CN113035996A - High-efficiency battery based on nano silicon slurry containing high-concentration boron and manufacturing method - Google Patents
High-efficiency battery based on nano silicon slurry containing high-concentration boron and manufacturing method Download PDFInfo
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 103
- 239000002002 slurry Substances 0.000 title claims abstract description 60
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 123
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 123
- 239000010703 silicon Substances 0.000 claims abstract description 123
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 59
- 239000011574 phosphorus Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000002161 passivation Methods 0.000 claims abstract description 51
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 43
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000007639 printing Methods 0.000 claims abstract description 39
- 239000004332 silver Substances 0.000 claims abstract description 39
- 229910052709 silver Inorganic materials 0.000 claims abstract description 39
- 238000009792 diffusion process Methods 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 26
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl chloride Substances ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 229910019213 POCl3 Inorganic materials 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 10
- 238000005530 etching Methods 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 18
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical group [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 7
- 230000003667 anti-reflective effect Effects 0.000 claims 1
- 230000006872 improvement Effects 0.000 abstract description 16
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 abstract description 4
- 235000012431 wafers Nutrition 0.000 description 76
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 238000009766 low-temperature sintering Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910004205 SiNX Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000007581 slurry coating method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000125205 Anethum Species 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- FGUJWQZQKHUJMW-UHFFFAOYSA-N [AlH3].[B] Chemical compound [AlH3].[B] FGUJWQZQKHUJMW-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000005360 phosphosilicate glass Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses a method for manufacturing a high-efficiency battery based on high-concentration boron-containing nano silicon slurry, which comprises the following steps of: s1, taking a silicon wafer, cleaning and texturing, setting an SE area on the front surface of the silicon wafer, and printing phosphorus-containing nano silicon slurry in the SE area; s2 in POCl3Performing phosphorus diffusion in the atmosphere to form a phosphorus-doped region in the SE region, thereby obtaining phosphorus-silicon glass; s3, removing the phosphorosilicate glass, etching the back, depositing an antireflection film on the front side of the silicon wafer, and depositing a passivation film on the back side of the silicon wafer; s4, printing high-concentration boron nano silicon slurry on the passivation film on the back of the silicon wafer, and scanning by laser to realize localized boron doping; s5, printing aluminum paste on the back surface of the silicon wafer, and printing silver paste on the SE structure on the front surface of the silicon wafer; and S6, sintering to form the battery. The invention also discloses a high-efficiency battery manufactured by the method. The invention relates to aAfter an SE structure is formed and local localized boron doping is carried out, the sintering temperature is reduced, and therefore the improvement of the battery efficiency is effectively realized.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a high-efficiency cell based on nano silicon slurry containing high-concentration boron and a manufacturing method thereof.
Background
The crystalline silicon solar cell is the mainstream of the current photovoltaic market due to the high conversion efficiency and long service life. Currently, the commercial production of crystalline silicon solar cells is mainly based on p-type cells. Compared with a p-type conventional battery, a p-type PERC (Passivated Emitter and reactor Contact) battery has mainly the following advantages: (1) the internal back reflection is enhanced, and the optical loss of long wave is reduced. (2) The high quality of the back passivation greatly improves the open circuit voltage (Voc) and short circuit current (Isc) of the PERC battery, so that the conversion efficiency is higher, and the highest conversion efficiency can approach or exceed 22%. Moreover, since the compatibility between the process for manufacturing the PERC cell (as shown in a in fig. 3) and the process for manufacturing the P-type conventional cell is high, the introduction of the process for manufacturing the P-type conventional cell into the PERC cell technology is low in cost and efficient, and the production capacity of the PERC cell is expected to completely replace the existing P-type conventional cell in the coming years.
However, the average efficiency of the PERC battery production is actually achieved by more than 22% by the conventional PERC process and technology reserve, and a plurality of advanced technologies need to be superimposed, which not only increases the cost and difficulty of battery manufacturing, but also requires significant addition and modification of equipment and processes on the existing production line, and these solutions cannot meet the application requirements of the industry exceeding the PERC battery.
At present, a method for improving performance of a PERC cell is to print a slurry of boron-doped silicon nanoparticles on a passivation film on a backside of the PERC cell, and upgrade the PERC structure to a PERL (Passivated Emitter Rear Localized) structure, which mainly includes: printing boron-containing nano silicon slurry on a passivation film on the back surface of the battery according to a designed pattern (the main stream is Al)2O3 and SiNxThe laminate construction of (a); by usingA suitable laser (disclosure data is shown as 532nm, which is pulsed but not limited to this type) is aligned with the borosilicate slurry coating film pattern after the preliminary drying, and then the borosilicate slurry coating film pattern is scanned one by one, and a passivation film (a contact channel between the back electrode and the substrate silicon wafer) under the coating film is opened by utilizing an instant high-temperature thermal effect generated by the laser, and the boron contained in the slurry is doped into a predetermined region on the back surface of the silicon wafer (i.e. the laser simultaneously performs two functions of opening the passivation film and partially doping boron); finally, aluminum paste is printed on the whole back surface of the battery, and the aluminum paste and the silver paste on the front surface of the battery are sintered together to form the improved PERC (PERL-like) high-efficiency battery containing the regions which are doped with boron partially. The BSF (Back Surface field) formed by the local high-concentration laser doping and boron-doping instead of the local aluminum paste thermal diffusion can significantly improve Voc (open circuit voltage) and FF (fill factor), thereby improving the conversion efficiency of the cell. However, this method has at least the following disadvantages, which results in unstable cell efficiency improvement effect and low cost performance for mass production introduction: (1) according to the conventional fabrication process of the PERC cell, after being doped with boron locally by laser, the back surface of the cell needs to be printed with aluminum paste on the whole, and then the front surface and the back surface of the cell need to be sintered simultaneously with silver paste on the front surface to form front and back electrodes in good contact with a silicon wafer, wherein the sintering temperature of the conventional silver paste for achieving good contact with the silicon wafer is generally required to be above 850 ℃, the forming temperature of aluminum-silicon alloy is only 577 ℃, and the diffusion temperature of boron is at least above 1000 ℃, in view of the fabrication cost and the productivity, high-temperature sintering (i.e. the sintering temperature is about 850) in cooperation with the front surface silver paste can be selected during mass production, such a high-temperature sintering process can cause an over-excited reaction between aluminum and silicon in the back surface aluminum paste, so that aluminum entering the silicon wafer from below the electrode can greatly exceed a B-BSF boron back field formed by doping with laser (the depth of boron can only, and the aluminum can penetrate into the silicon wafer by more than 10um at high temperature), thereby destroying or offsetting the efficiency improvement effect due to the laser doping of boron. (2) The boron content in the boron nano silicon slurry is limited by the silicon nanoparticle synthesis mode, the boron-silicon molar ratio is less than or equal to 0.02, and the efficiency improvement effect due to laser doping with boron is difficult to ensure under the condition that interference is caused by an over-excited reaction of aluminum and silicon under a high-temperature condition.
In addition, alsoOne method to improve the performance of the PERC cell, SE-PERC technology (where SE is a Selective Emitter), is to use the front face POCl of the PERC cell as shown in b of fig. 33The PSG (phosphosilicate glass) formed by phosphorus diffusion (phosphorus oxychloride) is doped with laser light under appropriate conditions to form the patterned phosphorus-doped region (SE), which can stably achieve a cell efficiency improvement of 0.15% or more on average over the standard PERC. The SE structure can greatly reduce the impedance between the silver electrode and the silicon chip, so that the silver paste on the front side of the battery can be well contacted with the silicon chip under the low-temperature sintering condition. In addition, from the perspective of achieving good contact between the front silver electrode and the silicon wafer, the SE structure with the higher phosphorus-doping concentration is more favorable for achieving good contact between the front silver paste and the silicon wafer at a lower temperature. However, in the SE-PERC technique, POCl is utilized3The phosphorus diffusion concentration realized by the PSG formed after diffusion is limited, the sintering temperature is difficult to be greatly reduced, the B-BSF formed by the over-excited reaction between aluminum and silicon cannot be effectively prevented, and the improvement of the battery efficiency is effectively realized; and too high phosphorus concentration can cause the loss of incident light of a window part which is exposed to sunlight and is outside the SE structure, so that the improvement effect of the conversion efficiency of the cell is not obvious. In order to achieve a higher-concentration phosphorus-doped SE structure, a higher phosphorus concentration is obtained under a higher-density laser condition, but this causes more damage to the silicon wafer (due to POCl)3The PSG formed by diffusion has almost no absorption to the used laser wavelength), and the improvement of the battery efficiency cannot be effectively realized.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-efficiency battery based on nanometer silicon slurry containing high-concentration boron and a manufacturing method thereof.
According to one aspect of the invention, a method for manufacturing a high-efficiency battery based on nano silicon slurry containing high-concentration boron is disclosed, and the technical scheme is as follows:
a manufacturing method of a high-efficiency battery based on nanometer silicon slurry containing high-concentration boron comprises the following steps:
s1, taking a silicon wafer, cleaning and texturing, setting an SE area on the front surface of the silicon wafer, and printing phosphorus-containing nano silicon slurry in the SE area;
s2, performing phosphorus diffusion in the POCl3 atmosphere, and forming a phosphorus-heavily-doped region in the SE region;
s3, removing phosphorosilicate glass formed on the surface of the silicon wafer in the phosphorus diffusion process, carrying out back etching, depositing an antireflection film on the front side of the silicon wafer, and depositing a passivation film on the back side of the silicon wafer;
s4, printing high-concentration boron nano silicon slurry on the passivation film on the back of the silicon wafer, and scanning by laser to realize localized boron doping;
s5, printing aluminum paste on the back surface of the silicon wafer, and printing silver paste on the SE structure on the front surface of the silicon wafer;
and S6, sintering to form the battery.
Preferably, in step S4, the high-concentration boron nano-silicon slurry is boron-silicon molar ratio of 0.2-2.5.
Preferably, in step S4, the printing area of the high-concentration boron nano-silicon slurry is larger than the set area of the localized boron doping.
Preferably, in step S4, the laser has a wavelength of 532nm to 1040 nm.
Preferably, in step S4, the thickness of the high-concentration boron nano-silicon paste printed on the passivation film on the back surface of the silicon wafer is 1.5 to 2.5 μm after being a dry film.
Preferably, the sintering temperature is 570-780 ℃.
Preferably, the step S1 further comprises drying the phosphorus-containing nano silicon slurry, wherein the average particle size of the silicon nano particles in the phosphorus-containing nano silicon slurry is not more than 50nm, and the phosphorus content is not less than 5x10^19atoms/cm 3; the drying temperature is 180 ℃ and 250 ℃, and the drying time is 8-15 min.
Compared with the prior art, the manufacturing method of the high-efficiency battery based on the high-concentration boron-containing nano silicon slurry has the following beneficial effects:
(1) at this stage, the mass-producible forming method of the back electrode only uses the aluminum paste, and for the battery without the front-side SE structure, the high-temperature sintering condition of the front silver must be matched, and the over-excited reaction between the aluminum and the silicon under the high-temperature condition must weaken or offset the efficiency improvement effect due to the local boron doping.
The B/Al-BSF (boron-aluminum mixed back field) formed by partially doping boron and sintering aluminum paste is adopted on the back surface to replace the Al-BSF (aluminum back field) in the traditional PERC (Passivated Emitter back field Contact) battery, the prepared battery is similar to a PERL (Passivated Emitter Rear Localized, Passivated Emitter back local diffusion) battery in structure, the conversion efficiency of the battery can be improved, and the absolute efficiency value of the battery can be improved by more than 0.4% compared with that of the traditional SE-PERC battery.
(2) Compared with the traditional method which adopts pure POCl3The gas diffusion method comprises the steps of presetting a region for forming an SE structure on the front surface of a silicon wafer, printing silicon nano particle slurry containing quantitative phosphorus concentration and capable of easily and efficiently achieving local high-concentration phosphorus diffusion in the SE region, and then performing POCl3Conventional thermal diffusion of phosphorus is performed in an atmosphere to form the desired SE structure with a higher concentration of phosphorus. The SE structure can greatly reduce the surface resistance Rs between the positive silver and the silicon wafer (the surface resistance Rs can be controlled to be 50-90ohm/sq), and the phosphorus-doped SE structure with higher concentration can reduce the sintering temperature, thereby furthest protecting the formed boron back surface field from being eroded by aluminum paste, further effectively improving the battery efficiency, and simultaneously reducing the sintering temperature, reducing the energy consumption and improving the productivity.
(3) Compared with the traditional method in which the SE structure is formed in a laser PSG mode, the method has the advantages that the thermal diffusion process is adopted, the damage to the silicon wafer possibly caused in the SE structure doping and forming stage is avoided, the improvement of the battery efficiency and the long-term stability are facilitated, the equipment requirement is low, a laser with the requirement on the mass production capacity is not needed, the compatibility with the existing PERC technology is high, only the phosphorus-containing silicon slurry is additionally used on the basis of the standard PERC technology, the printing process with the alignment function is added, the standard PERC production line can be upgraded to the production line required by the technology, and the cost can be reduced.
According to another aspect of the invention, a high-efficiency battery manufactured by the method is disclosed, and the technical scheme is as follows:
a high efficiency battery made by the above method comprising: silver electrode, anti-reflection film, silicon chip, aluminum paste layer and passive film,
a phosphorus heavily-doped region and a light-doped region are arranged on the front surface of the silicon wafer, the anti-reflection film is arranged on the outer layer of the light-doped region, the phosphorus heavily-doped region penetrates through the anti-reflection film to be in contact with the silicon wafer, and the silver electrode is arranged on the phosphorus heavily-doped region;
the passivation film is arranged on the back surface of the silicon wafer, a boron heavily-doped region is arranged on the passivation film, the boron heavily-doped region penetrates through the passivation film to be in contact with the silicon wafer, and the aluminum paste layer is arranged on the passivation film.
Preferably, the silicon wafer is a P-type monocrystalline silicon wafer.
Preferably, the Rs (i.e., surface resistance) of the phosphorus-doped region is 55-60ohm/sq, and the Rs of the boron-doped region is 12 ± 2 ohm/sq.
According to the high-efficiency cell disclosed by the invention, due to the SE structure with the high phosphorus concentration on the front surface, the silver electrode and the silicon wafer can be in good contact under the low-temperature sintering condition, and under the low-temperature sintering condition, the over-excited reaction between the back aluminum and the silicon can be inhibited, so that the B-BSF (boron back field) effect formed by doping boron with the local localized laser is protected, and the photoelectric conversion efficiency (absolute value) of the cell can be improved by more than 0.4%.
Drawings
Fig. 1 is a process flow diagram of a method for manufacturing a high-efficiency battery based on a nano-silicon slurry containing high-concentration boron in an embodiment of the present disclosure;
FIG. 2 is a schematic structural diagram of a high-efficiency battery (i.e., an SE-PERL battery) based on nano silicon slurry containing high-concentration boron in the embodiment of the disclosure;
FIG. 3 is a comparison of a manufacturing method of a high-efficiency battery based on nano-silicon slurry containing high-concentration boron in the embodiment of the present disclosure and a prior art process flow;
fig. 4 is a graph comparing the effect of the high-efficiency battery based on the nano-silicon slurry containing high concentration boron in the embodiment of the present disclosure with the battery in the prior art.
In the figure: 1-a silver electrode; 2-antireflection film; 3-a light doping area; 4-a phosphorus heavily doped region; 5-a silicon wafer; a 6-boron heavily doped region; 7-aluminum paste layer; 8-a passivation film;
a is a standard PERC; b is SE-PERC; c is SE-PERL.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Since in the prior art (especially in the PERC technology), due to the use of POCl3The phosphorus diffusion concentration realized by the PSG formed after diffusion is limited, and the sintering temperature is high, so that a series of defects cause the problem of low battery conversion efficiency. Therefore, in order to solve the above problems in the prior art, the present invention discloses a method for manufacturing a high efficiency battery based on a nano silicon slurry containing high concentration boron, comprising:
s1, taking a silicon wafer, cleaning and texturing, setting an SE area on the front surface of the silicon wafer, and printing phosphorus-containing nano silicon slurry in the SE area;
s2, performing phosphorus diffusion in the POCl3 atmosphere, forming phosphorus-silicon glass (PSG) on the surface of the silicon wafer, and forming a phosphorus-heavily-doped region in the SE region;
s3, removing phosphorosilicate glass formed on the surface of the silicon wafer in the phosphorus diffusion process, carrying out back etching, depositing an antireflection film on the front side of the silicon wafer, and depositing a passivation film on the back side of the silicon wafer;
s4, printing high-concentration boron nano silicon slurry on the passivation film on the back of the silicon wafer, and scanning by laser to realize localized boron doping;
s5, printing aluminum paste on the back surface of the silicon wafer, and printing silver paste on the SE structure on the front surface of the silicon wafer;
and S6, sintering to form the battery.
Correspondingly, the present disclosure also provides a high efficiency battery prepared by the above method, comprising: silver electrode, anti-reflection film, silicon chip, aluminium paste layer, passive film,
a phosphorus heavily-doped region and a light-doped region are arranged on the front surface of the silicon wafer, the anti-reflection film is arranged outside the light-doped region, the phosphorus heavily-doped region penetrates through the anti-reflection film to be in contact with the silicon wafer, and the silver electrode is arranged on the phosphorus heavily-doped region;
the passivation film is arranged on the back surface of the silicon wafer, a boron heavily-doped region is arranged on the passivation film, the boron heavily-doped region penetrates through the passivation film to be in contact with the silicon wafer, and the aluminum paste layer is arranged on the passivation film.
Example 1
As shown in fig. 1, the present embodiment discloses a method for manufacturing a high efficiency battery based on a nano silicon slurry containing high concentration of boron, which includes:
and step S1, taking the silicon wafer, cleaning and texturing, setting an SE area on the front surface of the silicon wafer, and printing phosphorus-containing nano silicon slurry in the SE area.
In this embodiment, the silicon wafer is a P-type monocrystalline silicon wafer, and certainly, other types of silicon wafers may also be used, which is not further limited in this embodiment.
In this embodiment, step S1 further includes drying the printed phosphorus-containing nano-silica slurry. Wherein the average grain diameter of silicon nano particles in the phosphorus-containing nano silicon slurry is not more than 50nm, and the phosphorus content is not less than 5x10^19atoms/cm3. The drying temperature is preferably 180 ℃ and 250 ℃, the drying time is preferably 8-15min, the thickness of the phosphorus-containing film layer formed after drying is preferably controlled to be about 1.8 μm, and the line width is preferably controlled to be about 148 μm.
It should be noted that the printing in this embodiment preferably uses a conventional screen printing technique, and the details are not described below.
Step S2, in POCl3Phosphorus diffusion is performed in the atmosphere, so that phosphorus-silicon glass (PSG, i.e., a silicon dioxide layer containing phosphorus atoms) is formed on the surface of the silicon wafer, and a phosphorus-heavily doped region (n + +) is formed in the SE region.
In the present embodiment, the phosphorus diffusion is performed under the conventional phosphorus thermal diffusion process conditions, so as to form a low-damage phosphorus-doped region (n + +) in the region printed with the phosphorus-containing nano-silicon paste, i.e., to form an SE structure, and the SE structure is a light-doped region (n +) opposite to the light-receiving portion (i.e., between the electrode and the electrode), which helps to ensure that the silver electrode on the front side of the battery and the silicon substrate are in good contact under the low-temperature sintering condition.
In this embodiment, the Rs (i.e., surface resistance) of the phosphorus heavily doped region is preferably controlled to be 55-60 ohm/sq.
And step S3, removing the phosphorosilicate glass, carrying out back etching, depositing an antireflection film on the front side of the silicon wafer, and depositing a passivation film on the back side of the silicon wafer.
In this embodiment, the phosphorosilicate glass is removed and the back etching is performed according to a method in a normal PERC process, which is not described herein again. Al is preferably used for both the antireflection film and the passivation film2O3Or SiNxThe material is deposited.
Step S4, printing high-concentration boron nano silicon slurry on the passivation film on the back of the silicon chip, and scanning with laser to realize the localized boron doping to form a boron heavily doped region (p + +).
In consideration of the improvement effect of the method of the embodiment of the present disclosure on the cell efficiency by partially doping with boron, the improvement effect is closely related to the total amount and the surface concentration of boron entering the silicon wafer through the opening of the passivation film under the printed high-concentration boron nano-silicon slurry pattern. In the high-concentration boron nano-silica slurry (organic solvent dispersion with solid content including silicon-boron composite nanoparticles being 5-10%, hereinafter referred to as borosilicate-containing slurry) in the embodiment, the boron-silicon molar ratio should be not less than 0.2, preferably 0.2-2.5. Because the thickness of the boron-containing silicon paste layer after the printed boron-containing silicon paste is dried under certain conditions (preferably, the drying temperature is 200 ℃, and the drying time is 10min) directly influences the total amount of boron entering the silicon wafer through the opening of the passivation film, in order to avoid the damage of laser to the passivation film and the silicon wafer except the opening of the passivation film, the wavelength of the laser should be under the premise of meeting the opening and doping of the passivation film, and the boron-containing silicon paste can absorb the boron-containing silicon paste, namely: the irradiation energy of the laser ensures that the passive film can be easily opened after the absorption of the boron-containing silicon slurry layer is passed through, and the boron amount required for effectively improving the battery efficiency is realized (practice proves that the boron doping amount is 10^ b21atoms/cm3When the battery is used, the battery efficiency can be effectively improvedThe doping effect can reach more than 0.4% in the silicon slice. In this embodiment, the laser wavelength is preferably 532nm to 1040nm, so as to avoid the problem that the laser energy density reaching the surface of the passivation film is too low to achieve a sufficient boron doping amount, and the problem that the laser energy is too high to possibly cause the cell efficiency to be low due to damage to the surrounding passivation film or the silicon wafer. Theoretically, the higher the boron content in the boron-containing silicon paste, the smaller the film thickness after drying, the more likely the desired boron doping amount can be achieved with the smaller laser energy density, and in practice, it is found that it is difficult to uniformly control the thickness of the boron-containing silicon paste after drying to be less than 1 μm by using the screen printing technique, and therefore, in this embodiment, the dry film thickness of the printed boron-containing silicon paste is preferably 1.5-2.5 μm. In addition, the thinner dry film thickness is also beneficial to meeting the mass production condition.
In addition, considering the problems of damage caused by direct irradiation of laser on the silicon wafer and the precision of laser alignment, the printing pattern of the high-concentration boron nano-silicon slurry is larger than the contact area of the preset back aluminum and the silicon wafer, that is, the printing area of the high-concentration boron nano-silicon slurry should be larger than the set area of localized boron doping, such as: good contact between the aluminum backing and the silicon wafer requires a line width of 40um, and the printing line width of the boron-containing silicon paste should be more than 80 um.
And step S5, printing aluminum paste on the back surface of the silicon chip, and printing silver paste on the SE structure on the front surface of the silicon chip.
In this embodiment, printing the aluminum paste on the back surface of the silicon wafer refers to: and (3) printing low-temperature sinterable aluminum paste (such as aluminum paste A special for a PERC battery) on the full face (single-face battery) or part (double-face battery) of the region capable of covering the boron-containing silicon paste printing area, and printing the silver paste on the front face by adopting silver paste B special for the PERC battery (obtaining a silver electrode after sintering).
And step S6, sintering to form the battery.
Specifically, on the premise of ensuring good contact between the front silver electrode and the silicon wafer, the front silver and the back aluminum are co-sintered at the lowest temperature, and are sintered at one time to form good contact between the front silver electrode and the silicon wafer and between the back aluminum paste layer and the silicon wafer, so as to finally form the high-efficiency cell with the SE-PERL structure, as shown in FIG. 2. In the embodiment, the sintering temperature is 570-780 ℃, which is lower than the sintering temperature (about 850 ℃) of the conventional RERC process, so that the low-temperature sintering is realized.
The embodiment also discloses a high-efficiency battery based on the high-concentration boron-containing nano silicon slurry prepared by the method, which comprises a silver electrode 1, an anti-reflection film 2, a silicon wafer 5, an aluminum slurry layer 7 and a passivation film 8, as shown in fig. 2. Wherein:
a silicon wafer 5, preferably a P-type monocrystalline silicon wafer is used as a substrate;
a phosphorus heavily-doped region 4 (namely an SE structure) and a lightly-doped region 3 are arranged on the front surface of the silicon wafer 5, an anti-reflection film 2 is arranged outside the lightly-doped region 3, the phosphorus heavily-doped region 4 penetrates through the anti-reflection film 2 to form good contact with the silicon wafer, and a silver electrode 1 (obtained by sintering silver paste) is arranged in the phosphorus heavily-doped region 4;
a passivation film 8 is arranged on the back surface of the silicon wafer 5, a boron heavily-doped region 6 is arranged on the passivation film 8, the boron heavily-doped region 6 penetrates through the passivation film 8 to form good contact with the silicon wafer 5, Rs of the boron heavily-doped region 6 is 12 +/-2 ohm/sq, and an aluminum paste layer 7 is arranged outside the passivation film 8.
According to the high-efficiency battery prepared by the method disclosed by the embodiment of the disclosure, due to the SE structure with high phosphorus concentration on the front surface, the silver electrode and the silicon wafer can form good contact under the low-temperature sintering condition, and under the low-temperature sintering condition, the over-excited reaction between the back aluminum and the silicon can be inhibited, so that the B-BSF (boron back field) effect formed by doping boron with the local localized laser is protected, and the improvement of the battery efficiency is realized.
According to the electrical property evaluation results of the test cells, optimization is performed on the type selection and sintering conditions of the low-temperature sintering aluminum paste and the low-temperature sintering silver paste, so that the local boron doping effect is maximized, and the photoelectric conversion efficiency (also referred to as cell efficiency, abbreviated as Eff) of the cell is improved by more than 0.4% compared with that of the SE-PERC cell.
Example 2
As shown in fig. 3 c, this embodiment discloses a method for manufacturing a high-efficiency battery based on a nano silicon slurry containing high-concentration boron, which specifically includes the following steps:
taking a p-type monocrystalline silicon wafer with the dimension of 156 mm and the thickness of 180 mu m, and cleaningAfter texturing, selecting a set SE area on the front surface of the silicon wafer, and printing silicon nanoparticles with the average particle size not more than 50nm and the phosphorus content not less than 5x10^ on the SE area19atoms/cm3The phosphorus-containing nano silicon slurry is dried for 10min at the temperature of 200 ℃, wherein the amount of the printed phosphorus-containing nano silicon slurry is ensured that the thickness of a dry film after the drying is finished is 1.8 mu m, and the line width is 148 mu m.
Then put into a diffusion furnace to be in POCl3Phosphorus diffusion is performed under the atmosphere, phosphorus-silicon glass PSG is formed on the surface of the silicon wafer, and a low-damage phosphorus-doped region (n + +) is formed in the region printed with the phosphorus-containing nano-silica paste, i.e., an SE structure is formed, wherein Rs of the phosphorus-doped region is controlled to be 55-60 ohm/sq.
Then, PSG is removed, back etching is carried out, an antireflection film (such as aluminum oxide, silicon nitride and the like) is deposited on the front surface of the silicon wafer, and a passivation film (such as aluminum oxide, silicon nitride and the like) is deposited on the back surface of the silicon wafer.
Then, a high-concentration boron-containing nano-silica slurry having a boron-silicon (B/Si) molar ratio of 2.2 (in which the solid content of the silicon-boron composite nanoparticles was 8%, the average particle diameter of the nanoparticles was about 20nm, and TEM photographs showed that most of boron was coated with silicon) was printed on the passivation film on the back surface. Drying at 200 deg.C for 10min, wherein the printed nanometer silicon slurry containing high concentration boron should ensure that the average thickness of dry film is 1.6 μm and the average line width is 94 μm after drying; and (3) scanning a laser with a pulse waveform having a flat top wave characteristic, a spot size of 40 μm × 40 μm and an output power of 40W by aligning the laser with the pattern of the printing region containing the high-concentration boron nano silicon paste to obtain a laser irradiation pattern with an average line width of about 42um, and controlling the Rs of the region partially doped with boron to be 12 +/-2 ohm/sq.
And then, printing aluminum paste A capable of being sintered at low temperature on the whole back surface, and printing silver paste B capable of being sintered at low temperature and slightly smaller than the pattern of the SE structure in the area of the front surface aligned with the SE structure.
And finally, carrying out co-sintering at 720 ℃ to obtain the high-efficiency battery with the SE-PERL structure.
Through tests, the average photoelectric conversion efficiency of 50 battery pieces prepared by the method is 22.05%, and the specific test result is shown in fig. 4.
Example 3
The embodiment discloses a manufacturing method of a high-efficiency battery based on high-concentration boron-containing nano silicon slurry, which is mainly different from the embodiment 2 in that an SE-PERC improved method developed by Diel laser company is adopted to form an SE structure, and the specific steps are as follows:
adopting a p-type monocrystalline silicon wafer with the dimension of 156 mm and the thickness of 180 mu m, cleaning and texturing, and directly putting the p-type monocrystalline silicon wafer into a diffusion furnace for POCl3Phosphorus was diffused in the atmosphere under the same conditions as in example 1 to form PSG;
then, the PSG formed by thermal phosphorus diffusion was irradiated with a pulse laser with a flat top wave characteristic with an output power of 20W, so as to form a SE structure equivalent to that of embodiment 1, wherein the line width of the laser processing region is about 120 μm, and the laser doping region Rs is about 70-90 ohm/sq;
then, after PSG removal and back etching, depositing an antireflection film on the front side and depositing a passivation film on the back side;
then, the same high-concentration boron-containing nano-silica slurry (i.e., B/Si molar ratio of 2.2, etc.) as in example 1 was printed on the passivation film on the back surface, and dried at 200 ℃ for 10min to obtain a dry film with an average thickness of about 1.7 μm and an average line width of 96 μm, and then aligned laser irradiation was performed under the same conditions as in example 1 to obtain a laser irradiation pattern with an average line width of about 44 μm, and the local boron-doped region Rs was controlled to be 12 ± 2 ohm/sq;
then, printing special PERC aluminum paste C on the back surface of the base plate, and printing silver paste D which is slightly smaller than an SE structure pattern and can be sintered at a low temperature in the area of the front surface aligned to the SE structure;
and finally, carrying out co-sintering at 780 ℃ to obtain the high-efficiency battery piece with the SE-PERL mechanism.
Through tests, the average photoelectric conversion efficiency of the 50 battery pieces manufactured by the method is 21.88%, and the specific test result is shown in fig. 4.
Comparative example 1
The cell produced by SE-PERC method using a dill laser was used as comparative example 1, and the production steps were as follows:
SE structure was prepared using the same method as example 3;
the rear surface passivation film is not printed with borosilicate-containing slurry (different from the examples 2 and 3), the pulse wave type of the laser for opening the holes of the passivation film still has flat top wave characteristics, the spot size is also 40 mu m by 40 mu m, the output power is 25W, and a slotted area with the average line width of 42 mu m is formed on the passivation film after laser scanning;
on the basis, the back surface of the base is printed with standard PERC aluminum paste, and the front surface of the base is printed with silver paste slightly smaller than the SE structure pattern in the area aligned with the SE structure;
and co-sintering the back aluminum and the front silver together at 840 ℃ to finally finish the manufacture of the SE-PERC battery.
Through tests, the average efficiency of the 50 battery pieces manufactured by the method is 21.65%, and the specific test result is shown in fig. 4.
As can be seen from fig. 4, the open-circuit voltage (Voc), the short-circuit current (Isc), the Fill Factor (FF), and the cell efficiency (Eff) of the cell fabricated according to the embodiment of the present disclosure are all better than those of the cell fabricated according to the comparative example, so that the method according to the embodiment of the present disclosure can effectively improve the cell efficiency, and the improvement of the cell efficiency of the cell having the SE structure formed by the method according to embodiment 2 of the present disclosure is more significant.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the embodiments of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (10)
1. A manufacturing method of a high-efficiency battery based on nanometer silicon slurry containing high-concentration boron comprises the following steps:
s1, taking a silicon wafer, cleaning and texturing, setting an SE area on the front surface of the silicon wafer, and printing phosphorus-containing nano silicon slurry in the SE area;
s2 in POCl3Performing phosphorus diffusion in the atmosphere to form a phosphorus-doped region in the SE region;
s3, removing phosphorosilicate glass formed on the surface of the silicon wafer in the phosphorus diffusion process, carrying out back etching, depositing an antireflection film on the front side of the silicon wafer, and depositing a passivation film on the back side of the silicon wafer;
s4, printing high-concentration boron nano silicon slurry on the passivation film on the back of the silicon wafer, and scanning by laser to realize localized boron doping;
s5, printing aluminum paste on the back surface of the silicon wafer, and printing silver paste on the SE structure on the front surface of the silicon wafer;
and S6, sintering to form the battery.
2. The method for manufacturing a high-efficiency battery based on high-concentration boron-containing nano silicon slurry according to claim 1, wherein in step S4, the high-concentration boron-containing nano silicon slurry is boron-silicon molar ratio of 0.2-2.5.
3. The method for manufacturing a high-efficiency battery based on high-concentration boron-containing nano-silicon slurry as claimed in claim 1, wherein in step S4, the printing area of the high-concentration boron-containing nano-silicon slurry is larger than the set area of localized boron doping.
4. The method for manufacturing a high-efficiency battery based on the nano silicon slurry containing high-concentration boron according to claim 1, wherein in step S4, the wavelength of the laser is 532nm-1040 nm.
5. The method for manufacturing a high-efficiency battery based on high-concentration boron-containing nano-silicon slurry as claimed in claim 1, wherein in step S4, the thickness of the high-concentration boron-containing nano-silicon slurry printed on the passivation film on the back surface of the silicon wafer is 1.5-2.5 μm after being a dry film.
6. The method as claimed in claim 1, wherein the sintering temperature is 570-780 ℃.
7. The method for manufacturing a high-efficiency battery based on the nano silicon slurry containing high concentration of boron according to claim 1, wherein the step S1 further comprises drying the nano silicon slurry containing phosphorus,
the average grain diameter of silicon nano particles in the phosphorus-containing nano silicon slurry is not more than 50nm, and the phosphorus content is not less than 5x10^19atoms/cm3；
The drying temperature is 180 ℃ and 250 ℃, and the drying time is 8-15 min.
8. A high-efficiency battery made by the method of any one of claims 1-7, comprising a silver electrode (1), an antireflective film (2), a silicon wafer (5), an aluminum paste layer (7) and a passivation film (8),
a phosphorus heavily-doped region (4) and a light-doped region (3) are arranged on the front surface of the silicon wafer, the anti-reflection film is arranged outside the light-doped region, the phosphorus heavily-doped region penetrates through the anti-reflection film to be in contact with the silicon wafer, and the silver electrode is arranged on the phosphorus heavily-doped region;
the passivation film is arranged on the back surface of the silicon wafer, a boron heavily-doped region (6) is arranged on the passivation film, the boron heavily-doped region penetrates through the passivation film to be in contact with the silicon wafer, and the aluminum paste layer is arranged on the passivation film.
9. The high-efficiency battery based on the nano silicon slurry containing high-concentration boron as claimed in claim 8, wherein the silicon wafer is a P-type monocrystalline silicon wafer.
10. The high efficiency battery according to claim 8, wherein the Rs of the phosphorus-heavily doped region (4) is 55-60ohm/sq, and the Rs of the boron-heavily doped region (6) is 12 ± 2 ohm/sq.
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