CN110518084B - Gallium local-area-doped PERC (Positive electrode collector) battery and preparation method thereof - Google Patents
Gallium local-area-doped PERC (Positive electrode collector) battery and preparation method thereof Download PDFInfo
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
- H01L31/0682—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
Abstract
The invention discloses a preparation method of a locally gallium-doped PERC (Positive electrode collector) battery, which can realize high local doping concentration and low sheet resistance of the PERC battery. The invention also discloses a locally gallium doped PERC cell which has high local doping concentration and low sheet resistance. A preparation method of a gallium local-area-doped PERC battery comprises the following steps: A. patterning gallium metal at a temperature not lower than the melting point of gallium; B. placing the patterned metal gallium on the surface of a silicon wafer, and cooling the surface of the silicon wafer to be below the melting point temperature of the gallium for solidification; C. carrying out laser doping on a gallium graphic region of the silicon wafer; D. and carrying out metallization to prepare a back electrode, wherein the back electrode is contacted with the gallium-doped region.
Description
Technical Field
The invention belongs to the field of crystalline silicon solar cells, and relates to a locally gallium-doped PERC cell and a preparation method thereof.
Background
PERC (Passive Emitter and reader cell) is becoming the conventional technology of the next generation of solar cells. Fig. 1 shows a conventional PERC cell structure. Referring to fig. 1, the conventional PERC cell includes a front passivation anti-reflection layer 2, a silicon substrate 3, a silicon oxide film 41, an aluminum oxide film 42, and a silicon nitride film 43, which are sequentially stacked, a front electrode 1 forming an ohmic contact with the silicon substrate 3 through the front passivation anti-reflection layer 2, and a rear electrode 5 forming an ohmic contact with the silicon substrate 3 through the silicon oxide film 41, the aluminum oxide film 42, and the silicon nitride film 43. The silicon oxide/aluminum oxide/silicon nitride laminated passivation dielectric layer on the back of the PERC battery has an excellent passivation effect on the surface of the battery, and can reduce the surface recombination current to 15fA/cm2In the following, the conversion efficiency of the battery is greatly improved. But the composite current of the back metallization region is as high as 600-1000fA/cm2This is the bottleneck in the performance shortening of the PERC cell and in the efficiency improvement of the PERC cell.
At present, when the mass production efficiency of 5BB-SE-PERC batteries in the industry reaches 22.2-22.5%, the improvement of the efficiency of the back metallization region is greatly determined by the composite current of the back metallization region. The university of new south Wilms proposes a PERL structure, and local heavy doping is carried out on a metalized region of a battery, and the realization method is that boron diffusion is carried out on the metalized region by taking the ultra-thick silicon oxide as a mask, so that the composite current of a back metalized region is greatly reduced. Patent CN103996746A proposes that a layer of boron paste is printed on a back passivation dielectric layer, and the layer of boron paste is advanced to a metallization region in a laser ablation process. However, the two methods have respective disadvantages, the structure and the method for locally and heavily doping boron greatly increase the boron content in the matrix, and researches on Light Induced Degradation (LID) find that the size of LID in the PERC battery is directly related to the boron content in the matrix, and the outdoor application stability of the PERC battery is reduced due to the excessive doping of boron.
If the recombination current in the back side metallization region needs to be reduced, the doping concentration needs to be increased in the metallization region, and the existing solution cannot be properly solved in mass production. The mask thermal diffusion method adopted by the university of new south Wilms can only adopt silicon oxide as a back passivation film, but an aluminum oxide dielectric passivation film is widely applied in mass production at present, the film can only bear the temperature of about 600 ℃, and the boron diffusion at 900 ℃ can cause the crystallization of aluminum oxide and lose the passivation effect. Similar to the scheme proposed in CN103996746A in which boron paste is printed first to realize doping in the laser ablation process, in practice, the doping is greatly limited due to the blocking effect of the dielectric film layer, and the doping concentration and depth cannot be sufficient, which is much lower than the 10 Ω doped sheet square resistance obtained by the university of wils, new south.
Disclosure of Invention
In view of the above technical problems, the present invention provides a method for manufacturing a locally gallium-doped PERC cell, which can achieve high local doping concentration and low sheet resistance of the PERC cell. The invention also provides a locally gallium doped PERC cell having a high local doping concentration and a low sheet resistance.
In order to achieve the purpose, the invention adopts a technical scheme as follows:
a preparation method of a gallium local-area-doped PERC battery comprises the following steps:
A. patterning gallium metal at a temperature not lower than the melting point of gallium;
B. placing the patterned metal gallium on the surface of a silicon wafer, and cooling the surface of the silicon wafer to be below the melting point temperature of the gallium for solidification;
C. carrying out laser doping on a gallium graphic region of the silicon wafer;
D. and carrying out metallization to prepare a back electrode, wherein the back electrode is contacted with the gallium-doped region.
Preferably, in the step C, the irradiation width of the laser on the gallium imaging region of the silicon wafer is less than or equal to the line width of the gallium pattern.
Preferably, in the step C, a trace of scanning irradiation of the laser on the silicon wafer is consistent with a shape of the gallium pattern.
Preferably, in the step A, the temperature for patterning gallium is greater than or equal to 29.76 ℃; and in the step B, after the graphical metal gallium is placed on the surface of the silicon wafer, cooling the surface of the silicon wafer to be below 29.76 ℃.
Preferably, in the step A, the characteristic width of the gallium pattern is 30-130 μm.
Preferably, in the step B, the cooling rate of the surface of the silicon chip is-20 to-5 ℃/s.
Preferably, in the step B, the thickness of the metal gallium on the surface of the silicon wafer is 2-20 μm.
Preferably, in the step B, patterned metal gallium is placed on the surface of the silicon wafer by a screen printing, spraying or laser transfer printing method.
Preferably, a dielectric film is formed on the surface of the silicon wafer, and the preparation method further includes the following steps before step B: processing the surface of the silicon wafer by laser die sinking, removing a dielectric film at a position corresponding to a gallium pattern region on the surface of the silicon wafer, and exposing the surface of the silicon wafer; and in the step B, the patterned metal gallium is placed on the exposed silicon surface of the silicon wafer surface.
The other technical scheme adopted by the invention is as follows:
the PERC cell further comprises a front electrode and a back electrode, wherein the front electrode penetrates through the front passivation antireflection layer and forms ohmic contact with the silicon substrate, the back electrode penetrates through the obtained back dielectric film and forms ohmic contact with the silicon substrate, a gallium doped region is formed on the silicon substrate, and the back electrode is in contact with the gallium doped region of the silicon substrate.
Preferably, the gallium-doped region is formed by: patterning gallium metal at a temperature not lower than the melting point of gallium; processing the surface of the silicon wafer by laser die sinking, removing a dielectric film at a position corresponding to a gallium pattern region on the surface of the silicon wafer, and exposing the surface of the silicon wafer; placing the patterned metal gallium on the exposed silicon surface of the silicon wafer surface, and cooling the silicon wafer surface to a temperature below the melting point temperature of the gallium for curing; and carrying out laser doping on the gallium pattern region of the silicon wafer.
Compared with the prior art, the invention has the following advantages by adopting the scheme:
according to the PERC battery and the preparation method thereof, the characteristic of low melting point of gallium metal is utilized, the graph is patterned when the melting point of the gallium metal is higher than the melting point of the gallium metal, the graph is rapidly cooled after falling on the surface of a silicon wafer, laser doping is adopted, high doping concentration of a back metallization region is realized, low sheet resistance is obtained, and the sheet resistance can be as low as 10 omega; according to the PERC battery prepared by the method, the composite current in the back metalized area can be reduced to 100 & lt 300 & gtfA/cm, the open-circuit voltage of the PERC battery can be increased by 5-7mV, and the conversion efficiency is increased by over 0.3%.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a schematic diagram of a conventional PERC cell;
fig. 2 is a schematic structural diagram of a PERC battery according to an embodiment.
Wherein;
1. a front electrode; 2. a front passivation antireflection layer; 3. a silicon substrate; 30. a gallium-doped region; 4. a back dielectric film; 41. a silicon oxide film; 42. an aluminum oxide film; 43. a silicon nitride film; 5. and a back electrode.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings so that the advantages and features of the invention may be more readily understood by those skilled in the art. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The embodiment provides a local gallium doped PERC cell and a preparation method thereof. Referring to fig. 1, the PERC battery includes: the device comprises a front electrode 1, a front passivation anti-reflection layer 2, a silicon substrate 3, a back dielectric film 4 and a back electrode 5, wherein the back dielectric film 4 consists of three layers, namely a silicon oxide film 41, an aluminum oxide film 42 and a silicon nitride film 43. The front passivation anti-reflection layer 2, the silicon substrate 3, the silicon oxide film 41, the aluminum oxide film 42, and the silicon nitride film 43 are stacked in this order from top to bottom. The front passivation anti-reflection layer 2 is provided with a plurality of windows extending downwards to the front surface of the silicon substrate 3, and the front electrode 1 is formed at the windows, namely the front electrode 1 penetrates through the front passivation anti-reflection layer 2 to form ohmic contact with the silicon substrate 3. The back electrode 5 is formed on the silicon nitride film 43, and the silicon nitride film 43, the aluminum oxide film 42 and the silicon oxide film 41 are opened with a plurality of windows extending upward to the back surface of the silicon substrate 3 to expose the back surface of the silicon substrate 3, and a portion of the back electrode 5 is located in the windows and forms ohmic contact with the silicon substrate 3. Specifically, the silicon substrate 3 is provided with a plurality of gallium doped regions 30, and the doped sheet resistance is 10-40 omega; the window on the back is opened corresponding to the gallium doped region 30, and the back electrode 5 is specifically contacted with the gallium doped region 30 of the silicon substrate 3.
The preparation process of the gallium-doped region 30 is as follows: firstly, preparing a layer of metal gallium by patterning, ensuring that the temperature of the gallium is more than or equal to 29.76 ℃ when patterning because the melting point of the gallium is 29.76 ℃, quickly cooling the silicon wafer to be below 29.76 ℃ after the gallium pattern falls on the surface of the silicon wafer, solidifying the gallium on the surface of the silicon wafer to form a pattern (the patterning method can be screen printing, spraying, laser transfer printing and other methods), then doping gallium metal into the silicon wafer by carrying out laser propulsion at the same position through laser, and finally forming gallium local doping. And then carrying out a metallization process to complete the preparation of the PERC battery with the locally-doped gallium on the back surface.
The preparation method of the local gallium doped PERC cell of the embodiment specifically comprises the following steps:
the method comprises the following steps: and patterning the metal gallium. By utilizing the characteristic of low melting point of gallium, the patterning temperature is ensured to be more than or equal to 29.76 ℃, and the characteristic width of the pattern is 30-130 mu m.
Step two: and rapidly cooling and solidifying the gallium pattern. After the gallium graph falls on the surface of the silicon wafer through screen printing, the surface temperature of the silicon wafer is rapidly reduced to be below 29.76 ℃, the cooling rate is minus 20 to minus 5 ℃/s (namely the surface temperature of the silicon wafer is reduced by 5 to 20 ℃ per second), and at the moment, gallium is cooled to form solid metal which is solidified on the surface of the silicon wafer. The printing thickness is 2-20 μm. The surface of the silicon chip can be a bare silicon chip, or a surface with a back dielectric film, wherein the back dielectric film can be one or a combination of a plurality of metal/nonmetal oxides and nitrides such as silicon oxide, aluminum oxide, silicon nitride, silicon carbide, zinc oxide, titanium oxide, tungsten oxide and the like. When the surface of the silicon wafer is provided with the passivation film and the gallium pattern is required to be in direct contact with the silicon wafer, laser film opening can be performed in the gallium pattern area through a laser film opening method in one step, and the dielectric film is locally removed.
Step three: and (4) laser doping. Performing laser treatment again in the pattern region by using the laser doping effect, wherein the width of a treatment laser line is less than or equal to that of a first-time gallium pattern line, and the patterns are consistent in shape;
step four: and (6) metallization. The preparation of the metal electrode can be realized by adopting metallization technologies adopted in various industries such as silk-screen sintering, PVD, CVD, electroplating and the like.
The existing scheme capable of realizing high local doping concentration and low sheet resistance cannot be applied to the PERC battery passivated by aluminum oxide, and the technical schemes in other patents cannot realize high doping concentration and low sheet resistance. The invention utilizes the low melting point characteristic of gallium metal, carries out patterning when the melting point of the gallium metal is higher than the melting point of the gallium metal, rapidly cools down after the pattern falls on the surface of a silicon wafer, carries out laser doping, realizes high doping concentration of a back metallization region, and simultaneously obtains low-level sheet resistance which can be as low as 10 omega. According to the PERC battery prepared by the method, the composite current in the back metalized area can be reduced to 100 & lt 300 & gtfA/cm, the open-circuit voltage of the PERC battery can be increased by 5-7mV, and the conversion efficiency is increased by more than 0.3% abs.
The PERC cells prepared by the conventional technical route were selected as comparative examples and tested for their quantum response curves with the PERC cells of the examples of the invention. It can be found that the quantum response of the PERC cell of the embodiment of the invention is more advantageous than the long-wave response of the comparative example, particularly the PERC cell of the embodiment of the invention. Further illustrating the low recombination current characteristic of backside metallization region protrusion in the PERC cell of embodiments of the present invention.
The PERC battery provided by the embodiment of the invention can be subjected to X-ray energy spectrum analysis (EDS), SIMS and XPS in a Scanning Electron Microscope (SEM) and doped region component analysis, so that the gallium content of a doped region is higher than that of a silicon substrate and other undoped regions.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and are preferred embodiments, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes or modifications made according to the principles of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of a local gallium doped PERC battery is characterized by comprising the following steps:
A. patterning gallium metal at a temperature not lower than the melting point of gallium;
B. placing the patterned metal gallium on the surface of a silicon wafer, and cooling the surface of the silicon wafer to be below the melting point temperature of the gallium for solidification;
C. carrying out laser doping on a gallium graphic region of the silicon wafer;
D. and carrying out metallization to prepare a back electrode, wherein the back electrode is contacted with the gallium-doped region.
2. The production method according to claim 1, wherein in the step C, the irradiation width of the laser light on the gallium-imaged region of the silicon wafer is less than or equal to the line width of the gallium pattern.
3. The production method according to claim 1 or 2, wherein in the step C, a trace of scanning irradiation of the silicon wafer by the laser coincides with a shape of the gallium pattern.
4. The preparation method according to claim 1, wherein in the step A, the temperature for patterning gallium is greater than or equal to 29.76 ℃; and in the step B, after the graphical metal gallium is placed on the surface of the silicon wafer, cooling the surface of the silicon wafer to be below 29.76 ℃.
5. The method according to claim 1, wherein in step A, the feature width of the gallium pattern is 30 to 130 μm.
6. The preparation method according to claim 1, wherein in the step B, the cooling rate of the surface of the silicon wafer is-20 to-5 ℃/s.
7. The preparation method according to claim 1, wherein in the step B, the thickness of the metal gallium on the surface of the silicon wafer is 2-20 μm.
8. The method according to claim 1, wherein a dielectric film is formed on the surface of the silicon wafer, and the method further comprises the following steps before the step B: processing the surface of the silicon wafer by laser die sinking, removing a dielectric film at a position corresponding to a gallium pattern region on the surface of the silicon wafer, and exposing the surface of the silicon wafer; and in the step B, the patterned metal gallium is placed on the exposed silicon surface of the silicon wafer surface.
9. The local gallium-doped PERC cell comprises a front passivation antireflection layer, a silicon substrate and a back dielectric film which are sequentially stacked, and further comprises a front electrode and a back electrode, wherein the front electrode penetrates through the front passivation antireflection layer and forms ohmic contact with the silicon substrate, the back electrode penetrates through a back dielectric film and forms ohmic contact with the silicon substrate, and the local gallium-doped PERC cell is characterized in that: the PERC cell is produced by the production method according to any one of claims 1 to 8, the silicon substrate having a gallium-doped region formed thereon, the back electrode being in contact with the gallium-doped region of the silicon substrate.
10. The PERC cell of claim 9, wherein said gallium doped region is formed by: patterning gallium metal at a temperature not lower than the melting point of gallium; processing the surface of the silicon wafer by laser die sinking, removing a dielectric film at a position corresponding to a gallium pattern region on the surface of the silicon wafer, and exposing the surface of the silicon wafer; placing the patterned metal gallium on the exposed silicon surface of the silicon wafer surface, and cooling the silicon wafer surface to a temperature below the melting point temperature of the gallium for curing; and carrying out laser doping on the gallium pattern region of the silicon wafer.
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| KR101925928B1 (en) * | 2013-01-21 | 2018-12-06 | 엘지전자 주식회사 | Solar cell and manufacturing method thereof |
| CN104716224A (en) * | 2013-12-13 | 2015-06-17 | 上海神舟新能源发展有限公司 | Back-passivation efficient PERL battery technology |
| CN104409570A (en) * | 2014-11-21 | 2015-03-11 | 广西智通节能环保科技有限公司 | Manufacturing method of crystalline silicon solar cell |
| CN109686814A (en) * | 2017-10-19 | 2019-04-26 | 上海神舟新能源发展有限公司 | A kind of production method that back is passivated efficient p-type PERL double-side cell |
| CN208538867U (en) * | 2018-04-26 | 2019-02-22 | 北京梦之墨科技有限公司 | A kind of bus bar and electrode on solar battery |
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