CN113206169A - Aluminum gettering method and aluminum gettering equipment - Google Patents
Aluminum gettering method and aluminum gettering equipment Download PDFInfo
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- CN113206169A CN113206169A CN202110415403.2A CN202110415403A CN113206169A CN 113206169 A CN113206169 A CN 113206169A CN 202110415403 A CN202110415403 A CN 202110415403A CN 113206169 A CN113206169 A CN 113206169A
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 140
- 238000000034 method Methods 0.000 title claims abstract description 80
- 238000005247 gettering Methods 0.000 title claims abstract description 76
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 147
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 146
- 239000010703 silicon Substances 0.000 claims abstract description 146
- 238000000137 annealing Methods 0.000 claims abstract description 52
- 238000001816 cooling Methods 0.000 claims abstract description 50
- 238000007650 screen-printing Methods 0.000 claims abstract description 33
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000005496 eutectics Effects 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 11
- 229910000838 Al alloy Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000010668 complexation reaction Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 24
- 238000005516 engineering process Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 12
- 238000001035 drying Methods 0.000 abstract description 9
- 235000012431 wafers Nutrition 0.000 description 103
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000012535 impurity Substances 0.000 description 11
- 230000000630 rising effect Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
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- 238000005530 etching Methods 0.000 description 3
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
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- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
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- 238000004904 shortening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- H01L31/18—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/12—Stencil printing; Silk-screen printing
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
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- 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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Abstract
The embodiment of the invention provides an aluminum gettering method and aluminum gettering equipment, wherein the method comprises the steps of forming aluminum paste on at least one surface of a silicon wafer by utilizing screen printing; and performing chain annealing on the silicon wafer with the aluminum paste, wherein the chain annealing comprises a heating stage, a constant temperature stage and a cooling stage, the heating stage raises the temperature of the silicon wafer to be higher than the aluminum-silicon eutectic temperature, the constant temperature stage is higher than the aluminum-silicon eutectic temperature, and the cooling stage lowers the temperature of the silicon wafer to be lower than the aluminum-silicon eutectic temperature. The processing scheme of the invention uses the screen printing superposition chain type annealing furnace technology to carry out aluminum gettering. The screen printing technology is mature and stable, and low-cost aluminum paste can be used, so that the production cost of the aluminum paste is greatly reduced. The chain type annealing furnace can quickly realize the drying and doping of the aluminum paste, can quickly realize the annealing, has shorter process time and obvious gettering effect, and is convenient for large-scale mass production.
Description
Technical Field
The invention relates to the technical field of solar cell preparation, in particular to an aluminum gettering method and aluminum gettering equipment, and more particularly relates to an aluminum gettering method and aluminum gettering equipment applied to a heterojunction cell silicon wafer.
Background
The silicon chip is an important material in the preparation of the solar cell, and the quality requirement of the high-efficiency solar cell for the silicon chip is higher and higher at present. However, in the process of forming and processing silicon wafers in the form of silicon rods, a large amount of metal impurities are dissolved in the silicon wafers due to the preparation process, and the existence of these impurities greatly reduces the minority carrier lifetime of the silicon wafers, thereby reducing the conversion efficiency of the solar cell.
Gettering is an important way for improving the quality of the silicon wafer, and aluminum gettering is used as an external gettering way, so that the quality of the solar cell silicon wafer can be greatly improved. The existing aluminum gettering method has the problems of high production cost, complex process, large difficulty in mass production and the like.
Disclosure of Invention
In view of the above, embodiments of the present invention provide an aluminum gettering method and an aluminum gettering apparatus that at least partially solve the above problems in the prior art.
In a first aspect, an embodiment of the present invention provides an aluminum gettering method, which is applied to gettering of a silicon wafer, and includes:
forming an aluminum paste on at least one surface of the silicon wafer by screen printing; and the number of the first and second groups,
and performing chain annealing on the silicon wafer with the aluminum paste, wherein the chain annealing comprises a heating stage, a constant temperature stage and a cooling stage, the heating stage raises the temperature of the silicon wafer to be higher than the aluminum-silicon eutectic temperature, the constant temperature stage is higher than the aluminum-silicon eutectic temperature, and the cooling stage lowers the temperature of the silicon wafer to be lower than the aluminum-silicon eutectic temperature.
According to a specific implementation manner of the embodiment of the invention, the peak temperature range of the temperature rise stage is 600-750 ℃, and the time range is 2-6 min;
the temperature range of the constant temperature stage is 600-750 ℃, and the time range is 2-10 min;
the time range of the cooling stage is 1min-3 min.
According to a specific implementation manner of the embodiment of the invention, the temperature rise stage comprises a first temperature rise stage and a second temperature rise stage, the peak temperature range of the first temperature rise stage is 280-320 ℃, and the second temperature rise stage raises the temperature of the silicon wafer to be higher than the aluminum-silicon eutectic temperature.
According to a specific implementation manner of the embodiment of the invention, a supplementary cooling stage is further included after the cooling stage, the supplementary cooling stage reduces the temperature of the silicon wafer to be below 100 ℃, and the cooling rate of the supplementary cooling stage is smaller than that of the cooling stage.
According to a specific implementation manner of the embodiment of the invention, the time range of the first temperature rise stage is 1min-3min, the time range of the second temperature rise stage is 1min-3min, the time range of the constant temperature stage is 2min-10min, the time range of the temperature reduction stage is 1min-3min, and the time range of the supplementary temperature reduction stage is 2min-6 min.
According to a specific implementation manner of the embodiment of the invention, the time range of the first temperature rise stage is 1.86-2.14 min, the time range of the second temperature rise stage is 1.86-2.14 min, the time range of the constant temperature stage is 3.71-4.29 min, the time range of the temperature reduction stage is 1.86-2.14 min, and the time range of the supplementary temperature reduction stage is 3.71-4.29 min.
According to a specific implementation manner of the embodiment of the invention, an aluminum paste is formed on at least one surface of the silicon wafer by using an aluminum back field screen printing plate, and the thickness of the aluminum paste ranges from 1 μm to 10 μm.
According to a specific implementation of the embodiment of the invention, before the step of forming the aluminum paste on at least one surface of the silicon wafer by screen printing, the method further comprises:
adopting 2-12% KOH solution by mass ratio, and corroding one side of the silicon wafer at the temperature of 70-90 ℃ to the corrosion depth of more than 1.5 mu m; and the number of the first and second groups,
and (3) carrying out neutralization and metal ion complexation by adopting an HF/HCl mixed solution with the mass ratio of 2-10%.
According to a specific implementation manner of the embodiment of the present invention, after the step of performing chain annealing on the silicon wafer on which the aluminum paste is formed, the method further includes:
removing the aluminum alloy gettering layer on the surface of the silicon wafer by adopting a phosphoric acid solution with the mass ratio of 2% -10%;
adopting a KOH solution with the mass ratio of 2-12%, controlling the temperature range to be 70-90 ℃, and corroding one side of the silicon wafer, wherein the corrosion thickness is more than 2 mu m; and the number of the first and second groups,
and cleaning the silicon wafer by adopting an HF/HCl mixed solution with the mass ratio of 2-10%.
In a second aspect, there is provided an aluminum gettering apparatus applied to gettering of a silicon wafer, the apparatus including:
a screen printing apparatus that forms an aluminum paste on at least one surface of the silicon wafer by screen printing; and
the chain annealing furnace is used for performing chain annealing on the silicon wafer formed with the aluminum paste, and comprises a heating stage, a constant temperature stage and a cooling stage, wherein the heating stage is used for heating the temperature of the silicon wafer to be higher than the aluminum-silicon eutectic temperature, the constant temperature stage is used for heating the temperature of the silicon wafer to be higher than the aluminum-silicon eutectic temperature, and the cooling stage is used for cooling the temperature of the silicon wafer to be lower than the aluminum-silicon eutectic temperature.
The invention provides a method for carrying out aluminum gettering by using a screen printing superposition chain type annealing furnace technology, aiming at the problems of high production cost, complex process and large mass production difficulty in the existing aluminum gettering technology, and has the advantages of greatly reduced aluminum gettering cost, simple process, short process time and improved production efficiency. Firstly, the screen printing technology is mature and stable, and low-cost aluminum paste can be used because the problem of fine patterns in an aluminum paste area does not need to be considered, so that the production cost of the aluminum paste is greatly reduced; secondly, the chain annealing furnace is dried, heated and melted, diffused with metal, rapidly cooled and discharged, so that the aluminum paste can be rapidly dried and doped, the annealing can be rapidly realized, the process time is shorter, the process time is greatly reduced, the production efficiency is improved, the back diffusion of metal impurities is avoided, the impurity absorption effect is more obvious, and the large-scale mass production is convenient to carry out.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flowchart of an aluminum gettering method of example 1 of the present invention;
FIG. 2 is a flowchart of chain annealing in example 1 of the present invention;
FIG. 3 is a timing chart of chain annealing in example 1 of the present invention;
FIG. 4 is a flowchart of an aluminum gettering method of example 2 of the present invention;
FIG. 5 is a flowchart of an aluminum gettering method of example 3 of the invention;
FIG. 6 is a flowchart of an aluminum gettering method of example 4 of the present invention;
fig. 7 is a block diagram of an aluminum gettering apparatus of embodiment 5 of the invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that various aspects of the embodiments are described below within the scope of the appended claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the disclosure, one skilled in the art should appreciate that one aspect described herein may be implemented independently of any other aspects and that two or more of these aspects may be combined in various ways. For example, an apparatus may be implemented and/or a method practiced using any number of the aspects set forth herein. Additionally, such an apparatus may be implemented and/or such a method may be practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention, and the drawings only show the components related to the present invention rather than the number, shape and size of the components in practical implementation, and the type, quantity and proportion of the components in practical implementation can be changed freely, and the layout of the components can be more complicated.
In addition, in the following description, specific details are provided to facilitate a thorough understanding of the examples. However, it will be understood by those skilled in the art that the aspects may be practiced without these specific details.
The invention provides a method for carrying out aluminum gettering by using a screen printing superposition chain type annealing furnace technology, aiming at the problems of high production cost, complex process and large difficulty in mass production in the existing aluminum gettering technology. The screen printing technology is mature and stable, and low-cost aluminum paste can be used, so that the production cost of the aluminum paste is greatly reduced. The chain type annealing furnace can quickly realize the drying and doping of the aluminum paste, can quickly realize the annealing, has shorter process time, avoids the back diffusion of metal impurities, has more obvious gettering effect, and is convenient for large-scale mass production.
Hereinafter, an aluminum gettering method and an aluminum gettering apparatus of an embodiment of the present invention, which can be applied to gettering of a solar cell substrate silicon wafer, particularly, gettering of a heterojunction cell substrate silicon wafer, are described. And the silicon wafer may be an N-type monocrystalline silicon wafer or a polycrystalline silicon wafer.
Example 1
First, with reference to fig. 1, a method of aluminum gettering of an embodiment of the present invention is described. As shown in fig. 1, the aluminum gettering method includes:
s101: aluminum paste printing: an aluminum paste is formed on at least one surface of the silicon wafer using screen printing. Specifically, a printing screen is used for printing aluminum paste on the surface of the silicon wafer so as to form a layer of aluminum paste with a certain thickness on the surface of the silicon wafer. In the embodiment of the invention, the silicon wafer can be a substrate silicon wafer of a heterojunction cell, in particular to a substrate silicon wafer of an N-type heterojunction cell, and the aluminum paste can be back printing aluminum paste for conventional photovoltaics or aluminum paste with a slightly lower quality grade, so that the cost is reduced.
The components of the aluminum paste may include aluminum powder, organic matter, inorganic glass, and the like. According to a particular embodiment, the aluminum paste may include, for example, aluminum powder, glass frit, inorganic additives, organic carriers, and organic additives. The glass frit can be, for example, borosilicate lead glass, the inorganic additive can be, for example, trivalent ions to improve the doping effect, and the organic carrier is composed of polymer resin, an organic solvent, a plasticizer and the like. The invention has lower preparation requirements on the aluminum powder and the glass body in the printed aluminum paste, and is convenient for further reducing the production cost.
In the embodiment of the invention, the aluminum paste can be formed on one surface of the silicon wafer, or both surfaces of the silicon wafer, and the effect of gettering by adopting the aluminum paste on both surfaces is better, which is not limited herein. It should be understood here that in the case where aluminum paste is formed on both sides of the silicon wafer, after the aluminum paste is printed on one side, the side is dried; and then, the other side is printed in a turning way, so that aluminum paste is formed on the two sides of the silicon wafer.
In one embodiment, in order to form doping with a certain lateral gradient in the silicon wafer, an aluminum paste may be formed on one part of the silicon wafer, and no aluminum paste may be formed on the other part, so that after subsequent chain annealing, the metal content in the silicon wafer has a certain lateral gradient.
In the process of forming aluminum paste on at least one surface of a silicon wafer by screen printing, the printing is carried out by utilizing the basic principle that the mesh part of a screen printing plate is penetrated with the paste and the non-mesh part is not penetrated with the paste. During printing, aluminum paste is poured into one end of the screen plate, a scraper is used for applying certain pressure on the paste part of the screen plate, and the screen plate moves towards the other end of the screen plate. The slurry is extruded from the mesh of the screen onto the silicon wafer by the squeegee while moving. In one particular embodiment, the pitch of the apertures in the screen may be set, for example, to 900 μm-1300 μm, and the squeegee speed may be set, for example, to 35 mm/s. In the embodiment of the invention, a conventional aluminum back field screen printing plate can be used, so that the cost is reduced and the operability of large-scale production is facilitated.
The embodiment of the invention forms the aluminum paste on the silicon chip by utilizing the screen printing technology, and has the advantages of mature and stable screen printing technology, simple and convenient process, low requirement on the quality of a fine pattern in an aluminum paste area compared with a grid electrode of a battery silicon chip, and capability of using the aluminum paste with low cost, so that the production cost of the aluminum paste can be greatly reduced.
In a specific embodiment, an aluminum paste is formed on at least one surface of the silicon wafer using an aluminum back field screen and the thickness of the aluminum paste formed is in the range of 1 μm to 10 μm, preferably 6 μm. The aluminum paste is formed on at least one surface of the silicon wafer by using the conventional aluminum back field screen printing plate, so that the operation is simple, the operability is strong, the cost is reduced, and the large-scale production is facilitated.
S102: chain annealing: and performing chain annealing on the silicon wafer with the aluminum paste. Specifically, a silicon wafer printed with aluminum paste is conveyed into a chain type annealing furnace, and organic matters in the aluminum paste are removed through drying; then, the aluminum paste is diffused into the silicon wafer through the high-temperature region to form an aluminum heavily doped region; and finally, carrying out rapid cooling annealing to separate out metal impurities in the aluminum alloy gettering layer.
After the aluminum paste is formed on the silicon wafer through the step S01, the silicon wafer is also required to be heat-treated to perform aluminum gettering on the silicon wafer. Specifically, in the embodiment of the present invention, the silicon wafer formed with the aluminum paste is conveyed to the chain annealing furnace by a conveying device (e.g., a conveyor belt) to perform the chain annealing. It should be understood that the overall process time may be adjusted by changing the belt speed of the conveyor belt transporting the silicon wafer.
Next, chain annealing in the embodiment of the present invention is described with reference to fig. 2. As shown in fig. 2, the chain annealing of the embodiment of the present invention includes:
s201: and a temperature rise stage, wherein the temperature rise stage is used for volatilizing organic matters in the aluminum paste and raising the temperature of the silicon wafer to be higher than the aluminum-silicon eutectic temperature, and the aluminum-silicon eutectic temperature is generally 577 ℃.
Specifically, the temperature raising stage comprises a first temperature raising stage and a second temperature raising stage, and is used for raising the temperature of the silicon wafer to be higher than the eutectic temperature of aluminum and silicon, so that the aluminum and the silicon can start melting and diffusing.
S202: and in the constant temperature stage, the temperature in the constant temperature stage is higher than the aluminum-silicon eutectic temperature of 577 ℃, so that aluminum heavy doping is formed on the surface of the silicon wafer, and metal impurities in the silicon wafer are diffused to the surface of the silicon wafer. In particular, the temperature range of the thermostatic stage may be 600 ℃ to 750 ℃.
S203: and in the cooling stage, the temperature of the silicon wafer is reduced to be lower than the aluminum-silicon eutectic temperature so that the metal in the silicon wafer body reaches the aluminum alloy gettering layer to form precipitate and precipitate. Specifically, the temperature of the silicon wafer is reduced to be lower than the aluminum-silicon eutectic temperature of 577 ℃ in the temperature reduction stage.
The silicon wafer in the embodiment of the invention is dried at a temperature rise stage to remove organic matters in the aluminum paste; then, at a constant temperature stage, the aluminum and the silicon form a liquid phase, aluminum atoms can be rapidly diffused into a silicon region under a liquid state, and different layered regions are formed from the surface of the aluminum paste to the silicon body; and finally, performing rapid cooling annealing in a cooling stage to separate out metal impurities in the aluminum alloy gettering layer, thereby realizing aluminum gettering.
The embodiment of the invention superposes the screen printing technology and the chain annealing furnace technology. The screen printing technology is mature and stable, and low-cost aluminum paste can be used, so that the production cost of the aluminum paste is greatly reduced. The chain type annealing furnace can quickly realize the drying and doping of the aluminum paste, can quickly realize the annealing, has shorter process time and obvious gettering effect, and is convenient for large-scale mass production.
According to a specific implementation manner of the embodiment of the invention, the peak temperature range of the temperature rise stage is 600-750 ℃, and the time range is 2-6 min. If the temperature rise temperature in the temperature rise stage is too low, aluminum and silicon cannot be melted and diffused, and if the temperature rise temperature is too high, defects such as cracks and the like may be generated in the silicon wafer because organic matters are not completely volatilized due to too fast temperature rise when aluminum and silicon start to be melted and diffused. In addition, if the time of the temperature raising stage is too short, organic matters in the aluminum paste may not be sufficiently volatilized, and defects such as cracks may be formed in the silicon wafer, and if the time is too long, it is not favorable for improving the production efficiency.
The temperature range of the constant temperature stage is 600-750 ℃, and the time range is 2-10 min. If the temperature in the constant temperature stage is too low, a sufficient aluminum-silicon liquid image cannot be formed, aluminum impurities diffuse into silicon slowly, the gettering effect is not obvious, and the overall process time is increased; if the temperature is too high, the subsequent cooling process may be too fast, and the silicon wafer has an increased fragmentation rate due to stress. In addition, if the time of the constant temperature stage is too short, the metal impurities cannot be fully diffused, the quality of the silicon wafer is affected, and if the time is too long, the overall process time is increased.
And in the cooling stage, the temperature of the silicon wafer is reduced to be below the aluminum-silicon eutectic temperature, the time range of the cooling stage is 1min-3min, if the time of the cooling stage is too short, the cooling process is too fast, the fragment rate of the silicon wafer is increased probably due to stress, and if the time is too long, the whole process time is increased. Preferably, ceramic roller way type annealing furnace is selected for use to the chain type annealing furnace, because the ceramic roller way does not shift out the heating area of annealing furnace, therefore its heat dissipation is very little, saves energy, can also rise the temperature fast simultaneously.
In the embodiment of the invention, the peak temperature range of the temperature rise stage is set to be 600-750 ℃, the time range is set to be 2-6 min, the temperature range of the constant temperature stage is set to be 600-750 ℃, the time range is set to be 2-10 min, and the time range of the temperature reduction stage is set to be 1-3 min, so that metal in a silicon wafer body can reach an aluminum alloy gettering layer to form precipitates and separate out, and the whole process time can be shortened. That is, the temperature and time of each stage are set so as to achieve the effect of sufficient gettering and shortening the process time as a whole, thereby facilitating mass production.
According to a specific implementation manner of the embodiment of the present invention, the temperature-raising stage may include a first temperature-raising stage and a second temperature-raising stage, the peak temperature of the first temperature-raising stage is 280 ℃ to 320 ℃, preferably 300 ℃, and the second temperature-raising stage raises the temperature of the silicon wafer to above the aluminum-silicon eutectic temperature.
A first temperature rise stage: in the first temperature rise stage, the silicon wafer passes through a drying area, the peak temperature range of the drying area can be controlled to be 280-320 ℃, if the peak temperature of the drying area is too low, organic matters in the slurry cannot be fully volatilized, and if the peak temperature of the drying area is too high, the organic matters are volatilized when aluminum and silicon start to be melted and diffused, so that the silicon wafer has defects of cracks and the like.
A second temperature rising stage: gradually heating to the aluminum-silicon eutectic temperature of 577 ℃ or above, and melting and diffusing aluminum and silicon.
In the embodiment of the invention, the organic matters in the aluminum paste are fully volatilized through the first temperature rising stage, so that the defects that the silicon chip is cracked and the like due to bubbles generated by volatilization of the organic matters in the second temperature rising stage are avoided, and the organic components in the paste can be fully volatilized at about 300 ℃ without interference on mutual dissolution of aluminum and silicon in the subsequent second temperature rising stage, so that the temperature can be quickly raised in the second temperature rising stage, and the overall process time is shortened.
According to a specific implementation manner of the embodiment of the invention, a supplementary cooling stage is further included after the cooling stage, the supplementary cooling stage reduces the temperature of the silicon wafer to be below 100 ℃, and the cooling rate of the supplementary cooling stage is smaller than that of the cooling stage.
Specifically, the temperature of the silicon wafer is quickly reduced to be lower than the aluminum-silicon eutectic temperature in the cooling stage, so that metal in the silicon wafer body can reach an aluminum alloy gettering layer to form a precipitate and be separated out; and then, the temperature of the silicon wafer is reduced at a slower cooling rate, so that the internal stress of the silicon wafer caused by too fast temperature reduction is prevented.
That is to say, in the cooling stage, at first with the cooling of faster speed, then with the cooling of lower speed, so can make the internal metal of silicon chip form the deposit and separate out through the rapid cooling stage, make the temperature of silicon chip reduce with slower cooling rate after that to shorten whole process time, when having improved efficiency, prevented the silicon chip internal stress that the too fast temperature drop leads to.
According to a specific implementation manner of the embodiment of the invention, the peak temperature range of the first temperature rise stage is 280-320 ℃, the time range is 1-3 min, the time range of the second temperature rise stage is 1-3 min, the temperature range of the constant temperature stage is 600-750 ℃, the time range is 2-10 min, the time range of the temperature drop stage is 1-3 min, and the time range of the supplementary temperature drop stage is 2-6 min.
By setting the temperature and time of each stage in this way, not only can defects such as cracks caused by volatilization of organic substances be prevented, but also the overall process time can be shortened while effective gettering is achieved. Specifically, the peak temperature range of the first temperature rise stage is set to be 280-320 ℃, the time range is set to be 1-3 min, if the time of the stage is too short, the volatilization of organic matters cannot be guaranteed, so that defects such as cracks and the like can be caused, and if the time of the stage is too long, the overall process time is increased. The peak temperature range of the second temperature rise stage is set to be 577-750 ℃, the time range is set to be 1-3 min, if the time of the stage is too short, aluminum and silicon can not be fully melted and diffused mutually, and if the time of the stage is too long, the whole process time is increased. The temperature range of the constant temperature stage is 600-750 ℃, the time range is set to be 2-10 min, if the time of the stage is too short, metal impurities in the silicon wafer body cannot be fully diffused to the surface of the silicon wafer, and if the time of the stage is too long, the whole process time is increased. And in the cooling stage, the temperature of the silicon wafer is reduced to be lower than the aluminum-silicon eutectic temperature from the temperature range of 600-750 ℃ in the constant temperature stage, and the time range is set to be 1-3 min, if the time of the stage is too short, the metal in the silicon wafer body cannot be fully precipitated and separated out, and if the time of the stage is too long, the overall process time is increased. The time range of the supplementary cooling stage is set to be 2min-6min, so that the silicon wafer is cooled and then is processed in the next procedure. If the period is too short, stress may be induced in the silicon wafer due to too rapid a temperature decrease, and if the period is too long, the overall process time is increased. That is, in the embodiment of the present invention, the combination of the temperature and the time range of each stage shortens the overall process time while ensuring the gettering effect.
Next, referring to fig. 3, an optimal time configuration of each stage of the chain annealing process is described to achieve an increase in the preparation efficiency of the silicon wafer without affecting the minority carrier lifetime, so as to facilitate mass production.
In fig. 3, the time period t0-t1 corresponds to a first temperature-raising stage, the time period t1-t2 corresponds to a second temperature-raising stage, the time period t2-t3 corresponds to a constant-temperature stage, the time period t3-t4 corresponds to a temperature-lowering stage, and the time period t4-t5 corresponds to a supplementary temperature-lowering stage. In one embodiment of the invention, the time period t0-t1 is 1min-3min, the time period t1-t2 is 1min-3min, the time period t2-t3 is 2min-10min, the time period t3-t4 is 1min-3min, and the time period t4-t5 is 2min-6 min. And determining parameter settings of each stage of the chain annealing by combining the minority carrier lifetime of the silicon wafer obtained after the chain annealing.
Table 1 shows the minority carrier lifetime under different process time conditions compared to the minority carrier lifetime without gettering. And table 2 shows the process times of the respective stages under the respective process time conditions.
TABLE 1 comparison of minority carrier lifetime under different process time conditions with minority carrier lifetime without gettering
TABLE 2 Process time at each stage under each Process time Condition
It can be seen from the results in table 1 that the minority carrier lifetime is increased rapidly and then maintained substantially unchanged by adjusting the overall process time, which indicates that the gettering effect of the further heavy doped aluminum is limited, and the process time is set to 13min to 15min in consideration of the productivity and the cost.
In this case, as can be seen from table 2, the time range of the first temperature-raising stage is set to 1.86min to 2.14min, the time range of the second temperature-raising stage is set to 1.86min to 2.14min, the time range of the constant-temperature stage is set to 3.71min to 4.29min, the time range of the temperature-lowering stage is set to 1.86min to 2.14min, and the time range of the supplementary temperature-lowering stage is set to 3.71min to 4.29 min. Therefore, the process time can be shortened as much as possible on the premise of ensuring the minority carrier lifetime, so that the conversion rate is improved, the productivity is improved, and the mass production is facilitated.
Example 2:
in embodiment 2 of the present invention, the method further includes a damaged layer removing step before the step of forming the aluminum paste on at least one surface of the silicon wafer by screen printing.
Referring to fig. 4, S401, a damaged layer removing step. Specifically, a chemical method of acid etching or alkali etching may be adopted to remove the damaged layer on the surface of the silicon wafer and perform surface cleaning.
According to a specific embodiment, a KOH solution with the mass ratio of 2-12% can be adopted, preferably, a KOH solution with the mass ratio of 5% is adopted, under the condition that the temperature range is controlled to be 70-90 ℃, the single side of the silicon wafer is etched with the depth of more than 1.5 μm, the damaged layer caused by cutting the silicon wafer is removed, and meanwhile, the single side etching depth range is controlled to be 1.5-10 μm in order to reduce silicon loss. In addition, HF/HCl mixed solution with the mass ratio of 2% -10% is adopted for neutralizing metal ion complexing, and the surface of the silicon wafer is cleaned.
In addition, in fig. 4, step S402 corresponds to step S101 in fig. 1, and step S403 corresponds to step S102 in fig. 1, which is not described herein again.
Example 3:
referring to fig. 5, in embodiment 3 of the present invention, after the step of chain annealing the silicon wafer on which the aluminum paste is formed, the method further includes a step S504 of removing the aluminum alloy gettering layer, thereby removing the surface aluminum metal, and corroding the aluminum-silicon alloy gettering layer on the surface of the silicon wafer, and cleaning.
According to a specific embodiment, a phosphoric acid solution with the mass ratio of 2% -10% is adopted to remove an aluminum alloy gettering layer on the surface of a silicon wafer, a KOH solution with the mass ratio of 2% -12% is adopted, the temperature range is controlled to be 70-90 ℃, one side of the silicon wafer is corroded, the corrosion thickness is larger than 2 microns, and all doped layers containing aluminum atoms are corroded. And cleaning the silicon wafer by adopting an HF/HCl mixed solution with the mass ratio of 2-10%.
In fig. 5, steps S501 to S503 correspond to steps S401 to S403 in fig. 4, respectively, and are not described again.
Example 4:
referring to fig. 6, in inventive example 4, the scheme of example 4 did not include a damaged layer removing step, compared to the scheme of example 3.
In addition, steps S601 to S603 in fig. 6 may be the same as steps S502 to S504 in embodiment 3, and are not repeated here.
Example 5:
referring to fig. 7, an embodiment of the present invention also provides an aluminum gettering apparatus 700, including:
a screen printing apparatus 701, the screen printing apparatus 701 forming an aluminum paste on at least one surface of the silicon wafer by screen printing; and
a chain annealing furnace 701, wherein the chain annealing furnace 701 performs chain annealing on the silicon wafer formed with the aluminum paste, and the chain annealing comprises a temperature rising stage, a constant temperature stage and a temperature lowering stage, wherein the temperature rising stage raises the temperature of the silicon wafer to be higher than the aluminum-silicon eutectic temperature, the temperature in the constant temperature stage is higher than the aluminum-silicon eutectic temperature, and the temperature lowering stage lowers the temperature of the silicon wafer to be lower than the aluminum-silicon eutectic temperature.
The process of forming the aluminum paste on at least one surface of the silicon wafer by the screen printing apparatus 701 and the process of performing the chain annealing in the chain annealing furnace 701 by using the screen printing apparatus 701 may refer to the corresponding descriptions in the above embodiments 1 to 4, and will not be described again here.
The aluminum gettering equipment provided by the embodiment of the invention performs aluminum gettering by using a screen printing superposition chain type annealing furnace technology. The screen printing technology is mature and stable, and low-cost aluminum paste can be used, so that the production cost of the aluminum paste is greatly reduced. The chain type annealing furnace can quickly realize the drying and doping of the aluminum paste, can quickly realize the annealing, has shorter process time and obvious gettering effect, and is convenient for large-scale mass production.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. An aluminum gettering method applied to gettering of a silicon wafer, characterized by comprising:
forming an aluminum paste on at least one surface of the silicon wafer by screen printing; and the number of the first and second groups,
and performing chain annealing on the silicon wafer with the aluminum paste, wherein the chain annealing comprises a heating stage, a constant temperature stage and a cooling stage, the heating stage raises the temperature of the silicon wafer to be higher than the aluminum-silicon eutectic temperature, the constant temperature stage is higher than the aluminum-silicon eutectic temperature, and the cooling stage lowers the temperature of the silicon wafer to be lower than the aluminum-silicon eutectic temperature.
2. The aluminum gettering method of claim 1, characterized in that, the peak temperature range of the temperature rise stage is 600-750 ℃, the time range is 2-6 min;
the temperature range of the constant temperature stage is 600-750 ℃, and the time range is 2-10 min;
the time range of the cooling stage is 1min-3 min.
3. The aluminum gettering method of claim 1, characterized in that, the temperature rise stage includes a first temperature rise stage and a second temperature rise stage, the first temperature rise stage having a peak temperature in a range of 280 ℃ to 320 ℃, the second temperature rise stage raising the temperature of the silicon wafer to above the aluminum-silicon eutectic temperature.
4. The aluminum gettering method of claim 3, characterized in that, a supplementary cooling stage is further included after the cooling stage, the supplementary cooling stage reduces the temperature of the silicon wafer to below 100 ℃, and a cooling rate of the supplementary cooling stage is smaller than that of the cooling stage.
5. The aluminum gettering method of claim 4, characterized in that the time range of the first temperature rise stage is 1min-3min, the time range of the second temperature rise stage is 1min-3min, the time range of the constant temperature stage is 2min-10min, the time range of the temperature drop stage is 1min-3min, and the time range of the supplementary temperature drop stage is 2min-6 min.
6. The aluminum gettering method of claim 5, characterized in that the time range of the first temperature rise stage is 1.86-2.14 min, the time range of the second temperature rise stage is 1.86-2.14 min, the time range of the constant temperature stage is 3.71-4.29 min, the time range of the temperature drop stage is 1.86-2.14 min, and the time range of the supplementary temperature drop stage is 3.71-4.29 min.
7. The aluminum gettering method of any one of claims 1 through 6, wherein an aluminum paste is formed on at least one surface of the silicon wafer using an aluminum back field screen, and the thickness of the aluminum paste ranges from 1 μm to 10 μm.
8. The aluminum gettering method of any one of claims 1 through 6, characterized in that, prior to the step of forming an aluminum paste on at least one surface of the silicon wafer by screen printing, the method further comprises:
adopting 2-12% KOH solution by mass ratio, and corroding one side of the silicon wafer at the temperature of 70-90 ℃ to the corrosion depth of more than 1.5 mu m; and the number of the first and second groups,
and (3) carrying out neutralization and metal ion complexation by adopting an HF/HCl mixed solution with the mass ratio of 2-10%.
9. The aluminum gettering method of any one of claims 1 through 6, characterized in that, after the step of chain annealing the silicon wafer formed with the aluminum paste, the method further comprises:
removing the aluminum alloy gettering layer on the surface of the silicon wafer by adopting a phosphoric acid solution with the mass ratio of 2% -10%;
adopting a KOH solution with the mass ratio of 2-12%, controlling the temperature range to be 70-90 ℃, and corroding one side of the silicon wafer, wherein the corrosion thickness is more than 2 mu m; and the number of the first and second groups,
and cleaning the silicon wafer by adopting an HF/HCl mixed solution with the mass ratio of 2-10%.
10. An aluminum gettering apparatus that is applied to gettering of a silicon wafer, characterized by comprising:
a screen printing apparatus that forms an aluminum paste on at least one surface of the silicon wafer by screen printing; and the number of the first and second groups,
the chain annealing furnace is used for performing chain annealing on the silicon wafer formed with the aluminum paste, and comprises a heating stage, a constant temperature stage and a cooling stage, wherein the heating stage is used for heating the temperature of the silicon wafer to be higher than the aluminum-silicon eutectic temperature, the constant temperature stage is used for heating the temperature of the silicon wafer to be higher than the aluminum-silicon eutectic temperature, and the cooling stage is used for cooling the temperature of the silicon wafer to be lower than the aluminum-silicon eutectic temperature.
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