CN109616530B - Process for forming electrode of solar cell - Google Patents
Process for forming electrode of solar cell Download PDFInfo
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- CN109616530B CN109616530B CN201811353980.8A CN201811353980A CN109616530B CN 109616530 B CN109616530 B CN 109616530B CN 201811353980 A CN201811353980 A CN 201811353980A CN 109616530 B CN109616530 B CN 109616530B
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- 238000000034 method Methods 0.000 title claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 66
- 239000010703 silicon Substances 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 66
- 238000010438 heat treatment Methods 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 43
- 238000007639 printing Methods 0.000 claims abstract description 37
- 239000002002 slurry Substances 0.000 claims abstract description 33
- 238000005516 engineering process Methods 0.000 abstract 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 13
- 238000000137 annealing Methods 0.000 description 10
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- 238000005468 ion implantation Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 8
- 229910004205 SiNX Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
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- 239000004332 silver Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
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- 229910052796 boron Inorganic materials 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- HYLLZXPMJRMUHH-UHFFFAOYSA-N 1-[2-(2-methoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOC HYLLZXPMJRMUHH-UHFFFAOYSA-N 0.000 description 2
- 229910017107 AlOx Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000004093 laser heating Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- -1 phosphorus ions Chemical class 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L31/18—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 Table
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
- Electrodes Of Semiconductors (AREA)
Abstract
A process for forming an electrode of a solar cell is disclosed. The process comprises the following steps: (1) printing a first pattern on a silicon substrate by using a first paste not containing metal powder; (2) carrying out first heat treatment on the silicon substrate to dry the first slurry; (3) printing a second pattern on the first pattern using a second paste containing a metal powder on a silicon substrate, at least a portion of the second pattern being in contact with the silicon substrate; (4) and carrying out second heat treatment on the silicon substrate to sinter the second slurry so as to form the electrode of the solar cell. The technology can form good ohmic contact by matching the first slurry without metal powder and the second slurry with metal powder, and can reduce the contact area between the grid line serving as an electrode and a silicon substrate.
Description
Technical Field
The present invention relates to a process for forming an electrode of a solar cell.
Background
The process of forming the electrodes of crystalline silicon solar cells typically involves printing a slurry containing a metal powder (e.g., silver powder) on the back and/or front side of the solar cell, followed by rapid low temperature baking and high temperature sintering in a sintering furnace to form good ohmic contact of the metal to the semiconductor. In order to obtain higher conversion efficiency, it is necessary to reduce the recombination degree of the metal and the semiconductor to increase the open circuit voltage (Voc), and specifically, to reduce the contact area of the metal and the semiconductor. However, the contact area between the metal and the semiconductor can be reduced by reducing the width of the metal grid line, but the cross-sectional area of the metal grid line is reduced, so that the resistance of the metal grid line is increased, and the Fill Factor (FF) of the solar cell is reduced; meanwhile, the risk of breaking the metal grid line can be increased by reducing the contact area of the metal grid line and the semiconductor. In order to ensure the continuity of the metal grid lines, the metal powder-containing slurry is sometimes printed twice, however, such a process requires very high operation precision to ensure that the fine metal grid lines printed twice have good contact ratio.
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide a process for forming an electrode of a solar cell, which can reduce the contact area of a metal grid line and a semiconductor and reduce or avoid the risk of breaking the metal grid line on the premise of not needing very high operation precision.
Technical scheme
In order to achieve the object, the following technical solutions are provided herein.
A process for forming an electrode of a solar cell, comprising the steps of:
(1) printing a first pattern on a silicon substrate by using a first paste not containing metal powder;
(2) carrying out first heat treatment on the silicon substrate to dry the first slurry;
(3) printing a second pattern on the first pattern using a second paste containing a metal powder on a silicon substrate, at least a portion of the second pattern being in contact with the silicon substrate;
(4) and carrying out second heat treatment on the silicon substrate to sinter the second slurry so as to form the electrode of the solar cell.
In the electrode metallization process of the solar cell piece, the following steps are carried out:
the first slurry in the step (1) is a slurry which cannot form ohmic contact with a silicon substrate.
Preferably, the first paste includes polyimide resin, titanium dioxide, 1, 3-dimethyl-1-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, diethylene glycol methyl butyl ether, etc., and the manufacturers include, but are not limited to, TOK IP-1600 in japan, Henkel3616 in han-gao, germany, etc., which are merely illustrative and not limitative, and other pastes having similar insulating and non-conductive functions may be used.
Preferably, in the step (1), the first pattern is composed of discontinuous grid lines, or the first pattern is composed of grid lines with hollow-out regions, or the first pattern is composed of the discontinuous grid lines and the grid lines with the hollow-out regions.
Preferably, the temperature of the first heat treatment in the step (2) is 200 to 950 ℃, further the temperature of the first heat treatment is 200 to 600 ℃, the treatment time is not less than 10s, and further the treatment time is 1 to 3 min.
And (3) the second slurry is a slurry capable of forming ohmic contact with the silicon substrate.
Preferably, the second paste is a sintered contact type paste widely used at present, and the components include conductive powder, a fire-through contact type glass frit, an organic solvent, and the like, such as PVJ06 of dupont, PV3N2 of heili, and the like, which are merely exemplary and not limiting, and other pastes having similar functions may be used.
The second pattern in step (3) is composed of continuous grid lines; the second pattern is formed of continuous gate lines for conducting current.
Optionally, for the back side of the back contact cell or the ordinary cell which does not need to consider the influence of front shading, the width of the grid lines printed with the second pattern is not limited, and the series resistance Rs of the solar cell can be reduced by printing the second pattern and adopting wider grid lines, so that the conversion efficiency of the cell is remarkably improved.
Preferably, the second pattern in step (3) forms an ohmic contact with the cell sheet at the break or hollowed-out region of the first pattern in step (1).
Preferably, the temperature of the second heat treatment in the step (4) is 500-950 ℃, further the temperature of the second heat treatment is 700-950 ℃, the treatment time is not less than 10s, and further the treatment time is 3-5 min.
Optionally, the first pattern in the step (1) and the second pattern in the step (3) are provided on the front side and/or the back side of the battery piece.
That is, the first pattern and the second pattern may be simultaneously disposed on the front surface of the battery piece, may be simultaneously disposed on the back surface of the battery piece, or may be separately disposed on the front surface and the back surface of the battery piece.
Preferably, the first pattern in step (1) and the second pattern in step (3) are produced by single printing or multiple printing.
That is, the first graphic may be formed by a single printing or multiple printing, and the second graphic may be formed by a single printing or multiple printing.
Technical effects
The invention has the following advantages:
(1) in the process, the first slurry without metal powder and the second slurry containing metal powder are matched to form the electrode, so that the contact area of the grid line can be reduced;
(2) according to the invention, through the electrode metallization process of the solar cell piece by adopting two times of heat treatment, the contact area can be reduced, and the line resistance can not be increased, so that the solar cell with high open-circuit voltage Voc and high fill factor FF and high conversion efficiency is finally obtained.
Drawings
Fig. 1 is a flow chart of a process for forming an electrode of a solar cell according to an embodiment of the present invention;
fig. 2 is a pattern structure of a discontinuous gate line in embodiment 1;
fig. 3 is a pattern structure of a gate line with a hollow region in example 2;
FIG. 4 is a schematic structural view illustrating a contact between the second pattern and the silicon wafer at the break of the first pattern in embodiment 1 and at the hollow region of the first pattern in embodiment 2;
fig. 5 is a schematic view of the structure of a continuous gate line in embodiment 1-2;
fig. 6 is a temperature treatment profile of the first heat treatment and the second heat treatment in example 1.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
Referring to fig. 1, fig. 1 is a flowchart of a process for forming an electrode of a solar cell according to an embodiment of the present invention, and as shown in fig. 1, the process for forming an electrode of a solar cell includes the following steps:
(1) printing a first pattern on a silicon substrate by using a first paste not containing metal powder;
(2) carrying out first heat treatment on the silicon substrate to dry the first slurry;
(3) printing a second pattern on the first pattern using a second paste containing a metal powder on a silicon substrate, at least a portion of the second pattern being in contact with the silicon substrate;
(4) and carrying out second heat treatment on the silicon substrate to sinter the second slurry so as to form the electrode of the solar cell.
In the above embodiment, a first pattern not containing metal powder is first formed on the silicon substrate through the steps (1) and (2), and then a second pattern is printed using a second paste containing metal powder in a manner to cover the first pattern through the step (3), and since at least a portion of the second pattern is in contact with the silicon substrate, the outline of the second pattern can be considered to be larger than that of the first pattern, and thus after sintering, another portion of the second pattern is not in ohmic contact with the silicon substrate due to the shielding of the first pattern, and the contact area with the silicon substrate is also reduced. Therefore, the contact area with the silicon substrate can be reduced on the premise of not reducing the resistance of the second pattern (for example, the second pattern is a plurality of auxiliary grid lines), so that the open-circuit voltage is improved.
In the step (1), the first slurry containing no metal powder is a slurry incapable of forming ohmic contact with a silicon substrate.
In the step (1), the metal-free powder is a powder that does not contain metals such as silver (Ag), gold (Au), palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh), osmium (Os), iridium (Ir), rhenium (Re), titanium (Ti), niobium (Nb), tantalum (Ta), aluminum (Al), copper (Cu), nickel (Ni), molybdenum (Mo), vanadium (V), zinc (Zn), magnesium (Mg), yttrium (Y), cobalt (Co), zirconium (Zr), iron (Fe), tungsten (W), tin (Sn), chromium (Cr), manganese (Mn), and the like.
The first paste is not particularly limited as long as it can be cured and attached to the surface of the silicon substrate after being heated. In some embodiments, the first slurry may contain a polymer, an organic solvent, and the like. The polymer may be a high temperature resistant resin such as polyimide resin, which is advantageous in the heat resistance of the first paste, i.e., the high temperature resistant resin does not undergo decomposition reaction or undergoes little decomposition reaction after the first heat treatment. The polyimide resin may be a commercially available product. The organic solvent may be a solvent capable of dissolving or swelling the above-mentioned polymer, and examples thereof include 1, 3-dimethyl-1-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, and diethylene glycol methyl butyl ether. The organic solvent may be a commercially available product. For the first slurry, commercially available products such as TOK IP-1600 in Japan, Henkel3616 in Henkel, Germany, and the like can be used. In addition, a small amount of glass frit may be contained in the first paste.
For the first pattern printed in step (1), it may be any arrangement of discontinuous grid lines (as shown in fig. 2), or a linear pattern with hollow-out regions (as shown in fig. 3), or a combination thereof.
In the step (2), the temperature of the first heat treatment is not particularly limited as long as the first slurry can be dried to be fixedly attached to the surface of the silicon substrate. The maximum temperature of the first heat treatment can be 200-950 ℃, and the treatment time can be more than 10 s. Preferably, the temperature of the first heat treatment in the step (2) is 200-600 ℃, and the treatment time is 1-3 min. The method of the first heat treatment is not particularly limited, and for example, oven heating, laser heating, radiation heating, or the like can be used. In one embodiment, oven heating may be used. Since the first paste does not contain metal powder, it forms an insulating layer on the surface of the silicon substrate after the first heat treatment. The temperature of the first heat treatment can be adjusted by those skilled in the art according to the components of the first slurry, and generally, the temperature of the first heat treatment needs to be 200 ℃ or more. The maximum temperature of the first heat treatment is not particularly limited, but is preferably 950 ℃ or less. Although the temperature of 950 ℃ is already higher than the decomposition temperature of the heat-resistant polymer, a certain time is required in view of heat transfer, so that the time for the first heat treatment can be reduced, for example, to 10 seconds or less, for example, 9s, 8s, 7s, 6s, 5s, 4s, 3s, 2s, 1s, etc., when the temperature is higher.
The second slurry containing metal powder in step (3) is a slurry capable of forming ohmic contact with the silicon wafer substrate, preferably a silver slurry. The metal powder in step (3) may be a powder of at least one metal selected from the group consisting of silver (Ag), gold (Au), palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh), osmium (Os), iridium (Ir), rhenium (Re), titanium (Ti), niobium (Nb), tantalum (Ta), aluminum (Al), copper (Cu), nickel (Ni), molybdenum (Mo), vanadium (V), zinc (Zn), magnesium (Mg), yttrium (Y), cobalt (Co), zirconium (Zr), iron (Fe), tungsten (W), tin (Sn), chromium (Cr), manganese (Mn), etc., such as a silver powder, or a mixture of a silver powder and other metal powders, such as a mixture of a silver powder and an aluminum powder, a mixture of a silver powder and a copper powder, or a mixture of an aluminum powder and a copper powder.
The particle size (particle size) of the metal powder in the step (3) may be in the nano-or micro-size range. For example, the particle size of the above metal powder may be several tens nanometers to several hundreds nanometers or several micrometers to several tens micrometers or several tens nanometers to several tens micrometers. In an embodiment, the metal powder may be a mixture of two or more silver powders having different particle sizes.
The metal powder in step (3) may have a spherical, flake, or amorphous particle shape, the median particle diameter (D50) of the metal powder in step (3) may be 0.1 to 10 micrometers, e.g., 0.5 to 5 micrometers, or less than 0.1 micrometer, the average particle diameter may be measured using, for example, a model 1064D (CI L AS co., L td.) device after dispersing the metal powder in isopropyl alcohol (IPA) via ultrasonic treatment at room temperature (20 to 25 ℃) for 3 minutes, within this average particle diameter range, the second slurry may provide low contact resistance and low line resistance, the content of the metal powder may be 60 to 95 weight% based on 100 weight% for the second slurry, in one embodiment, the content of the metal powder may be 70 to 90 weight%, if within this range, lower resistance is guaranteed.
The second paste containing the metal powder may be a sintered contact type paste which is widely used at present, and the second paste may contain a fire through contact type glass frit, an organic solvent, etc. in addition to the metal powder, such as PVJ06 of dupont, PV3N2 of heili, etc., which are merely exemplary and not limiting, and other pastes having similar functions may be used.
And (4) printing a second pattern in the step (3) as a continuous grid line. A continuous gate line (i.e., a continuous electrode) can provide an output of current.
In the step (4), the temperature of the second heat treatment is not particularly limited as long as sintering of the second paste to the silicon substrate and ohmic contact with the silicon substrate can be achieved. The maximum temperature of the second heat treatment can be 500-950 ℃, and the treatment time can be more than 10 s. Preferably, the temperature of the second heat treatment in the step (4) is 700 to 950 ℃, and the treatment time is more than 3min, for example, 3 to 5 min. The method of the second heat treatment is not particularly limited, and for example, oven heating, laser heating, radiation heating, or the like can be used. In one embodiment, oven heating may be used. Since the second paste contains the metal powder, the metal powder in the second paste forms an ohmic contact with the silicon substrate after the second heat treatment. The temperature of the second heat treatment may be adaptively adjusted by those skilled in the art according to the components of the second slurry, and generally, the temperature of the second heat treatment needs to be 500 ℃ or more because sintering is required to form an ohmic contact. The maximum temperature of the second heat treatment is not particularly limited, but is preferably 950 ℃ or less. Because the maximum temperature is too high, more energy needs to be consumed. However, if the time for the second heat treatment is additionally reduced, the temperature for the second heat treatment may be appropriately increased. When the temperature of the second heat treatment is 950 ℃ or higher, the time of the second heat treatment can be appropriately reduced, for example, to 10 seconds or less, for example, 9 seconds, 8 seconds, 7 seconds, 6 seconds, 5 seconds, 4 seconds, 3 seconds, 2 seconds, 1 second, and the like.
In one embodiment, the second heat treatment is performed to contact the second paste to the silicon substrate at the hollowed-out portion of the first pattern and to sinter the second paste to form a conductive path.
Alternatively, the printing of the first pattern in step (1) may be on the front side of the sheet-shaped silicon substrate (the sheet-shaped silicon substrate is also referred to as a silicon wafer for short), the back side of the silicon wafer or the front and back sides of the silicon wafer, and may be a single printing or a plurality of times of printing, that is, step (1) may be repeated a plurality of times, or step (1) and step (2) may be repeated a plurality of times at the same time. The front surface of the silicon wafer generally refers to the light receiving surface of the silicon wafer, which is obliquely oriented upward. The back side of the silicon wafer refers to the side opposite to the front side of the silicon wafer.
Optionally, the printing of the second pattern in step (3) may be on the front side of the silicon wafer (silicon substrate), the back side of the silicon wafer or both the front side and the back side of the silicon wafer, and may be a single printing or a plurality of printings. That is, step (3) may be repeated a plurality of times.
Optionally, the printed second pattern in step (3) is brought into contact with the silicon wafer at the break or hollow of the first pattern in step (1) (fig. 4).
Optionally, for the back side of a back contact cell or a common cell which does not need to consider the influence of front shading, the width of the grid lines printed with the second pattern is not limited any more, and the series resistance of the solar cell can be reduced by printing the second pattern with wider grid lines, so that the conversion efficiency of the cell is improved remarkably.
The method of the invention can be used for forming main grid lines (main electrodes) of the solar cell and can also be used for forming auxiliary grid lines (auxiliary electrodes) of the solar cell. Preferably used to form the subgrid of a solar cell.
Example 1
(1) Selecting a P-type single crystal silicon substrate with the size of 156.75mm × 156.75.75 mm, and texturing the front surface of the P-type single crystal silicon substrate by using NaOH solution with the concentration of 15 g/L, wherein the texturing time is 20min, the texturing temperature is 80 ℃, the resistivity of the P-type single crystal silicon substrate is 0.5-2 omega-cm, and the thickness is 180 mu m;
(2) performing phosphorus ion implantation doping on the front surface of the P-type monocrystalline silicon by adopting an ion implantation mode, wherein the dosage of the phosphorus ion implantation is 6 × 1015/cm2；
(3) And (3) placing the P-type monocrystalline silicon substrate treated in the step (2) in an annealing furnace for high-temperature annealing treatment, wherein the peak annealing temperature is 900 ℃, and the annealing time is 200 min. Forming a front emitter after annealing;
(4) depositing a SiNx film on the front surface of the P-type single crystal silicon substrate treated in the step (3) by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, wherein the thickness of the SiNx film is 80nm, and the SiNx film is used for passivation of the front surface and antireflection of incident light, and the PECVD method is carried out under the conditions that: SiH as a reaction gas4Flow rate of 10sccm, NH3The flow is 50sccm, the air pressure of the cavity is 10Pa, the temperature is 400 ℃, the radio frequency power is 40W, and the reaction time is 3 min. And depositing AlOx and SiNx films on the back surface of the P-type monocrystalline silicon substrate in sequence by using PECVD (plasma enhanced chemical vapor deposition), wherein the thickness of AlOx is 10nm, the thickness of SiNx is 80nm, and the film is used for passivating the back surface, wherein the PECVD is carried out under the conditions that: SiH as a reaction gas4Flow rate of 10sccm, NH3The flow is 50sccm, the air pressure of the cavity is 10Pa, the temperature is 400 ℃, the radio frequency power is 40W, and the reaction time is 3 min;
(5) grooving the back of a P-type single crystal silicon substrate by using laser, printing aluminum paste, and then drying the aluminum paste for leading out the back current of the silicon substrate;
(6) printing a first pattern
Printing a back pattern by using a conventional pattern, and printing a front first pattern by using a first paste (the first paste used in the embodiment is Henkel3616 of hangao company, germany) without containing metal powder, wherein the first pattern uses interrupted grid lines as shown in fig. 2, the width W21 of each row of interrupted grid lines is 65 μm, the distance P21 of two adjacent rows of interrupted grid lines is 2mm, the length L22 of each grid line segment in the same row of interrupted grid lines is 200 μm, and the distance P22 of two adjacent grid line segments in the same row of interrupted grid lines is 100 μm;
(7) first heat treatment
Placing the flaky silicon substrate from the step (6) in a drying oven, keeping the temperature within the range of 300-420 ℃ for 2.5 minutes, and taking the flaky silicon substrate out of the drying oven; the temperature profile of the first heat treatment is shown in fig. 6.
(8) Printing a second graphic
Performing a second printing with a second paste containing metal powder (the second paste used in this embodiment is PVJ06 from dupont), using continuous grid lines as shown in fig. 5 for the second pattern, and covering the continuous grid lines on the first printed pattern, wherein after drying, the width W51 of each row of continuous grid lines is 65 μm, and the pitch P51 between two adjacent rows of continuous grid lines is 2 mm;
a schematic structural diagram of the second pattern forming ohmic contact with the sheet silicon substrate through the break in the first pattern is shown in fig. 4;
(9) second heat treatment
Placing the flaky silicon substrate from the step (8) in a sintering furnace, keeping the temperature within the range of 700-800 ℃ for 34 seconds, and taking the flaky silicon substrate out of the oven to obtain the crystalline silicon solar cell; the temperature profile of the heat treatment is shown in fig. 6.
The performance of the solar cell obtained in example 1 was tested, and the test results are shown in table 1 below. 432 solar cells were tested.
Table 1 performance of the solar cell of example 1
Example 2
(1) Selecting an N-type single crystal silicon substrate with the size of 156.75mm × 156.75.75 mm, and texturing the front surface of the N-type single crystal silicon substrate by using NaOH solution with the concentration of 15 g/L, wherein the processing time is 20min and 80 ℃, the resistivity of the N-type single crystal silicon substrate is 0.5-2 omega cm, and the thickness is 180 mu m;
(2) respectively carrying out boron ion implantation doping and phosphorus ion implantation doping on the front surface and the back surface of the N-type monocrystalline silicon by adopting an ion implantation mode, wherein the boron ion implantation is carried out on the front surface, and the dosage of the boron ion implantation is 1.0 × 1015/cm2Implanting phosphorus ions at a dose of 6 × 1015/cm2。
(3) And (3) placing the N-type monocrystalline silicon substrate treated in the step (2) into an annealing furnace for high-temperature annealing treatment, wherein the peak annealing temperature is 900 ℃, and the annealing time is 200 min. Forming a front emitter and a back field after annealing;
(4) and (4) depositing a SiNx dielectric film on the front surface and the back surface of the N-type crystalline silicon substrate treated in the step (3) by using a PECVD method respectively, wherein the SiNx dielectric film is 80nm in thickness and is used for passivation of the front surface and the back surface and antireflection of incident light on the front surface. The conditions for performing PECVD were: SiH as a reaction gas4Flow rate of 10sccm, NH3The flow is 50sccm, the air pressure of the cavity is 10Pa, the temperature is 400 ℃, the radio frequency power is 40W, and the reaction time is 3 min;
(5) printing a first pattern
The front first pattern was printed using a first paste containing no metal powder (the first paste used in this example was Henkel3616, han height, germany), and the first pattern used was a line pattern with a hollowed-out region as shown in fig. 3, in which the width W31 of each line pattern (grid line) was 50 μm, the pitch P31 of two adjacent lines of the line pattern was 2mm, the length of each hollowed-out region P32 in the same line was 80 μm, the pitch L32 of two adjacent hollowed-out regions in the same line was 100 μm, and the length L31 of each line pattern (grid line) was 150 mm.
(6) The same printing process as the step (5) can be adopted for the back of the battery;
(7) first heat treatment
Placing the flaky silicon substrate from the step (6) in a drying oven, keeping the temperature within the range of 300-420 ℃ for 2.5 minutes, and taking the flaky silicon substrate out of the drying oven; the temperature profile of the heating is shown in fig. 6;
(8) printing a second graphic
Performing a second printing on the front surface of the cell by using a second paste containing metal powder (the second paste used in the embodiment is PV3N2 of heili corporation), wherein a second pattern uses continuous grid lines as shown in fig. 5, and the continuous grid lines cover the first pattern printed for the first time, after drying, the width W51 of each row of the continuous grid lines is 50 μm, and the distance P51 between two adjacent rows of the continuous grid lines is 2 m;
(9) the same printing process as in step (8) was again performed for the back surface of the battery, wherein the second paste containing the metal powder used a contact type paste PVJ06 of dupont;
(10) second heat treatment
Placing the flaky silicon substrate from the step (9) in a sintering furnace, keeping the temperature within the range of 700-800 ℃ for 34 seconds, and taking the flaky silicon substrate out of the oven; the temperature profile of the heat treatment is shown in FIG. 6;
the performance of the solar cell obtained from the above example 2 was tested, and the test results are shown in table 2 below. 305 solar cells were tested.
Table 2 comparison of the performance of the solar cell of this example with that of the conventional metallization process
Claims (11)
1. A process for forming an electrode of a solar cell, comprising the steps of:
(1) printing a first pattern on a silicon substrate by using a first paste not containing metal powder;
(2) carrying out first heat treatment on the silicon substrate to dry the first slurry;
(3) printing a second pattern on the first pattern using a second paste containing a metal powder on a silicon substrate, at least a portion of the second pattern being in contact with the silicon substrate;
(4) performing a second heat treatment on the silicon substrate to sinter the second paste, thereby forming an electrode of the solar cell;
wherein, the first slurry in the step (1) is a slurry which can not form ohmic contact with a silicon substrate.
2. The process of forming an electrode for a solar cell of claim 1, wherein: in the step (1), the first graph is composed of discontinuous grid lines, or the first graph is composed of grid lines with hollow-out regions, or the first graph is composed of discontinuous grid lines and grid lines with hollow-out regions.
3. The process of forming an electrode for a solar cell of claim 2, wherein: the temperature range of the first heat treatment in the step (2) is 200-950 ℃, and the treatment time is not less than 10 s.
4. The process of forming an electrode for a solar cell of claim 2, wherein: the temperature range of the first heat treatment in the step (2) is 300-420 ℃, and the treatment time is 1-3 min.
5. The process of forming an electrode for a solar cell according to claim 3 or 4, wherein: and (3) the second slurry is a slurry capable of forming ohmic contact with the silicon substrate.
6. The process of forming an electrode for a solar cell of claim 5, wherein: and (4) the second graph in the step (3) is composed of continuous grid lines.
7. The process of forming an electrode for a solar cell of claim 6, wherein: in the step (3), the second pattern forms ohmic contact with the silicon substrate at the break or the hollow-out region of the first pattern in the step (1).
8. The process of forming an electrode for a solar cell of claim 7, wherein: the temperature range of the second heat treatment in the step (4) is 500-950 ℃, and the treatment time is not less than 10 s.
9. The process of forming an electrode for a solar cell of claim 7, wherein: the temperature range of the second heat treatment in the step (4) is 700-950 ℃, and the treatment time is 0.2-3 min.
10. The process of forming an electrode for a solar cell of claim 1, wherein: and (3) the first graph in the step (1) and the second graph in the step (3) are arranged on the front surface and/or the back surface of the silicon substrate.
11. The process of forming an electrode for a solar cell of claim 1, wherein: the first graph in the step (1) and the second graph in the step (3) are made through single printing or multiple printing.
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| US5112409A (en) * | 1991-01-23 | 1992-05-12 | Solarex Corporation | Solar cells with reduced recombination under grid lines, and method of manufacturing same |
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| CN102738302A (en) * | 2012-06-15 | 2012-10-17 | 上海中智光纤通讯有限公司 | Method for forming electrodes of heterojunction with intrinsic thin layer (HIT) solar cell |
| CN102916087B (en) * | 2012-11-09 | 2015-06-17 | 上饶光电高科技有限公司 | Solar cell and manufacturing method thereof |
| CN203536447U (en) * | 2013-11-15 | 2014-04-09 | 英利能源（中国）有限公司 | Grid line structure of solar cell and solar cell comprising same |
| TWI556455B (en) * | 2014-03-04 | 2016-11-01 | 茂迪股份有限公司 | Solar cell, module comprising the same and method of manufacturing the same |
| CN204271093U (en) * | 2014-12-15 | 2015-04-15 | 常州天合光能有限公司 | The grid line structure of solar cell front surface localized contact |
| CN104465805B (en) * | 2014-12-15 | 2017-05-10 | 常州天合光能有限公司 | Gate line structure making local contact with obverse surface of solar battery and manufacturing method thereof |
| CN104638033A (en) * | 2015-02-11 | 2015-05-20 | 苏州金瑞晨科技有限公司 | Nano silicon boron slurry and method for preparing PERL solar battery by utilizing nano silicon boron slurry |
| CN104752562A (en) * | 2015-03-17 | 2015-07-01 | 晶澳（扬州）太阳能科技有限公司 | Preparation method of local boron back surface passive field solar cell |
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