (PV) effect when absorbing sunlight. Currently, the solar cell is made of a silicon-based material, since for the most parts, silicon is the second most abundant and accessible element in the world. Also, silicon is cost-effective, nontoxic, and chemically stable, and becomes broadly used in semiconductor applications.
There are three kinds of silicon-based materials for fabricating solar cells, i.e., single-crystal silicon (mono-Si), polysilicon (poly-Si), and amorphous silicon (a-Si). Poly-Si is much less expensive than mono-Si when produced by Czochralski method (CZ method) or floating zone method (FZ method), so it is usually used as a raw material of the solar cell due to the economic concern.
Conventionally, poly-Si for solar cells is fabricated by a common casting process. That is, it is prior art to produce poly-Si for solar cells by a casting process. In brief, the poly-Si solar cell is fabricated by melting high purity silicon in a mold like quartz crucible, then cooling with a controlled solidification to form a poly-Si ingot, followed by slicing it into wafers that fit compactly into a PV cell module for further application. The ingot formed by the above process is in fact in the form of an aggregation of silicon crystals having random crystal orientations.
It's difficult to texture (roughen) the surface of the poly-Si chip due to the random crystal orientations of grains. Surface texturing can enhance the efficiency of the PV cell by reducing light reflection and thus increasing solar energy absorption on the surface of the cell. In addition, “kinks” that form in the boundaries between the grains of conventional multi-crystalline silicon tend to nucleate structural defects in the form of clusters or lines of dislocations. These dislocations, and the impurities tended to be attracted by dislocations, are believed to cause a fast recombination of electrical charge carriers in a photovoltaic cell made from conventional multi-crystalline silicon, reducing the power output of the solar cell. Thus, the poly-Si PV cell usually has lower efficiency than the equivalent mono-Si PV cell, even a radial distribution of defects exists in the latter manufactured by the current technique. However, because of the relatively simple fabricating process and lower cost for the poly-Si solar cell and also the effective defect passivation step in processing the solar cell, poly-Si is still more broadly used as the silicon source of the PV cell.
Currently, it has been developed that crystalline silicon ingot is fabricated using a mono-Si seed layer and based on directional solidification, in which a large-sized, (100)-oriented mono-Si cubic is generally employed as a seed. Unfortunately, during the competition among the (100)-oriented grain and the random nucleation grain, the latter is prevailing. For maximizing the seeded crystalline volume in an ingot, the current technique takes advantage of the boundaries in (111)-oriented silicon to surround the regions occupied by the (100)-oriented silicon seeds, thereby impeding successfully the growth of crystals having other orientations. In this way, a high quality ingot of mono-Si or bi-crystal silicon block may be obtained, in which the lifetime of the minority charge carriers is maximized in the resultant wafer employed for fabricating the high-performance solar cell. Herein, the term “single crystal silicon (mono-Si)” is referred to a bulk of mono-Si that has a single uniform crystal orientation throughout the bulk, while the term “bi-crystal silicon” is referred to a silicon bulk that has one uniform crystal orientation in or over 50% of the volume of the bulk, and has another uniform crystal orientation in the rest of the volume of the bulk. For example, such bi-crystal silicon may include a body of single crystal silicon having one crystal orientation next to another body of single crystal silicon having a different crystal orientation making up the balance of the volume of crystalline silicon. Additionally, conventional multi-crystalline silicon refers to crystalline silicon having cm-scale grain size distribution, with multiple randomly oriented crystals located within a body of silicon. However, the crystalline silicon ingot fabricated by the current technique described above where the expensive mono-Si is used as a seed is rather costly.
There are other techniques without using expensive mono-Si as a seed. Laterally grown crystals are spread over the bottom of the crucible by partial undercooling first, and then columnar crystals are grown upwards. The large-sized silicon grains of thus obtained ingots have a low bulk defect density. Therefore, the solar cell made from silicon wafers sliced from the crystalline silicon ingot fabricated by the above techniques may have higher photoelectric conversion efficiency.
However, the above current techniques using poly-Si are only proved successful in the laboratory, while in an industrial level production, it's usually more difficult to perform the poly-Si casting by controlling the growth of the dendrites to be spread over the bottom of the crucible using partial undercooling. Industrial-scale multi-crystalline silicon casting is affected by the heating uniformity of the crucible and the entirety, which increases variance of the initial undercooling controlling. Therefore, the poly-Si at the bottom of the crucible tends to grow into a large-sized grain and the defect density in this area will become elevated. The defect density becomes higher rapidly as the large-sized grains proceed to grow, resulting in poor quality of the entire crystalline silicon ingot and the solar cell with reduced photoelectric conversion efficiency.
This summary is provided to introduce a selection of concepts that are further described below in the detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.
In one aspect, a method of fabricating the crystalline silicon ingot includes the following steps. As a first step, a nucleation promotion layer is loaded onto a bottom of a mold, and the mold itself defines a vertical direction. Next, a silicon source is provided on the nucleation promotion layer in the mold, followed by heating the mold until the silicon source is melted into a silicon melt completely. Then, at least one thermal control parameter regarding the silicon melt is controlled to enable a plurality of silicon grains from the silicon melt to nucleate on the nucleation promotion layer such that a final average grain size of silicon grains grown in the vertical direction is about two to three-fold of an initial average grain size grown. As the final step, the at least one thermal control parameter is proceed to be controlled for growing the plurality of the silicon grains in the vertical direction until the silicon melt is solidified completely to obtain the crystalline silicon ingot.
In one or more embodiments, the nucleation promotion layer functions to inhibit the increase of the defect density of the plurality of the silicon grains during the growth process. The defect density's increment rate of thus obtained silicon crystalline ingot in the vertical direction ranges from 0.01%/mm to 10%/mm.
In one or more embodiments, the silicon grains that are immediately adjacent to the nucleation promotion layer have an average grain size of less than about 10 mm.
In one or more embodiments, the nucleation promotion layer is composed of a plurality of crystal particles with random geometry, each of which has a grain size of less than about 50 mm.
In one or more embodiments, the plurality of the crystal particles are poly-Si particles, mono-Si particles, single crystal silicon carbide or other crystal particles having a melting point higher than 1400° C. and capable of facilitating nucleation.
In one or more embodiments, the nucleation promotion layer is a plate made of a material having a melting point higher than about 1400° C. The interface between the plate and the silicon melt has a roughness of 300 μm to 1000 μm to provide multiple nucleation sites for the plurality of the silicon grains.
In one or more embodiments, a heater is located above the mold, and a directional solidification block is located below the mold. The at least one thermal control parameter may be for example a first temperature gradient from the heater to the mold, a second temperature gradient from the bottom of the silicon melt to the top of the directional solidification block or a heat transfer flux.
In another aspect of the invention, a method of fabricating the crystalline silicon ingot includes the following steps. As a first step, a nucleation promotion layer is loaded onto a bottom of a mold, wherein the nucleation promotion layer is formed by jointing a plurality of crystal particles with random geometry together and the mold itself defines a vertical direction. Next, a silicon source is provided on the nucleation promotion layer in the mold, followed by heating the mold until the silicon source is melted into a silicon melt completely. Then, at least one thermal control parameter regarding the silicon melt is controlled to enable a plurality of silicon grains from the silicon melt to nucleate on the nucleation promotion layer such that a final average grain size of silicon grains grown in the vertical direction is about two to three-fold of an initial average grain size grown. As the final step, the at least one thermal control parameter is proceed to be controlled for growing the plurality of the silicon grains in the vertical direction until the silicon melt is solidified completely to obtain the crystalline silicon ingot.
In one aspect, embodiments disclosed herein relate to a method of fabricating a poly-crystalline silicon ingot that includes: (a) loading a nucleation promotion layer onto a bottom of a mold, the mold itself defining a vertical direction; (b) providing a silicon source on the nucleation promotion layer in the mold; (c) heating the mold until the silicon source is melted into a silicon melt completely; (d) controlling at least one thermal control parameter regarding the silicon melt continually to enable the silicon melt to nucleate on the nucleation promotion layer such that a plurality of silicon grains grow in the vertical direction from the bottom of the silicon melt; (e) controlling the at least one thermal control parameter to enable the plurality of the silicon grains to continuously grow with an average grain size increasing progressively in the vertical direction until entirety of the silicon melt is solidified to obtain the poly-crystalline silicon ingot, wherein the nucleation promotion layer is loaded by spreading a plurality of mono-Si particles over the bottom of the mold.
In another aspect, embodiments disclosed herein relate to a method of fabricating a poly-crystalline silicon ingot that includes: (a) loading a nucleation promotion layer onto a bottom of a mold, the mold itself defining a vertical direction; (b) providing a silicon source on the nucleation promotion layer in the mold; (c) heating the mold until the silicon source is melted into a silicon melt completely; (d) controlling at least one thermal control parameter regarding the silicon melt continually to enable the silicon melt to nucleate on the nucleation promotion layer such that a plurality of silicon grains grow in the vertical direction from the bottom of the silicon melt; (e) controlling the at least one thermal control parameter to enable the plurality of the silicon grains to continuously grow with an average grain size increasing progressively in the vertical direction until entirety of the silicon melt is solidified to obtain the poly-crystalline silicon ingot, wherein the nucleation promotion layer is loaded by spreading a plurality of single crystal silicon carbide particles over the bottom of the mold.
The crystalline silicon ingot of the present disclosure includes a plurality of silicon grains grown in a vertical direction of the ingot itself and a nucleation promotion layer at the bottom thereof. Besides, the silicon grains that are immediately adjacent to the nucleation promotion layer have an average grain size of less than about 10 mm.
Contrary to prior art where the particular size, shape, and alignment/orientation of expensive mono-Si seeds and partial undercooling are involved to form silicon grains on the bottom of the crucible, the present disclosure provides the silicon melt with dense nucleation sites by using a nucleation promotion layer with lower cost materials. A high-density grain distribution is achieved to inhibit the generation of certain fast-grown orientations, thereby greatly decreasing the distribution ratio of large-sized silicon grains. Since the competition is much less frequently occurred between small-sized grains during the growth process, and small-sized grains tend to grow upward in a generally single direction due to great denseness in grain population, the situation that the small-sized grains are overwhelmed by the large-sized grains is effectively diminished so that the columnar crystals are allowed to grow completely. In addition, during the growth of the crystals, the grain boundaries distributed densely in the ingot of the invention by stress field thereof attract defects to agglomerate or to slip on the grain boundaries to release thermal stress. Accordingly, the increase of defects such as dislocation is hindered effectively, thereby leading to a better quality of the crystalline silicon ingot and a higher photoelectric conversion efficiency of the solar cell made therefrom.
Other aspects and advantages of the claimed subject matter will be apparent from the following description and the appended claims.
These and other features and advantages of the various embodiments disclosed herein will be better understood with respect to the following description and drawings, in which like reference numerals refer to like parts throughout, and in which:
In practice, the mold 16 may be a crucible; both the base 17 and the directional solidification block 18 may be made of graphite; the inert gas duct 11 is configured to introduce argon (Ar) gas into the heat insulating cage 12.
The method of the invention begins with loading a nucleation promotion layer 2 onto the bottom of the mold 16 which defines a vertical direction V, followed by providing a silicon source 30 on the nucleation promotion layer 2 in the mold 16. The mold 16 containing the nucleation promotion layer 2 and the silicon source 30 is placed in the base 17.
Next, the mold 16 is heated until the silicon source 30 is melted down into a silicon melt 32 completely, as shown in
Then, at least one thermal control parameter regarding the silicon melt 32 such as heat transfer flux is controlled to enable the nucleation of a plurality of silicon grains 34 from the silicon melt 32 on the nucleation promotion layer 2, and the silicon grains 34 with an average grain size of two to three-fold larger are grown in the vertical direction V, as shown in
As the final step, the at least one thermal control parameter is proceeded to be controlled subsequently for growing the plurality of the silicon grains 34 in the vertical direction V until the silicon melt 32 is solidified completely. Thus the silicon crystalline ingot is obtained.
In one or more embodiments, the nucleation promotion layer 2 also functions to inhibit the increase of the defect density of the plurality of the silicon grains 34 during the growth process. The defect density's increment rate of thus obtained silicon crystalline ingot in the vertical direction ranges from 0.01%/mm to 10%/mm determined by the following formula:
(Dx2Dx1)/(x2−x1)
where x1 and x2 indicate respectively two different levels in the vertical direction of the ingot, and Dx1 and Dx2 indicate respectively the defect densities of the ingot in the tangent planes taken at levels x1 and x2.
Even small-sized silicon grains can inhibit the increment rate effectively. In the ingot of the invention, there is a higher possibility for the small-sized silicon grains (<10 mm) to appear in the center of the bottom, while around the side or corner of the bottom of the ingot, only a smaller number of the small-sized silicon grains (<10 mm) appear. It is found that the ratio of area occupied by the small-sized silicon grains in a tangent plane along the vertical direction V affects the growth rate and the increment rate of the defect density of the grains.
In one or more embodiments, the silicon grains 34 that are immediately adjacent to the nucleation promotion layer 2 have an average grain size of less than about 10 mm.
In one or more embodiments, the nucleation promotion layer 2 is composed of a plurality of crystal particles 22 with random geometry, each of which has a grain size of less than about 50 mm.
In one or more embodiments, the plurality of the crystal particles 22 may be poly-Si particles, mono-Si particles, single crystal silicon carbide or other crystal particles having a melting point higher than 1400° C. and capable of facilitating nucleation. In particular, the plurality of the crystal particles 22 may be commercially available single crystal silicon carbide, poly-Si or mono-Si chips or chunks that cost much less significantly than conventional mono-Si seeds. Next, the single crystal silicon carbide, poly-Si or mono-Si chips or chunks are spread over the bottom of the mold 16 to form a nucleation promotion layer 2 as shown in
In one or more embodiments, as shown in
Referring back to
In one or more embodiments, the method of fabricating the crystalline silicon ingot is disclosed as follows. First, a nucleation promotion layer 2 is loaded onto the bottom of the mold 16. The nucleation promotion layer 2 is formed by jointing multiple crystal particles 22 with random geometry. The mold 16 itself defines a vertical direction V. In practice, the nucleation promotion layer 2 is obtained by cutting the lower part of another crystalline silicon ingot fabricated with the method of the invention. In this way, the nucleation promotion layer 2 may be recovered for subsequent uses.
Afterwards, the mold 16 is heated until the silicon source 30 is melted completely into a silicon melt 32. Subsequently, at least one thermal control parameter regarding the silicon melt 32 is controlled to enable the nucleation of a plurality of silicon grains 34 from the silicon melt 32 on the nucleation promotion layer 2 such that a final average grain size of silicon grains grown in the vertical direction V is about two to three-fold of an initial average grain size grown. At last, the at least one thermal control parameter is proceeded to be controlled for growing the plurality of the silicon grains 34 in the vertical direction V until the silicon melt 32 is solidified completely. Thus the silicon crystalline ingot is obtained.
In one or more embodiments, the nucleation promotion layer 2 also functions to inhibit the increase of the defect density of the plurality of the silicon grains 34 during the growth process. The defect density's increment rate of thus obtained silicon crystalline ingot in the vertical direction ranges from 0.01%/mm to 10%/mm.
In one or more embodiments, the silicon grains 34 that are immediately adjacent to the nucleation promotion layer 2 have an average grain size of less than about 10 mm.
In one or more embodiments, the nucleation promotion layer 2 is composed of a plurality of crystal particles 22 with random geometry, each of which has a grain size of less than about 50 mm. In one or more embodiments, the grain size of the plurality of crystal particles used in the nucleation promotion layer may be related to the size of the bottom of the base of the mold or crucible used to fabricate the crystalline silicon ingot, where the inner dimensions of the bottom of the base of the mold or crucible essentially defines the dimensions of the base of the silicon ingot formed. In one or more embodiments, a ratio of the size of the bottom of the base of the mold or crucible to the grain size of the plurality of the crystal particles in the nucleation promotion layer may be greater than or equal to 3. For example, in some embodiments, the bottom of the base of a mold or crucible may be substantially square, having sides that are about 150 mm in length. Thus, a plurality of crystal particles used in the nucleation promotion layer having grain sizes of 50 mm or less would satisfy the ratio expressed above. Similar relationships may also hold for molds/crucibles with a circular base/bottom, where the diameter may be used as the dimension for calculating the aforementioned ratio. In embodiments where the bottom of the mold or crucible has a shape that possesses non-equal dimensions (e.g. a rectangle or an ellipse), then the largest dimension may be used as the determinative dimension for calculating the aforementioned ratio.
The crystalline silicon ingot of the invention includes a plurality of silicon grains growing in a vertical direction and a nucleation promotion layer. Also, in the ingot, the silicon grains 34 are those immediately adjacent to the nucleation promotion layer 2 have an average grain size of less than about 10 mm. Further, the defect density's increment rate of thus obtained silicon crystalline ingot in the vertical direction ranges from 0.01%/mm to 10%/mm.
In one or more embodiments, the nucleation promotion layer 2 is composed of a plurality of crystal particles 22 with random geometry, each of which has a grain size of less than about 50 mm.
In one or more embodiments, the plurality of the crystal particles 22 may be poly-Si particles, mono-Si particles, single crystal silicon carbide or other crystal particles having a melting point higher than 1400° C. and capable of facilitating nucleation.
In yet another preferred embodiment, the nucleation promotion layer may be a plate made of a material having a melting point higher than about 1400° C. such as high purity graphite, silicon, or ceramic materials like aluminum oxide, silicon carbide, silicon nitride, aluminum nitride. The interface between the plate and the silicon melt has a roughness of 300 μm to 1000 μm to provide multiple nucleation sites for the plurality of the silicon grains.
It is obvious from
From the above description of the invention, it is manifest that various techniques can be used for implementing the concepts of the invention without departing from the scope thereof. Moreover, while the invention has been described with specific reference to certain embodiments, a person of ordinary skills in the art would recognize that changes can be made in form and detail without departing from the spirit and the scope of the invention. The described embodiments are to be considered in all respects as illustrative and not restrictive. It is intended that the scope of the invention is defined by the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 100143484 A | Nov 2011 | TW | national |
This Application is a Continuation-in-part of application Ser. No. 13/416,525 filed on Mar. 9, 2012 and hereby claims all benefits of U.S. utility application Ser. No. 13/416,525. U.S. utility application Ser. No. 13/416,525 claims priority to Taiwanese application serial number 100143484, filed on Nov. 28, 2011. The above-referenced applications are hereby incorporated by reference in their entireties.
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| Number | Date | Country | |
|---|---|---|---|
| 20170057829 A1 | Mar 2017 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13416525 | Mar 2012 | US |
| Child | 15351035 | US |
