The present invention relates to a method of providing a boron doped region in a silicon substrate.
U.S. Pat. No. 5,928,438 (Salami et al.) discloses a solar cell with a selective (boron) emitter. The solar cell comprises a semiconducting substrate having first and second surfaces, a first plurality of emitter regions formed in one of the first and second surfaces with a relatively low dopant concentration, a second plurality of emitter regions formed in said one of the first and second surfaces to a substantially greater depth than the first plurality of regions preferably with a relatively higher dopant concentration than the first plurality of regions. The semiconductor substrate preferably comprises n-type doped silicon, and the first plurality of emitter regions are preferably formed using a p+ type dopant material, such as boron. The second plurality of emitter regions is preferably formed from a p+ type dopant material comprising either pure aluminium or an alloy of aluminium and silicon. The dopant region formed in a second one of the substrate surfaces is preferably formed using an n+ type dopant material, such as phosphorus.
A lowly doped boron layer in a substrate and a selective low-high doping profile to allow the use of selective emitters in solar cells is disclosed in the article by N. Bateman et al., ‘High quality ion implanted boron emitters in an interdigitated back contact solar cell with 20% efficiency’, Energy Procedia 8 (2011), p 509-514. This however, requires costly processing steps.
The present invention seeks to provide a method of providing improved homogenous and selective boron doped regions or emitters having higher efficiencies at reasonable cost.
According to the present invention, a method according to the preamble is provided, wherein the method comprises:
a) depositing a boron doping source over a first surface of the substrate;
b) annealing the substrate for diffusing boron from the boron doping source into the first surface, thereby yielding a boron doped region;
c) removing the boron doping source from at least part of the first surface (i.e. completely or selectively);
d) depositing undoped silicon oxide over the first surface;
e) annealing the substrate for lowering a peak concentration of boron in the boron doped region through boron absorption by the undoped silicon oxide.
The processing steps (a) and (b) may be combined in a single process, which as such is known to the skilled person. Annealing (step (b) and also step (e)) involves increasing the temperature of the substrate and subsequent cooling down of the substrate. Again, this may be accomplished using several techniques, which as such are known to the skilled person.
The boron doped region may be implemented as an emitter in an n-type substrate. Alternatively, the boron doped region may also be implemented when the substrate is a p-type substrate. In some applications, the p-type substrate is already doped with boron, but in low concentration. The term boron doped region is then to be understood as a highly doped region, where the boron concentration is much higher (e.g. at least a factor 100) than in the rest of the substrate.
Dependent on what type of boron doped region is to be obtained, removing the boron doping source (c) comprises complete or selective (partial) removal of the boron doping source. In particular, the complete removal of the boron doping source from the first surface implies obtaining a homogenous boron doped region, whereas the selective (partial) removal of the boron doping source from the first surface implies obtaining a selective boron doped region.
The method of the present invention embodiments thus yields a boron doped region comprising a continuous boron doped layer having a generally low homogenous boron concentration, i.e. a homogenous boron doped emitter, or a continuous boron doped layer having smoothly interspersed regions of higher and lower boron concentration, i.e. a selective boron doped emitter.
The annealing of deposited undoped silicon oxide pulls out boron atoms from the emitter, thus reducing the doping level. In the case of a selective emitter embodiment, annealing of the selectively remaining boron doping source keeps the high doping level for contacting. As a result, a selective emitter is obtained in the substrate having a high contrast of the boron doping level.
According to the present invention, the annealing (e) may further comprise diffusing phosphorus into a second surface of the substrate for yielding a phosphorus doped layer e.g. acting as a back surface field (BSF), wherein boron absorption and phosphorus diffusion occurs in the same processing step during the annealing. In practice, the annealing (e) requires at least 900° C., while phosphorus diffusion takes place between 780-860° C. Therefore the annealing and phosphorus diffusion do not necessarily take place simultaneously, but can be done consecutively in one process chamber. There is no necessity of heating up step for the phosphorus diffusion because it utilizes the cooling down sequence of the annealing (e). In this process step, the undoped silicon oxide film plays two roles: boron puller/absorber during anneal and diffusion barrier during phosphorus diffusion.
The present invention will be discussed in further detail hereinafter based on a number of exemplary embodiments with reference to the drawings, wherein:
According to the present invention,
The substrate 1 defined above and depicted in
Depicted in
Depicted in
Conventionally, the peak concentration of a boron-doped region 8 made by diffusion is the same as its solid solubility limit, i.e. 2E20/cm3. To improve the surface passivation and to decrease minority carrier recombination in the boron-doped region 8, the peak concentration should be lowered significantly, particularly between the contact fingers in the case of a selective emitter, i.e. the illuminated or transparent areas.
According to the present invention, the term “annealing” refers to a heat treatment of a specimen followed by the cooling of said specimen, such as heating the substrate 1 to a predetermined temperature for a predetermined time period after which the substrate 1 is actively or passively cooled, e.g. cooled to an ambient temperature.
The further processing step in the method according to the present invention is the removal of at least part of the boron doping source 6. In
Depicted in
In practice, some residue could stay on the region 8 after the boron doping source 6 is removed. When the doping source is BSG, B2O3, or spin coating of boron, the most part of the source can be easily removed by a wet chemical process at the room temperature. The residue, typically a few nm of boron silicide (BxSi, x=1˜6), is hard to remove. It is also called a “boron-rich layer”, or BRL. In other case, stronger etchant (the etching solution is heated in most of the cases) may be used to remove the BRL completely. In this case, some surface part of the region 8 is then also etched together with the BRL. This etching depth is not deeper than that of the region 8. In practice, it is between almost 0 nm and half of the depth of the region 8. In both cases, the final boron peak concentration after the anneal (e) can be tuned to 5E19/cm3 at highest. The boron in the BRL can also be pulled out into the undoped silicon oxide film.
In an embodiment, the removing (c) comprises etching the boron doping source 6 for removing the boron doping source 6 completely or selectively. In another embodiment, the removing (c) may further comprise removing a small surface area of the first surface 2 of the substrate 1. This would allow further shaping of the doping profile of the region 8 near the first surface 2 of the substrate 1.
In summary, in case a homogenous boron doped region is to be obtained, the removing (c) comprises removing (c) the boron doping source 6 completely. In case a selective boron doped region (emitter) is to be obtained, the removing (c) comprises removing (c) the boron doping source 6 selectively to obtain a grid-like structure for the boron doping source 6.
Depicted in
In an embodiment, the depositing (d) comprises chemical vapor deposition of undoped silicon oxide. In a further embodiment, the depositing (d) comprises baking a liquid coating of undoped silicon oxide, and typically the liquid comprises silanol (SiH3OH). In all embodiments, the term silicon oxide (film) is used, which is understood to include depositions with the formula SiO2, SiOx (1<x≤2), or SiOx:H (1<x≤2). It is noted that CVD silicon oxide and spun-on silicon oxide are normally not stoichiometric.
Depicted in
In the embodiment shown in
In the embodiment of
The lowly doped regions 8a refer to the areas which will be illuminated during actual use of the solar cell, i.e. between surface contacts (e.g. electrodes) of the substrate 1. The highly doped regions 8b on the other hand refer to the areas of the surface 2 to which surface contacts will be applied, and which therefore need a low as possible contact resistance.
In an embodiment, the selective lowly boron doped region 8a has a peak concentration lower than 5E19/cm3 or even lower than 3E19/cm3, and wherein a sheet resistance of the lowly doped region 8a is between 30 and 200 ohm/sq. The peak concentration of boron at the opaque spots of highly doped regions 8b remains relatively high (in the order of 1E20/cm3 since the annealing (e) further anneals the selective boron doping source 6 only). That is, undoped silicon oxide 10 cannot absorb boron from the highly doped regions 8b as silicon oxide is blocked by the selective boron doping source 6 during the annealing step (e).
In advantageous embodiments, the annealing (e) comprises heating the substrate 1 to a temperature of at least 900 degree Celsius, e.g. 940 degree Celsius. E.g. the annealing is performed in a temperature range between 900-1150° C., e.g. between 940-1100° C.
Depicted in
According to an embodiment of the present invention, the annealing (e) at a sufficiently high temperature allows for a one step process wherein boron absorption at the first surface 2 and the phosphorus diffusion at the second surface 4 is accomplished simultaneously or consecutively (i.e. at different temperature ranges during the annealing (e)). This one step process is made possible as the undoped silicon oxide layer 10 acts as a boron absorber as well as a diffusion barrier against phosphorus, preventing phosphorus diffusion into the homogenous or selective boron doped region 8.
In an embodiment, the phosphorus doped layer 12 has a surface concentration higher than 1E20/cm3. In another embodiment, the step of diffusing phosphorus into the second surface 4 comprises a POCl3 process. In a specific embodiment a specific processing step is further applied to remove thin oxide that may have formed during the annealing (e).
In view of the detailed method step (a) to (e) disclosed so far, the method of the present invention can thus be summarized as a method of providing a boron doped region 8 in a silicon substrate 1, comprising the steps of:
a) depositing a boron doping source 6 over a first surface 2 of the substrate 1;
b) annealing the substrate 1 for diffusing boron from the boron doping source 6 into the first surface 2, thereby yielding a boron doped region 8;
c) removing the boron doping source 6 completely or selectively;
d) depositing undoped silicon oxide 10 over the first surface 2 for boron absorption;
e) annealing the substrate 1 for lowering a peak concentration of boron in the boron doped region 8 through boron absorption by the undoped silicon oxide.
The annealing step (e) may further comprise diffusing phosphorus into a second surface 4 of the substrate 1 for yielding a phosphorus doped layer 12, wherein the boron absorption and phosphorus diffusion occurs simultaneously, or consecutively in a single process step. That is, the annealing step (e) can be combined with phosphorous diffusion for obtaining a back surface field (BSF) using the silicon oxide as the diffusion barrier. In an embodiment, the depositing (a) and annealing (b) can be combined in a single processing step, i.e. requiring only one loading/unloading process with one process chamber
It is important to note that the annealing (b) generally yields a homogenous boron doped region 8. The removing (c) then offers the choice of whether to retain a homogenous boron dope region 8 by removing the boron doping source 6 completely or obtain a selective boron doped emitter by selectively (partially) removing the boron doping source 6 for obtain e.g. a grid-like structure.
The present invention therefore provides an efficient method for providing a boron doped emitter 8. Depending on the removal step (c), the emitter 8 comprises a continuous boron doped layer having a generally homogenous concentration of boron, i.e. a homogenous boron doped emitter, or a continuous boron doped layer provided with smoothly interspersed regions 8a, 8b of higher and lower boron concentration, i.e. a selective boron doped emitter 8.
The present invention embodiments may also be applied for further types of solar cells, such as interdigitated back contact solar cells. In such interdigitated back contact solar cells, the boron-doped emitter 8 is provided on the back surface of the substrate 1, alternating with a phosphorus doped layer 12, e.g. in a strip-like manner. The present method embodiments may also be applied, and the boron extraction and phosphor diffusion may be achieved in a single annealing step (e) in the adjoining areas of the interdigitated back contact solar cell, after undoped silicon oxide 10 has been applied to the areas for the boron-doped emitter 8 only (d).
This sequence of processing steps is also shown schematically in
Up until the boron diffusion, the processing is similar to that depicted in
As shown in
Consecutively, the substrate 1 is annealed, and a selective boron doping layer is formed (low doped region 8a and high doped region 8b directly under the boron source 6, as shown in
Also, in the same processing chamber, the step indicated in
Then the undoped silicon oxide 10 is removed, as well as the boron source 6, as shown in
In an experimental set-up, the formation of a selective boron-doped emitter for a solar cell has been verified. In the examples, a BBr3 process was applied to provide a boron doping source 6 on the surface 2 of the substrate 1 (a).
In a first example, the boron doping source 6 was removed (c) after the boron-doped emitter 8 was formed (b). Then a silicon oxide layer was applied using plasma enhanced chemical vapor deposition (PECVD) (d), and the resulting substrate 2 was annealed in an N2 environment at 940° C. for 60 minutes (e).
In a second example, the boron doping source 6 was not removed, and the other steps were similarly applied (representing the part of the surface where the boron doping layer is not removed in actual applications.
Finally, a third, comparative, example was prepared without formation of the silicon oxide layer, but also the annealing was performed in an N2 atmosphere at 940° C. for 60 minutes.
The resulting doping profiles are shown in
The peak concentration went down from 1E+20/cm3 near the surface for the second example to about 3E+19/cm3 for the first example. Without the undoped silicon oxide, the decrease of the peak concentration is less as shown in the doping profile (large dash line). It is estimated that the peak concentration for first example can still be lowered even further by tuning the depositing and annealing while keeping the peak concentration of the second example.
According to further embodiments of the present invention, the method of the present invention further comprises processing steps to provide a complete solar cell. This involves providing the conductive contacts to the substrate, as e.g. already shown and described in relation to the interdigitated solar cell embodiment shown in the
The method then includes the further processing of the substrate, in general by removing the silicon oxide 10, at least in areas where conductive (e.g. metal) electrodes are to be formed on the substrate, passivation of the first and the second surface 2, 4, and providing conductive electrodes 22, 23. Removing the silicon oxide film 10 also includes removing the doping source 6 in case of the embodiments shown in
The actual contacting of the conductive electrodes 22, 23 with the substrate 1 can be accomplished in two different ways:
First is to provide the conductive electrodes 22, 23 on the first and/or second surface (e.g. using printing techniques, aligned with the high boron doped areas of the region 8 where applicable), and to fire through anneal the substrate so that the printed contact penetrates through the passivation film 21 to reach the region 8.
Alternatively, the passivation film is removed above the areas where the conductive electrodes 22, 23 are to be positioned (e.g. region 8b in case of
The present invention is also embodied as a solar cell comprising a boron-doped region 8 as obtained by the method according to any one of the method embodiments described above. This can be visible in the doping profile as obtained for the boron-doped emitter (see
The normal process flow of an n-substrate solar cell 1 with boron emitter 8 and phosphorus BSF 12 has a process flow:
(i) boron diffusion on the front side and boron source removal,
(ii) undoped silicon oxide film on the front side as the diffusion barrier, and
(iii) phosphorus diffusion on the rear side.
One novel aspect of the present invention is having the annealing step (e) in prior to (iii) which can be done consecutively in one process chamber. The invention does not increase the number of steps from the normal process flow, but only two extra procedures: (A) selective boron source removal at (i) and (B) annealing at higher temperature than phosphorus diffusion prior to (iii).
The new technology of the present invention embodiments is keeping the boron diffusion source under the diffusion barrier where metal contact will be formed. The boron surface concentration is kept high which enables low contact resistance.
The present invention embodiments have been described above with reference to a number of exemplary embodiments as shown in and described with reference to the drawings. Modifications and alternative implementations of some parts or elements are possible, and are included in the scope of protection as defined in the appended claims.
Number | Date | Country | Kind |
---|---|---|---|
2010116 | Jan 2013 | NL | national |
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/NL2014/050007 | 1/9/2014 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO2014/109639 | 7/17/2014 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
5928438 | Salami et al. | Jul 1999 | A |
6218270 | Yasunaga | Apr 2001 | B1 |
6444552 | Docter | Sep 2002 | B1 |
7615393 | Shah | Nov 2009 | B1 |
7704866 | Vanheusden | Apr 2010 | B2 |
20050133835 | Bu et al. | Jun 2005 | A1 |
20080176384 | Ko | Jul 2008 | A1 |
20090205712 | Cousins | Aug 2009 | A1 |
20090250793 | Sokolov | Oct 2009 | A1 |
20100015756 | Weidman | Jan 2010 | A1 |
20100055822 | Weidman | Mar 2010 | A1 |
20100009315 | Fujii | Apr 2010 | A1 |
20110146782 | Gabor | Jun 2011 | A1 |
20110300697 | Kohira | Dec 2011 | A1 |
20120024371 | Funakoshi | Feb 2012 | A1 |
20120167968 | Lossen et al. | Jul 2012 | A1 |
20130112260 | Bazer-Bachi et al. | May 2013 | A1 |
20130267059 | Kim | Oct 2013 | A1 |
20140065764 | Scardera | Mar 2014 | A1 |
Number | Date | Country |
---|---|---|
10 2009 041546 | Oct 2010 | DE |
10 2011 002748 | Jul 2012 | DE |
2011135249 | Nov 2011 | WO |
Entry |
---|
Kim et al., “Silicon solar cells with boron back surface field formed by using boric acid”, 2007, Proc. 22nd Eur. PV Solar Energy Conf. Exhib. 2007. All Pages. |
Thomas Krygowski et al.: “A Simultaneously Diffused, Textured, In Situ Oxide AR-Coated Solar Cell Process (STAR Process) for High-Efficiency Silicon Solar Cells” IEEE Transactions on Electron Devices, IEEE Service Center, Pisacataway, NJ, US, vol. 45, No. l, Jan. 1, 1998 (Jan. 1, 1998), XP011016393, ISSN: 0018-9383 the whole document. |
Arai E et al:“Applicability of Phosphorus and Boron Diffusion Parameters Extracted From Predeposition to Drive-In Diffusion for Bulk Silicon and Silicon-On-Insulator”, Japanese Journal of Applied Physics, The Japan Society of Applied Physics, Japan Society of Applied Physics, Tokyo; JP, vol. 42, No. 4A, Part 01, Apr. 1, 2003 (Apr. 1, 2003), pp. 1503-1510, XP001191392, ISSN: 0021-4922, DOI: 10.1143/JJAP.42.1503 the whole document. |
International Search Report, dated Apr. 1, 2014, from corresponding PCT application. |
Number | Date | Country | |
---|---|---|---|
20150357499 A1 | Dec 2015 | US |