CN113224178A - Production method of silicon wafer, silicon wafer produced by using production method and solar cell - Google Patents

Production method of silicon wafer, silicon wafer produced by using production method and solar cell Download PDF

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CN113224178A
CN113224178A CN202110467033.7A CN202110467033A CN113224178A CN 113224178 A CN113224178 A CN 113224178A CN 202110467033 A CN202110467033 A CN 202110467033A CN 113224178 A CN113224178 A CN 113224178A
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silicon wafer
substrate
silicon
wafer
thin
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CN113224178B (en
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高文秀
赵百通
佐佐木实
高向曈
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YIXING YUYUAN ENERGY EQUIPMENT TECHNOLOGY DEVELOPMENT CO LTD
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YIXING YUYUAN ENERGY EQUIPMENT TECHNOLOGY DEVELOPMENT CO LTD
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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
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the 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
    • 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
    • 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

Abstract

The invention discloses a production method of a silicon wafer, and the silicon wafer and a solar cell produced by the method, which comprises the following steps: (1) storing the substrate; (2) detecting a substrate; (3) manufacturing a thin silicon wafer; (4) annealing the substrate thin silicon wafer; (5) p-type or n-type diffusion of the substrate silicon wafer; (6) and annealing the substrate silicon wafer for forming the pn junction. The method can realize the silicon film with the thickness of less than 50 microns, theoretically save more than 80 percent of silicon materials, directly and naturally grow the silicon wafer on the surface of the substrate, has uniform thickness, directly manufactures the solar cell on the silicon wafer of the substrate, and improves the power generation efficiency.

Description

Production method of silicon wafer, silicon wafer produced by using production method and solar cell
Technical Field
The invention relates to photovoltaics, in particular to a production method of a silicon wafer, and the silicon wafer and a solar cell produced by the method.
Background
The silicon wafer is the most basic part of the crystalline silicon solar cell. Without a silicon wafer, a photo-generated current cannot be generated, and the silicon wafer cannot become a solar photovoltaic power generation cell, so that the manufacturing of the silicon wafer is one of the most important processes of the photovoltaic solar cell.
According to the basic principle of photovoltaic silicon-based power generation, the effective power generation thickness of the optimal silicon-based battery is calculated to be about 50 microns. The thin power generation layer is extremely thin, direct transition photovoltaic elements such as germanium and gallium can be purposefully introduced, and the potential possibility of breaking through the theoretical photovoltaic power generation efficiency limit is realized. However, the current process route cannot realize large-scale manufacturing of the thin silicon wafer, and industrial wire cutting is difficult to realize.
In the prior art, polycrystalline or monocrystalline silicon wafers are required to be subjected to a mechanical process of wire cutting, critical power generation pn junctions are only several microns, cutting inevitably causes hard fine scratches on the surfaces of the silicon wafers, and the silicon lattice structures on the surfaces are damaged.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the production method of the silicon wafer and the solar cell produced by the method, the method can realize a silicon film with the thickness of less than 50 microns, theoretically more than 80% of silicon materials can be saved, the silicon wafer directly and naturally grows on the surface of a substrate, the thickness is uniform, the solar cell is directly manufactured on the substrate silicon wafer, and the photovoltaic power generation efficiency is improved.
In order to achieve the technical purpose, the invention adopts the following technical scheme: the production method of the silicon chip comprises the following steps
Manufacturing a thin silicon wafer: fixing a substrate in a closed system, injecting a liquid silicon material onto the substrate, rotating the substrate to enable the liquid silicon material to form a layer of thin film on the substrate, and adding a cold source on the upper surface of the thin film to enable the thin film to be solidified downwards from the surface to form a p-type or n-type crystal thin silicon wafer;
annealing the thin silicon wafer: annealing the thin silicon wafer formed on the substrate;
p-type or n-type diffusion: when the thin silicon wafer on the substrate is of a p type, carrying out diffusion by taking phosphorus as a diffusion source to form a pn junction; when the thin silicon wafer on the substrate is of an n type, carrying out diffusion by taking boron as a diffusion source to form a pn junction;
pn junction annealing: and annealing the substrate thin silicon wafer with the pn junction formed to form a silicon wafer.
Further, when injecting the liquid silicon material, the method comprises the following steps: and placing the solid silicon in a silicon material adding system, keeping the solid silicon at a constant temperature, quickly heating the solid silicon to a temperature above the melting point of the silicon material, so that the solid silicon is changed into a liquid silicon material, and injecting the liquid silicon material onto the substrate by the silicon material adding system.
Further, in a closed system for making thin silicon wafers, the argon pressure range: 40-80 kPa, constant temperature range: 1250-1400 ℃; keeping the constant temperature of the solid silicon by a heating device, wherein the temperature range is as follows: keeping the temperature of 1300-1400 ℃ for 1-5 seconds, and then instantly heating the solid silicon to over 1450 ℃ by another heating device.
Further, in the closed system, set up one and get rid of piece mechanism, it is fixed with on the piece mechanism and gets rid of the piece platform to get rid of piece mechanism, the base plate is fixed get rid of on the piece platform, it is connected with argon gas to add silicon material system, and argon gas pushes away liquid silicon material extremely on the base plate, it drives to get rid of piece mechanism get rid of piece platform rotary motion.
Further, get rid of a piece mechanism and drive get rid of the rotatory speed of piece platform and carry out the variable speed motion by slow to fast, and reach within 1 ~ 10 seconds and set for rotational speed, rotational speed scope: 300 to 5000 rpm.
Furthermore, the crystal thin silicon wafer and the substrate are integrated, and the crystal thin silicon wafer is a monocrystalline silicon wafer or a polycrystalline silicon wafer and is several micrometers to several thousands of micrometers in thickness.
Further, the crystalline thin silicon wafer is a single-crystal silicon wafer which is an extremely thin columnar high mobility thin layer.
Further, during annealing of thin silicon wafers, the argon pressure constant range: 40-80 kPa, constant temperature range: 1250-1400 ℃; the annealing time range is as follows: the annealing temperature is the lowest temperature of the pn junction formed by diffusion and ranges from 800 ℃ to 1000 ℃ for 0.5-12 hours.
A silicon wafer produced by the method described above.
The solar cell comprises the silicon wafer, and a layer of antireflection film is arranged on the surface of the silicon wafer.
In conclusion, the invention achieves the following technical effects:
1. the substrate is fixed in a closed system, liquid silicon material is injected onto the substrate, the substrate is rotated to enable the liquid silicon material to form a layer of thin film on the substrate, a cold source is added on the upper surface of the thin film to enable the thin film to be solidified downwards from the surface, a p-type or n-type crystal thin silicon wafer is formed, the crystal thin silicon wafer and the substrate are integrated, the thin silicon wafer grows on the substrate, the crystal thin silicon wafer is a single crystal thin silicon wafer or a polycrystal thin silicon wafer, the thickness of the crystal thin silicon wafer is several micrometers to thousands of micrometers, and the naturally grown thickness can be extremely thin;
2. the constant temperature of the solid silicon is maintained, and then the solid silicon is instantly heated to form a liquid silicon material, so that the silicon wafer is convenient to spin;
3. the invention utilizes a flail mechanism to drive the substrate to rotate and drive the liquid silicon material on the substrate to be flaked to form a layer of film with uniform thickness, and the flail mode leads the silicon material to be completely contacted with the substrate and naturally grows crystals on the substrate;
4. the invention can automatically form silicon wafers, theoretically can realize a silicon film with the thickness of less than 50 microns, theoretically can save more than 80 percent of silicon materials, save the silicon materials, has low cost, does not need cutting and other abrasion, and has higher efficiency;
5. the silicon wafer formed by the invention can be cut and cut at will to form shapes such as a circle, a quadrangle, a pentagon, a hexagon, a pentagon and the like, and the shape and the area are controllable.
Drawings
FIG. 1 is a flow chart of a production method provided by an embodiment of the present invention;
FIG. 2 is a schematic diagram of the overall structure of a production facility provided by an embodiment of the present invention;
FIG. 3 is a schematic view of an initial storage section provided by an embodiment of the present invention;
FIG. 4 is a schematic structural diagram of a detection portion provided in an embodiment of the present invention;
FIG. 5 is a schematic illustration of transport away at the inspection section provided by an embodiment of the present invention;
FIG. 6 is a schematic structural diagram of a silicon wafer forming part according to an embodiment of the present invention;
FIG. 7 is a schematic diagram illustrating an operation of a silicon wafer forming portion according to an embodiment of the present invention;
FIG. 8 is a schematic structural view of an annealing portion provided in an embodiment of the present invention;
FIG. 9 is a schematic structural view of a pn junction forming portion provided in an embodiment of the present invention;
fig. 10 is a schematic structural diagram of a buffering portion according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Example (b):
a method for producing a silicon wafer comprises the following steps:
(1) substrate storage: the automatic substrate storage device is used for storing a certain number of substrates in advance, the substrates are visually qualified at the moment, and the substrates are transported to the next step by utilizing a manipulator and a conveying mechanism;
(2) substrate detection: the substrate defect detection device is used for detecting the defects of the substrate, removing the unqualified substrate, and enabling the qualified substrate to enter the next step by utilizing the manipulator and the conveying mechanism;
(3) manufacturing a thin silicon wafer: fixing a substrate in a closed system, injecting a liquid silicon material onto the substrate, rotating the substrate to enable the liquid silicon material to form a layer of thin film on the substrate, and adding a cold source on the upper surface of the thin film to enable the thin film to be solidified downwards from the surface to form a p-type or n-type crystal thin silicon wafer;
(4) annealing the thin silicon wafer: annealing the thin silicon wafer formed on the substrate; wherein, the argon pressure constant range: 40-80 kPa, constant temperature range: 1250-1400 ℃; the annealing time range is as follows: the minimum annealing temperature is the temperature for forming a pn junction by diffusion and ranges from 800 ℃ to 1000 ℃ for 0.5-12 hours;
(5) p-type or n-type diffusion: when the thin silicon wafer on the substrate is of a p type, carrying out diffusion by taking phosphorus as a diffusion source to form a pn junction; when the thin silicon wafer on the substrate is of an n type, carrying out diffusion by taking boron as a diffusion source to form a pn junction;
(6) pn junction annealing: and annealing the substrate thin silicon wafer with the formed pn junction to further eliminate the internal stress.
Before describing the above six steps, the equipment used is described: as shown in fig. 2, including an initial storage section R1, a detection section R2, a silicon wafer forming section R3, an annealing section R4, a pn junction forming section R5, a buffer section R6, and a conveying mechanism provided between the adjacent sections, which are arranged in this order; the six parts respectively correspond to the six steps; the silicon wafer forming part R3 is internally provided with a silicon material adding system 7, a wafer throwing mechanism 8 and a wafer throwing platform 9, the wafer throwing mechanism 8 drives the wafer throwing platform 9 to rotate, and the silicon material adding system 7 injects liquid silicon materials onto the substrate 1 on the wafer throwing platform 9.
Each part comprises a cavity, a valve is arranged at the inlet end and the outlet end of each cavity, the valve enables the corresponding cavity to form a closed system, the valve can be opened or closed to enable the corresponding cavity to be capable of opening and transporting substrates or being closed to implement production processes of substrate silicon wafers, diffusion or annealing and the like, a conveying mechanism is arranged between the valve positioned at the outlet end of the previous cavity and the valve positioned at the inlet end of the next cavity, and the conveying mechanisms are provided with a plurality of conveying mechanisms and used for conveying the processed substrate of the previous part to the next part to continue processing or directly conveying the processed substrate of a finished product.
Further elaboration is as follows: the conveying mechanism comprises an initial conveying mechanism p1, a first conveying mechanism a2, a second conveying mechanism b2, a third conveying mechanism c2, a fourth conveying mechanism d2, a fifth conveying mechanism e2, a sixth conveying mechanism f2, a seventh conveying mechanism g2 and an eighth conveying mechanism h 2. The conveying mechanism is further provided with buffer channels, specifically a first buffer channel a3, a second buffer channel b3, a third buffer channel c3, a fourth buffer channel d3, a fifth buffer channel e3, a sixth buffer channel f3 and a seventh buffer channel g3 which respectively correspond to the buffer channels.
Further, the related hardware equipment comprises substrate detection equipment for detecting whether the substrate has defects, a plurality of conveying mechanisms for conveying the substrate, automatic isolation valve control equipment for controlling the opening and closing of a valve, laser heating equipment for heating the silicon wafer in the silicon wafer forming part R3, silicon feeding equipment for conveying liquid silicon materials to the silicon wafer forming part R3, a heat radiation prevention camera for collecting images, a temperature sensor for sensing the internal temperature, cavity constant-temperature heating equipment for ensuring the temperature in the cavity, vacuum pumping equipment for vacuumizing the cavity, argon filling equipment for filling argon into the cavity, and blade throwing equipment for rotationally scattering and diffusing the liquid silicon. All automation equipment of the equipment are controlled by a PLC program, manual work is replaced, automatic production is realized, and production efficiency is improved.
The above six steps are described in sequence as follows:
(1) substrate storage: the automatic substrate storage device is used for storing a certain number of substrates in advance, the substrates are visually qualified at the moment, and the substrates are transported to the next step by utilizing a manipulator and a conveying mechanism;
as shown in fig. 3, this step involves an initial storage section R1, and the initial storage section R1 includes a first cavity a1, which has a main function of storing the substrates, so that the visually acceptable substrates can be subjected to the next process according to the manufacturing process. A storage rack 21 is fixed in the first cavity a1, the storage rack 21 is used for storing the substrates 1, and 100-10000 substrates can be stored on the support according to the thickness of the substrates.
Specifically, the first chamber a1 is connected to a vacuum extractor (not shown), a first heater 31, and an argon gas source (not shown).
Specifically, an initial closing valve P is provided at an inlet end of the first chamber a1, an initial transfer mechanism P1 is connected to an outside of the initial closing valve P, and the initial transfer mechanism P1 transfers the substrate 1 into the first chamber a 1; a first closing valve a (a valve a described below) is provided at an outlet end of the first chamber a1, a first transfer mechanism a2 is connected to an outside of the valve a, and the first transfer mechanism a2 transfers the substrate 1 to a next portion.
In this step, the substrate 1 is externally placed on an automatic initial transfer mechanism P1 controlled by a PLC, the initial transfer mechanism P1 transfers the substrate to an initial close valve P, the initial close valve P (valve P described below) senses the presence of the substrate, the valve P is automatically opened, the substrate enters the first chamber a1 through the initial close valve P, and a robot a (not shown) sequentially places the substrate on the storage shelf 21. Other automatic valves are always closed during substrate storage. When the storage procedure is completed, that is, the number of the stored substrates reaches the set value, the storage chamber stops operating the initial conveying mechanism P1, and the valve P is closed until the next substrate storage procedure is started.
After the valve P is closed, a vacuum-pumping device (not shown) is started to vacuum the first chamber a1, and when the vacuum degree reaches below 10Pa, an argon-filling procedure is started to heat the inside of the first chamber a1, so that the inside of the first chamber a1 is kept at a constant temperature and a constant pressure. Argon pressure range in the first chamber a 1: 30-80 kPa, temperature range: 300 to 600 ℃. When the constant temperature and the constant pressure reach the set time, the detecting section R2 of the next section is programmed to transport the substrates on the shelves one by one to the next section by the robot arm by the first transport mechanism a 2.
(2) Substrate detection: the substrate defect detection device is used for detecting the defects of the substrate, removing the unqualified substrate, and enabling the qualified substrate to enter the next step by utilizing the manipulator and the conveying mechanism;
as shown in fig. 4, this step involves a detecting portion R2, the detecting portion R2 includes a second cavity b1, and a detecting platform 22 for detecting the substrate 1 is disposed in the second cavity b 1; the inlet end of the second cavity B1 is provided with a second closed valve B (the valve B is described below), and the outside of the valve B is butted with the first conveying mechanism a 2; the outlet end of the second chamber b1 is provided with a third close valve C (valve C described below), and a second transfer mechanism b2 is connected to the outside of the valve C, and the second transfer mechanism b2 transfers the substrate 1 to the next portion.
The first conveyance mechanism a2 is provided with a first buffer passage a3, and the second conveyance mechanism b2 is provided with a second buffer passage b 3.
The detection part R2 mainly has the function that quality inspection equipment (not shown) further detects whether the substrate has defects at the temperature of 300-600 ℃, qualified substrates enter the next step, unqualified substrates are transported out of the second cavity b1 through a special channel (not shown), and crushing, re-sintering and re-die pressing are carried out. The precision of the detection equipment is in the micron level, the quality of the photovoltaic module is greatly improved, and the photoelectric conversion efficiency of the photovoltaic module is improved. Second cavity b1 environment: the argon intensity was 100 kPa.
In this step, as shown in fig. 5, the method specifically includes the following steps:
in the first chamber a1, the robot a sequentially puts the substrates on the first transfer mechanism a2 of the first buffer passage a3 in accordance with the order of the substrates stored on the racks in which the substrates are at constant temperature and pressure by the robot a. PLC controlled automatic valve opening sequence: when the robot a in the first chamber a1 "carries" the substrate, and when the robot a moves to a set position, the automatic valve a receives a sensor signal, the robot a in the first chamber a1 puts the substrate into the first buffer channel a3, and the valve a is automatically opened. The hand a places the substrate on the first transfer mechanism a2, the hand a withdraws from the first buffer passage a3, the hand a withdraws to the set position, and the valve a is closed. When the first transfer mechanism a2 transfers the substrate to the set position sensed by the automatic valve B, the valve B is automatically opened, the robot B in the second chamber B1 places the substrate in the first buffer passage a3 into the second chamber B1, the substrate is waiting for inspection, the valve B is automatically closed, and the quality inspection device (not shown) starts the process of inspecting the substrate.
The device is used for detecting the quality of a substrate in the second cavity b1, and the main purpose is to manufacture a high-quality photovoltaic cell assembly. The quality inspection equipment sets a certain substrate quality inspection standard, qualified substrates meeting the standard enter the next cavity to be subjected to subsequent procedures, and unqualified substrates are sent to a special channel to exit the second cavity b 1. The substrate quality inspection standards were as follows: the appearance shape has no broken pieces, cracks, unfilled corners, gaps, stains, falling off and the like; the external dimension-side length deviation is less than plus or minus 0.5mm, and the diagonal deviation is less than plus or minus 0.3 mm; thickness dimension-indentation deviation of + -10 um, warp degree of <50um, bow of <75um, thickness variation of < 5% nominal thickness; the edge breakage requirement is that the length is less than 1mm, the depth is less than 0.5mm, and the number is less than or equal to 2; the straight line verticality of the two adjacent sides is less than 90 +/-0.3 degrees. The substrate not meeting the above standard will exit the second cavity b1 through a dedicated channel, and the substrate meeting the above standard will enter the next silicon wafer fabrication cavity.
(3) Manufacturing a thin silicon wafer: fixing a substrate in a closed system, injecting a liquid silicon material onto the substrate, rotating the substrate to enable the liquid silicon material to form a layer of thin film on the substrate, and adding a cold source on the upper surface of the thin film to enable the thin film to be solidified downwards from the surface to form a p-type or n-type crystal thin silicon wafer;
the thin crystal silicon wafer formed in the above steps and the substrate are integrated, the thin silicon wafer grows on the substrate, and the thin crystal silicon wafer is a single crystal thin silicon wafer or a polycrystalline thin silicon wafer with the thickness of 10-2000 um. When the crystalline thin silicon wafer is a monocrystalline silicon wafer, the monocrystalline silicon wafer is an extremely thin columnar high mobility thin layer.
As shown in fig. 6, this step involves a silicon wafer forming part R3, the silicon wafer forming part R3 includes a third cavity c1, a wafer throwing platform 9 and a silicon feeding system 7 are disposed in the third cavity c1, the silicon feeding system 7 injects silicon material onto a substrate on the wafer throwing platform 9, and the wafer throwing platform 9 rotates. Further, the flail platform 9 is connected with a flail mechanism 8 for driving the flail platform 9 to rotate; the third cavity c1 is further provided therein with a second heating device (such as the first laser heater 51, the second laser heater 52, and the constant temperature heater 32 shown in fig. 6), a first temperature sensor 41, an image sampling device employing camera 6, a vacuum extraction mechanism (not shown), and an argon gas charging system (not shown).
Wherein, get rid of piece mechanism 8 and can adopt structures such as servo motor, step motor or other structures to drive and get rid of piece platform 9 rotatory.
The functions of the above hardware devices are as follows: the silicon material adding system 7 is used for weighing silicon materials (the weight of the silicon materials is calculated according to the thickness of a silicon wafer and the area of a substrate and is set as a fixed value), the silicon material adding system 7 utilizes first laser heating 51 to keep the silicon materials at a constant temperature, under the assistance of second laser heating 52, the temperature of the silicon materials is quickly increased to be higher than the melting point of the silicon materials, solid silicon is changed into liquid silicon, and the liquid silicon is injected onto the substrate on the wafer throwing mechanism; the first temperature sensor 41 detects the temperature of c in the closed system, keeping the temperature constant; the first laser heating 51 is used for keeping the silicon material at a constant temperature to provide heat energy, and the second laser heating 52 is used for changing solid silicon into liquid silicon to provide instant heat energy, wherein the first laser heating and the second laser heating are used for adjusting laser power and laser pulses to achieve the required heat energy; the camera 6, namely a heat radiation prevention camera, has the function of recording each detail and process of the flail, so that the production technology is improved conveniently; the constant temperature heater 32 is used for keeping the third cavity c1 constant in temperature to provide heat; the main function of the wafer throwing mechanism 8 is to form the required silicon wafer on the substrate at a certain rotating speed by the liquid silicon on the substrate.
Further, a fourth closed valve D is arranged at an inlet end of the third cavity c1, and the fourth closed valve D is in butt joint with the second conveying mechanism b 2; the outlet end of the third chamber c1 is provided with a fifth sealing valve E, and a third transfer mechanism c2 is provided outside the fifth sealing valve E, and the third transfer mechanism c2 transfers the substrate 1 with the silicon wafer to the next portion.
The silicon wafer forming part R3 has the main function of throwing out silicon wafers on the surface of a qualified substrate, and throwing out silicon wafers with different thicknesses according to different use requirements of the silicon wafers. The environment requirement in the third cavity c1 is high, the whole system for manufacturing the silicon wafer cavity is closed, the whole system is vacuumized by a vacuum pump (not shown), and then high-purity argon gas (not shown) is filled; then, vacuumizing and filling high-purity argon gas are carried out, so that the system is repeatedly cleaned for many times, the whole system is kept in the high-purity argon atmosphere, and the silicon wafer is not polluted by the external environment in the process of forming the silicon wafer. The argon pressure in the third chamber c1 is kept within the required range: 40-80 kPa, constant temperature requirement: 1250-1400 ℃, and the constant temperature is different according to the thickness of the silicon wafer.
In this step, as shown in fig. 7, the qualified substrate in the substrate inspection chamber enters the third chamber c1, and the automatic transportation process is similar to the above-mentioned transportation process, and will not be described redundantly. The method comprises the following specific steps:
(31) qualified substrates in the second cavity b1 pass through a second buffer channel b3 and enter a third cavity c1 through a second conveying mechanism b2, and the substrates are placed at a specified position of a platform of a sheet throwing mechanism by a manipulator c (not shown) and are fixed on the platform; at the moment, the substrate is heated to the temperature in an environment with the temperature of 1250-1400 ℃, so that partial liquid silicon solidification is prevented from occurring at the moment that the liquid silicon is dripped onto the substrate;
(32) the silicon charge is metered into the feed system, for example 50 microns thick, 210mm side length2The silicon wafer of (a) requires a silicon mass weight of about 5.2 g;
(33) after the silicon material enters the feeding system, the silicon material is heated by the first laser 51 to keep constant temperature, and the temperature range is as follows: 1300-1400 ℃;
(34) after keeping for 1-5 seconds, the second laser heating 52 heats the silicon material to above 1450 ℃ instantly, and the solid silicon becomes liquid silicon instantly;
(35) the silicon material adding system is connected with an argon gas charging port, and the pulsed argon gas pushes the liquid silicon to a substrate on a wafer throwing mechanism platform;
(36) the throwing piece is quickly started, the action of the throwing piece mechanism is accurately controlled, and the speed is changed from slow to fast; get rid of the base plate that piece mechanism drove on the platform and rotate and get rid of the piece, reach within 1 ~ 10 seconds and set for the rotational speed, the rotational speed scope: 300-5000 rpm;
(37) when the liquid silicon is thrown away on the substrate, a layer of film is formed, and a cold source is added on the upper surface of the film, wherein the cold source is solid or inert gas with the temperature lower than 1000 ℃; the film is solidified from the surface downwards, so that the melted silicon material forms a p-type or n-type layer of thin crystal silicon wafer on the substrate material; the formed silicon wafers are uniform in thickness and are polycrystalline or monocrystalline thin silicon wafers.
In the step, one surface of the substrate is completely contacted with liquid silicon according to the preheating temperature of the substrate, the melting temperature of the silicon material, and the precise action mode and the action parameters of the flaker mechanism which are set in the process, so that the substrate is in close contact with the silicon wafer. The thickness of the manufactured silicon chip is related to the technical parameters such as the temperature of liquid silicon, the temperature of a substrate, the temperature of a cold source, the rotating speed of a wafer throwing mechanism and the like. The thinner the silicon wafer manufactured on the substrate is, the higher parameters such as the temperature of the substrate, the temperature of liquid silicon, the rotating speed of the wafer throwing mechanism and the like are required.
(4) Annealing the thin silicon wafer: annealing the substrate on which the thin silicon wafer is formed; wherein, the argon pressure constant range: 40-80 kPa, constant temperature range: 1250-1400 ℃; the annealing time range is as follows: the minimum annealing temperature is the temperature for forming a pn junction by diffusion and ranges from 800 ℃ to 1000 ℃ for 0.5-12 hours;
as shown in fig. 8, this step involves an annealing section R4, the annealing section R4 includes a fourth chamber d1, an annealing support 23 is provided in the fourth chamber d1, and the substrate 1 with silicon wafer is held on the annealing support 23; the fourth cavity d1 is also internally provided with a third heating device (an annealing heater 33 and an annealing heater 34) and a second temperature sensor 42; a sixth sealing valve F is arranged at the inlet end of the fourth cavity d1 and is in butt joint with a third conveying mechanism c 2; a seventh closed valve G is arranged at an outlet end of the fourth cavity d1, a fourth conveying mechanism d2 and a fifth conveying mechanism e2 are arranged outside the seventh closed valve G, an eighth closed valve H is arranged between the fourth conveying mechanism d2 and the fifth conveying mechanism e2, and the fifth conveying mechanism e2 conveys the annealed substrate 1 to the next part.
The annealing part R4 mainly functions to lower the temperature of the silicon wafer formed on the substrate according to the temperature curve and remove the stress of the substrate, the contact surface of the substrate and the silicon wafer, the silicon wafer and the like. The equipment in the fourth chamber d1 includes an annealing heater, a temperature sensor and an annealing support. The internal environmental requirements in the fourth chamber d1 are the same as in the third chamber c 1. Before use, the whole system is vacuumized by a vacuum pump, and then high-purity argon is filled; then, vacuumizing and filling high-purity argon gas are carried out, so that the system is repeatedly cleaned for many times, the whole system is kept in a high-purity argon atmosphere, and the silicon wafer forming process is not polluted by the external environment. The argon pressure and the constant temperature in the fourth chamber d1 are also maintained to be the same as those in the third chamber c1, so that the quality of the silicon wafer and the substrate is not affected by the pressure and the temperature during the transportation from the third chamber c1 to the fourth chamber d 1. The argon pressure is required to be constant, the setting range is 40-80 kPa, the constant temperature setting range is 1250-1400 ℃, and in order to ensure the performance of the silicon wafer, the temperature of the fourth cavity d1 before annealing is consistent with that of the third cavity c 1. The annealing support in the fourth cavity d1 can hold substrates with silicon wafers in the number range: 100 to 10000 tablets.
When the substrate on which the silicon wafer is formed enters the fourth chamber d1 from the third chamber c1 through the third buffer passage c3 by the third transfer mechanism c2, the silicon wafer is placed on the annealing support by the robot d. When the number of the silicon wafers reaches a set value, the annealing temperature curve and the annealing time which start to decrease from the constant temperature in the fourth cavity d1 are different according to the thickness of the formed silicon wafers and the thickness of the substrate, and the annealing time range is as follows: the annealing temperature is the lowest temperature of the pn junction formed by diffusion and ranges from 800 ℃ to 1000 ℃ for 0.5-12 hours. And a thin silicon wafer formed on the surface of the substrate enters an annealing cavity to carry out crystal growth heat treatment, and internal stress formed during solidification is eliminated so as to improve the manufacturing qualification rate of subsequent processes.
(5) p-type or n-type diffusion: when the thin silicon wafer on the substrate is of a p type, carrying out diffusion by taking phosphorus as a diffusion source to form a pn junction; when the thin silicon wafer on the substrate is of an n type, carrying out diffusion by taking boron as a diffusion source to form a pn junction;
as shown in fig. 9, this step involves a pn junction forming portion R5, the pn junction forming portion R5 includes a fifth cavity e1, and the pn junction making system 10 is disposed in the fifth cavity e 1; a ninth closing valve J is arranged at the inlet end of the fifth cavity e1 and is in butt joint with the fifth conveying mechanism e 2; a tenth closed valve K is arranged at the outlet end of the fifth cavity e1, a sixth conveying mechanism f2 and a seventh conveying mechanism g2 are arranged outside the tenth closed valve K, an eleventh closed valve L is arranged between the sixth conveying mechanism f2 and the seventh conveying mechanism g2, and the seventh conveying mechanism g2 conveys the substrate 1 forming the pn junction to the next part.
The pn junction forming portion R5 mainly functions to p-type or n-type diffusion of the annealed silicon wafer, that is, diffusion in the pn junction forming system 10. When the ultra-thin silicon chip on the substrate is p-type, diffusion with phosphorus as a diffusion source is required to be carried out in the cavity; the ultra-thin silicon wafer on the substrate is n-type, and diffusion with boron as a diffusion source is required in the cavity. Different diffusion types and different diffusion equipment are used, and the diffusion equipment can be in a market model.
In order to prevent the diffusion gas in the fifth chamber e1 from affecting the entire production line and the external environment, the annealed substrate with the very thin silicon wafer is transported from the fourth chamber d1 into the fifth chamber e1 through the fourth buffer passage d3 and the fifth buffer passage e 3. In the fourth chamber d1, the annealed silicon wafers are sequentially loaded onto the fourth transfer mechanism d2 in the fourth buffer channel d3 by the robot d according to the order of the silicon wafers on the annealing support. Automatic valve opening sequence: and a mechanical arm d in the fourth cavity d1 carries silicon wafers, and when the mechanical arm d runs to a set position, the valve G is automatically opened. The robot d puts the substrate on the robot transport d, the robot d withdraws from the fourth buffer path d3, and the valve G is closed. When the fourth conveying mechanism d2 conveys the silicon wafer to the set position sensed by the automatic valve H, the valve H is automatically opened, the silicon wafer enters the fifth buffer channel e3, and the valve H is automatically closed. The fourth buffer passage d3 is closed at this time, and the atmosphere is restored to the same atmosphere as the fourth chamber d1 by gas replacement. When the fifth conveying mechanism e2 conveys the silicon wafer to the set position sensed by the automatic valve J, the manipulator e in the fifth cavity e1 places the silicon wafer in the fifth buffer channel e3 into the fifth cavity e1, and the valve J is automatically closed after the diffusion process. And when the silicon wafers reach the set number, the diffusion equipment starts a diffusion program.
In this embodiment, an n-type silicon wafer is used for boron diffusion. In this example, the conventional boron diffusion process is used for the n-type silicon wafer, and trimethyl borate B (CH3O) is usually used for the liquid source boron diffusion3Tripropylborate and boron tribromide B (Br)3Anhydrous trimethyl borate B (CH3O)3The trimethyl borate is colorless transparent liquid, is formed by volatilization at room temperature, has higher true air pressure, is easy to decompose when meeting water, and is converted into boric acid and methanol. The gaseous boron source is commonly used for boron chloride diffusion, and the solid boron source is commonly used for boron nitride.
The doping element of the n-type silicon wafer material substrate is phosphorus, and boron element needs to be driven into the surface of the silicon wafer to achieve the purpose of forming a pn junction. An n-type silicon wafer is used as a substrate material, and a pyramid texture surface is formed on the surface of the silicon wafer through alkaline corrosion; RCA cleaning and drying are carried out on the surface of the processed silicon wafer; preparing a pn junction on the surface of a silicon wafer, placing the dried n-type silicon wafer in a diffusion furnace tube, controlling the temperature at 850-900 ℃, and depositing a boron source on the surface of the silicon wafer. And (3) when the deposition time reaches a set value, raising the temperature to 900-950 ℃, diffusing boron atoms to the surface of the silicon wafer, wherein the diffusion depth is less than 5 microns, and forming a pn junction. The whole diffusion process is carried out in the environment of nitrogen, oxygen and nitrogen with boron source, and the diffusion pressure is stabilized by nitrogen. The whole diffusion is operated in a closed system, and is nontoxic and pollution-free.
(6) pn junction annealing: and annealing the thin silicon wafer with the pn junction formed to form the silicon wafer.
As shown in fig. 10, this step involves a buffer portion R6, the buffer portion R6 includes a sixth chamber f1, the sixth chamber f1 accommodates therein substrates forming a pn junction, a twelfth sealing valve M (valve M described below) is provided at an inlet end of the sixth chamber f1, the valve M is abutted against the seventh transporting mechanism g2, a thirteenth sealing valve O (valve O described below) is provided at an outlet end of the valve M, and the valve O is connected to the eighth transporting mechanism h 2.
The buffer part R6 mainly functions to take out the silicon wafer with pn junction formed after diffusion, prevent diffusion gas from leaking out, and simultaneously anneal the silicon wafer through the buffer cavity.
To prevent the diffusion gas from leaking, two buffer channels are needed from the fifth chamber e1 to the sixth chamber f1, and the silicon wafer transportation process is similar to that from the fourth chamber d1 to the fifth chamber e1, and will not be described redundantly. Because the silicon wafer diffusion process is carried out in an environment of 850-950 ℃, the temperature of the silicon wafer needs to be reduced to room temperature, and then the process for manufacturing the battery and the assembly is carried out. The silicon wafer is annealed and cooled in the sixth cavity f1 of the buffer cavity. The main method for cooling is to introduce nitrogen for cooling, wherein the flow rate of nitrogen gas is 5-13 l/min, and the cooling rate is 6-15 ℃/min.
In another embodiment, a silicon wafer is provided, which is produced by the method described in the above step.
In another embodiment, a solar cell is provided, wherein the solar cell comprises the silicon wafer, and an antireflection film is arranged on the surface of the silicon wafer.
The invention can easily realize the silicon film with the thickness of less than 50 mu m, and can save more than 80 percent of silicon material theoretically. Under the condition that parameters such as substrate temperature, liquid silicon temperature, throwing speed and the like are different, uniform crystalline silicon with the thickness of 5-5000 microns can be formed.
In the prior art, a polycrystal or monocrystal silicon wafer is required to be subjected to a mechanical process of wire cutting, hard fine scratches are inevitably caused on the surface of the silicon wafer, the structure of a silicon lattice on the surface is damaged, and a critical power generation pn junction is only a few microns. The surface of the invention is naturally grown, and an almost perfect lattice structure can be obtained, which is undoubtedly a positive factor for improving the power generation efficiency. The invention utilizes the auxiliary online measuring means which can be added such as infrared Raman scattering and the like to measure the growth condition and purity estimation of the columnar crystal and implement the processes of melting, crystallization and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not intended to limit the present invention in any way, and all simple modifications, equivalent variations and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.

Claims (10)

1. A method for producing a silicon wafer is characterized in that: comprises the following steps
Manufacturing a thin silicon wafer: fixing a substrate in a closed system, injecting a liquid silicon material onto the substrate, rotating the substrate to enable the liquid silicon material to form a layer of thin film on the substrate, and adding a cold source on the upper surface of the thin film to enable the thin film to be solidified downwards from the surface to form a p-type or n-type crystal thin silicon wafer;
annealing the thin silicon wafer: annealing the thin silicon wafer formed on the substrate;
p-type or n-type diffusion: when the thin silicon wafer on the substrate is of a p type, carrying out diffusion by taking phosphorus as a diffusion source to form a pn junction; when the thin silicon wafer on the substrate is of an n type, carrying out diffusion by taking boron as a diffusion source to form a pn junction;
pn junction annealing: and annealing the substrate thin silicon wafer with the pn junction formed to form a silicon wafer.
2. The method for producing silicon wafers as claimed in claim 1, comprising the steps of, when injecting the liquid silicon material: and (3) placing the solid silicon in a silicon material adding system (7), keeping the temperature of the solid silicon constant, rapidly heating the solid silicon to be higher than the melting point of the silicon material, changing the solid silicon into a liquid silicon material, and injecting the liquid silicon material onto the substrate by the silicon material adding system (7).
3. The method for producing a silicon wafer according to claim 2, wherein in the closed system for producing a thin silicon wafer, the argon pressure range: 40-80 kPa, constant temperature range: 1250-1400 ℃; keeping the constant temperature of the solid silicon by a heating device, wherein the temperature range is as follows: keeping the temperature of 1300-1400 ℃ for 1-5 seconds, and then instantly heating the solid silicon to over 1450 ℃ by another heating device.
4. The silicon wafer production method according to claim 2, wherein a wafer throwing mechanism (8) is arranged in the closed system, a wafer throwing platform (9) is fixed on the wafer throwing mechanism (8), the substrate is fixed on the wafer throwing platform (9), the silicon feeding system (7) is connected with argon gas, the argon gas pushes liquid silicon materials onto the substrate (1), and the wafer throwing mechanism (8) drives the wafer throwing platform (9) to rotate.
5. The silicon wafer production method according to claim 4, wherein the wafer throwing mechanism (8) drives the wafer throwing platform (9) to rotate at a speed which is variable from slow to fast, and the set rotating speed is reached within 1-10 seconds, and the rotating speed range is as follows: 300 to 5000 rpm.
6. The method for producing the silicon wafer according to claim 5, wherein the thin crystal silicon wafer is integrated with the substrate, and the thin crystal silicon wafer is a single crystal silicon wafer or a polycrystalline silicon wafer and has a thickness of several micrometers to several thousands of micrometers.
7. The method for producing a silicon wafer according to claim 6, wherein the crystalline thin silicon wafer is a single crystal silicon wafer which is an extremely thin columnar high mobility thin layer.
8. The method for producing a silicon wafer according to any one of claims 1 to 7, wherein in the annealing of the thin silicon wafer, the argon pressure is in a constant range of: 40-80 kPa, constant temperature range: 1250-1400 ℃; the annealing time range is as follows: the annealing temperature is the lowest temperature of the pn junction formed by diffusion and ranges from 800 ℃ to 1000 ℃ for 0.5-12 hours.
9. A silicon wafer produced by the method according to any one of 1 to 8 above.
10. A solar cell comprising the silicon wafer of claim 9, wherein an anti-reflective film is disposed on the surface of the silicon wafer.
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