CN117393654B - Photovoltaic cell preparation method and photovoltaic cell - Google Patents
Photovoltaic cell preparation method and photovoltaic cell Download PDFInfo
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- CN117393654B CN117393654B CN202311670387.7A CN202311670387A CN117393654B CN 117393654 B CN117393654 B CN 117393654B CN 202311670387 A CN202311670387 A CN 202311670387A CN 117393654 B CN117393654 B CN 117393654B
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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
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/20—Bonding
- B23K26/32—Bonding taking account of the properties of the material involved
- B23K26/324—Bonding taking account of the properties of the material involved involving non-metallic parts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
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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
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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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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- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
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- Photovoltaic Devices (AREA)
Abstract
The invention discloses a photovoltaic cell preparation method and a photovoltaic cell, wherein the photovoltaic cell preparation method comprises the following steps: providing a silicon wafer with a metal electrode; pre-sintering the silicon wafer with the metal electrode, and removing impurities in the metal electrode to obtain a pre-sintered silicon wafer; carrying out laser sintering on the pre-sintered silicon wafer to obtain a laser sintered silicon wafer; and carrying out microwave sintering on the silicon wafer subjected to laser sintering to obtain the photovoltaic cell. According to the invention, the rapid temperature rise of the metal electrode area is realized by utilizing laser sintering, so that ohmic contact between the metal electrode and silicon is improved; the microwave technology is utilized to carry out microwave sintering on the silicon wafer after laser sintering, so that the porosity of the metal electrode can be reduced, the metal electrode is more compact, the pre-sintering time of the silicon wafer with the metal electrode is shortened, the metal electrode is prevented from diffusing to a relatively deep depth at a PN junction, the recombination between the metal electrode and silicon is reduced, and meanwhile, the energy consumption is reduced.
Description
Technical Field
The invention relates to the technical field of photovoltaic, in particular to a photovoltaic cell preparation method and a photovoltaic cell.
Background
The TOPCon (Tunnel Oxide Passivated Contact) technology is to prepare an ultrathin tunneling oxide layer and a high-doped polycrystalline silicon thin layer on the back of the battery, so that carrier selectivity can be realized by blocking minority carrier hole recombination. The chemical passivation of the oxide layer and the field passivation effect of the highly doped polysilicon can further improve the open-circuit voltage and the short-circuit current of the battery, and the conversion efficiency of the battery has a larger improvement space.
The sintering process of the silver paste comprises three stages of drying, burning and sintering. The sintering of positive silver has an optimal sintering point, and the sintering risk exists when the temperature is too high, and the sintering phenomenon exists when the temperature is too low. When the over-firing exists, the silver-silicon mixed layer can cause larger series resistance, and silver paste easily enters a PN junction region to cause partial short circuit, so that the parallel resistance is smaller; when there is an underburn, the silver paste cannot sufficiently penetrate the silicon nitride into the N-type layer, and a good ohmic contact cannot be formed.
At present, the front and back surfaces of a silicon wafer are printed and sintered after a PE battery is usually used, and then annealing is performed, so that organic matters are removed, metallization and ohmic contact are formed through a plurality of temperature areas in the sintering process, but the following problems exist: the relatively long time of heat treatment may not only make the metal and silicon complex more serious, but also make the hydrogen in the silicon nitride dielectric layer enter into the battery matrix more, so the technical problem to be solved in the field is needed.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a photovoltaic cell, which is used to solve the problem that it is difficult to achieve effective heating of a metal electrode in a very short time, and the metal diffuses to a relatively deep depth at a PN junction due to long-time heating.
In a first direction, the present application provides a method for preparing a photovoltaic cell, comprising the steps of:
providing a silicon wafer with a metal electrode;
pre-sintering the silicon wafer with the metal electrode, and removing impurities in the metal electrode to obtain a pre-sintered silicon wafer;
carrying out laser sintering on the pre-sintered silicon wafer to obtain a laser sintered silicon wafer;
and carrying out microwave sintering on the silicon wafer subjected to laser sintering to obtain the photovoltaic cell.
Optionally, the microwave sintering of the silicon wafer after laser sintering includes: and processing the surface layer of the metal electrode in the laser sintered silicon wafer by utilizing a microwave technology.
Optionally, the conditions of the microwave sintering are: the microwave frequency range is 2-20GHz, and the microwave power range is 2-20KW.
Optionally, the microwave temperature range in the microwave sintering is 700-900 ℃, and the time in the microwave sintering is not more than 20s.
Optionally, a deflection voltage is applied at the same time as the laser sintering.
Optionally, the voltage range of the deflection voltage is-10V to-16V.
Optionally, the conditions of the laser sintering are: the laser wavelength range is 310-1064 nm, the laser spot range is 30-200 mu m, and the laser power range is 20-100w.
Optionally, photo-thermal annealing is performed after microwave sintering the laser sintered silicon wafer.
Optionally, the providing the silicon wafer with the metal electrode includes:
preparing the metal electrode on the surface of the silicon wafer by utilizing a screen printing technology; or,
and preparing the metal electrode on the surface of the silicon wafer by utilizing a laser transfer printing technology.
In a second aspect, the present application provides a photovoltaic cell, including a photovoltaic cell prepared by the photovoltaic cell preparation method described above.
Compared with the prior art, the photovoltaic cell preparation method and the photovoltaic cell provided by the invention have the following beneficial effects:
the invention provides a photovoltaic cell preparation method and a photovoltaic cell, wherein the photovoltaic cell preparation method comprises the following steps: firstly, providing a silicon wafer with a metal electrode; and finally, the silicon wafer after laser sintering is subjected to microwave sintering by utilizing a microwave technology, so that the porosity of the metal electrode can be reduced, the metal electrode is denser, the presintering time of the silicon wafer with the metal electrode is shortened, the metal electrode is prevented from diffusing to a relatively deep depth at a PN junction, the recombination between the metal electrode and silicon is reduced, and the energy consumption is reduced.
Of course, it is not necessary for any one product embodying the invention to achieve all of the technical effects described above at the same time.
Other features of the present invention and its advantages will become apparent from the following detailed description of exemplary embodiments of the invention, which proceeds with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
Fig. 1 is a schematic flow chart of a photovoltaic cell manufacturing method provided by the invention;
FIG. 2 is a second schematic flow chart of the method for manufacturing a photovoltaic cell according to the present invention;
fig. 3 is a schematic structural diagram of a photovoltaic cell provided by the invention.
Detailed Description
Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that: the relative arrangement of the components and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless it is specifically stated otherwise.
The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate.
In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of exemplary embodiments may have different values.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further discussion thereof is necessary in subsequent figures.
Fig. 1 is a schematic flow chart of a photovoltaic cell manufacturing method provided by the invention; referring to fig. 1, the present embodiment provides a method for manufacturing a photovoltaic cell, including the steps of:
s1, providing a silicon wafer with a metal electrode;
specifically, the silicon wafer can be a semi-finished silicon wafer, the silicon wafer can be an N-type silicon wafer or a P-type silicon wafer, the metal electrode can be one of a silver electrode, a copper electrode, a gold electrode and a silver aluminum electrode, the metal electrode is arranged on the silicon wafer and can be positioned on the front surface and the back surface of the silicon wafer or can be positioned on the back surface of the silicon wafer, the metal electrode comprises a main grid line and a thin grid line, the main grid line is intersected with the thin grid line, optionally, the thin grid line can be mutually perpendicular to the main grid line, the thin grid line is electrically connected with the main grid line, and the main grid line is used for collecting current of the thin grid line; alternatively, the metal electrode is not provided with a main grid line, and includes only a plurality of thin grid lines, and the main grid line is replaced with a bonding wire, which is not limited thereto.
S2, pre-sintering the silicon wafer with the metal electrode, and removing impurities in the metal electrode to obtain a pre-sintered silicon wafer;
specifically, the metal electrode can be one of a silver electrode, a copper electrode, a gold electrode and a silver-aluminum electrode, and the silver electrode is exemplified by the silver electrode, wherein the main component of the silver electrode consists of silver powder, glass oxide (or resin) and organic matters, and the silver powder can be high-purity silver powder, and the silver content in the high-purity silver powder is not less than 99.99%; glass powder can be selected as glass oxide, and is scratch-resistant high-transparency powder with small particle size, good dispersibility, high transparency and good anti-sinking effect; the surface is improved, the crystal transparent primer has good affinity, strong steric hindrance, and can be conveniently dispersed in the paint, the fullness of the paint can be increased after the film is formed, and the prepared crystal transparent primer not only keeps clear transparency, but also provides good scratch resistance; the resin containing polar groups and having an affinity for silver powder is selected from at least one of hydroxy acrylic resin, polyvinylpyrrolidone, polyvinyl butyral, aldehyde ketone resin and ethyl cellulose resin; typical organics may be involved in: the organic carrier and the solvent are at least one selected from alcohol ester-12, butyl carbitol acetate, dimethyl adipate, dimethyl glutarate, ethylene glycol phenyl ether and tributyl citrate.
The presintering is carried out in a traditional sintering furnace, and the traditional sintering furnace is divided into a presintering stage, a sintering stage and a cooling stage. The presintering stage aims at melting and removing impurities in a metal electrode (such as a silver electrode) through high-temperature treatment so as to obtain a metallized surface, wherein the impurities in the metal electrode (such as the silver electrode) can be organic matters, the temperature of the stage is slowly increased, the temperature range of the presintering stage is 300-350 ℃, the melting point of the organic matters is generally lower than 350 ℃, and the organic matters volatilize at a higher temperature; in the sintering stage, various physicochemical reactions are completed in the sintering body to form a resistor film structure, so that the resistor film structure really has the resistance characteristic, the temperature reaches a peak value in the stage, the peak value temperature range is 670-720 ℃, when the peak value is set too high, the accumulated heat processing time of the metal electrode is long, the probability of diffusion of the metal electrode into the interior is increased, and when the peak value is set too low, the resistor film structure is not beneficial to being formed, therefore, the peak value temperature range is set between 670-720 ℃, the accumulated heat processing of the metal electrode can be shortened, the probability of diffusion of the metal electrode into the interior is reduced, and the resistor film structure is beneficial to being formed; and in the cooling stage, the glass oxide is cooled, hardened and solidified, so that the resistor film structure is fixedly adhered to the substrate.
It should be noted that: the peak temperature in the conventional sintering furnace ranges from 700 ℃ to 750 ℃, and in the embodiment, the peak temperature ranges from 670 ℃ to 720 ℃, and the peak temperature is lower than that in the common sintering furnace, so that the power consumption of the sintering furnace can be greatly reduced.
S3, carrying out laser sintering on the pre-sintered silicon wafer to obtain a laser sintered silicon wafer;
specifically, the pre-sintered silicon wafer is scanned by laser to increase ohmic contact between the metal electrode and silicon (such as polysilicon), for example, the metal electrode (front metal electrode and back metal electrode, or back metal electrode) on the pre-sintered silicon wafer is irradiated by a low-power picosecond laser beam to scan, so that the metal electrode (front metal electrode and back metal electrode, or only back metal electrode) is sintered, and the metal electrode (silver electrode) and the silicon (such as polysilicon) are mutually diffused, and a silver-silicon alloy is formed between the metal electrode and the silicon (such as polysilicon) after cooling, so as to obtain the silicon wafer after laser sintering.
And S4, carrying out microwave sintering on the silicon wafer subjected to laser sintering to obtain the photovoltaic cell.
Specifically, microwave equipment is used for microwave sintering of the laser sintered silicon wafer, and microwaves refer to electromagnetic waves with the frequency of 300MHz-3000GHz, and are short for one limited frequency band in radio waves. Typically the wavelength of the microwaves is relatively long, highly transmissive for silicon materials, which are not prone to heating. In addition, as the microwave has stronger penetrating power, the microwave can penetrate into the silicon wafer after laser sintering, firstly, the center temperature of the silicon wafer after laser sintering is rapidly increased to reach the ignition point and combustion synthesis is initiated, and the sintering wave is spread from inside to outside along the radial direction, so that the whole silicon wafer after laser sintering can be almost uniformly heated. The metal electrode is made denser by the skin effect of microwave technology. The model of the microwave device may be ZY-GW-6HM.
The energy absorption of the metal electrode is related to the frequency of the microwave radiation, the conductivity of the metal electrode and the polarization mode of the radiation. In general, highly conductive metal electrodes (e.g., silver electrodes) generally absorb microwave energy more effectively than less conductive metal electrodes (copper and aluminum electrodes).
The embodiment comprises the steps of pre-sintering in a traditional sintering furnace, performing laser sintering by using laser after the pre-sintering is finished to obtain a laser sintered silicon wafer, performing microwave sintering on the laser sintered silicon wafer, and performing densification of a metal electrode by using a skin effect of a microwave technology in metal, wherein the laser sintering and the microwave sintering can be performed on a metal electrode area in a very short time, for example, the laser sintering can be used for realizing rapid temperature rise of the metal electrode area, thereby improving ohmic contact between the metal electrode and silicon (such as polysilicon), simultaneously avoiding damaging a passivation (such as silicon nitride dielectric layer) structure and preventing hydrogen in the silicon nitride dielectric layer from entering the pre-sintered silicon wafer; the porosity of the metal electrode can be reduced by utilizing microwave sintering, so that the compactness of the metal electrode is improved, and the time for pre-sintering a silicon wafer with the metal electrode is shortened, so that the metal electrode is prevented from diffusing to a relatively deep depth at a PN junction, the recombination between the metal electrode and silicon is reduced, and the energy consumption is reduced. In addition, since the laser sintering and the microwave sintering are sequentially performed in the embodiment, the peak value in the traditional sintering furnace is set at 670-720 ℃, the peak value is not required to be set at 721-750 ℃, and the power consumption of the traditional sintering furnace can be reduced. In the scheme, the presintering, the laser sintering and the microwave sintering are mutually related, the execution sequence is irreversible, and the technical effects cannot be realized after the splitting.
Compared with the prior art, the photovoltaic cell preparation method provided by the embodiment at least has the following beneficial effects:
the preparation method of the photovoltaic cell provided by the embodiment comprises the steps of firstly providing a silicon wafer with a metal electrode; and finally, the silicon wafer after laser sintering is subjected to microwave sintering by utilizing a microwave technology, so that the porosity of the metal electrode can be reduced, the metal electrode is denser, the presintering time of the silicon wafer with the metal electrode is shortened, the metal electrode is prevented from diffusing to a relatively deep depth at a PN junction, the recombination between the metal electrode and silicon is reduced, and the energy consumption is reduced.
In an alternative embodiment, microwave sintering the laser sintered silicon wafer comprises: and processing the surface layer of the metal electrode in the laser sintered silicon wafer by utilizing a microwave technology.
Specifically, induction heating is a method of generating a high-frequency alternating electromagnetic field by a transformer, and generating an induction current to a metal electrode to heat. The induction heating has the advantages of rapid heating, production efficiency improvement and the like. It should be noted that: the microwave technology is only suitable for materials of metal electrodes with strong conductivity. Microwave technology also has the ability to rapidly heat metal particles. In general, as the frequency of the microwaves increases, the skin effect becomes shallower, and the surface layer of the metal electrode can be heat-treated with the high-frequency microwaves.
The penetration depth (skin depth) of microwaves is an important parameter of the interaction of microwaves with a substance and can be defined as the depth at which the field strength of the microwaves decays to 1/e (36.8%) of the field strength at the surface of the metallic material. The calculation formula for deducing the penetration depth of the microwave in the metal according to Maxwell's equation is shown as formula (1): （1）
in the above formula, delta is the penetration depth of microwaves, pi is the circumference rate, ƒ is the microwave frequency, sigma is the conductivity, mu is the magnetic permeability, rho is the resistivity of the material, and lambda is 0 Is the wavelength of the microwaves (0.12 m for a microwave field wavelength of 2.45 GHz).
From the above formula: the higher the microwave frequency, the shorter the wavelength, and the shallower the corresponding penetration depth. The penetration depth of the common metal material in the microwave with the frequency of 2.45GHz is about 2.7 μm for copper, about 2.5 μm for nickel, about 1.3 μm for iron and about 1 μm for silver, so that the penetration depths of the different metal materials are slightly different.
The metal electrode in the silicon wafer after laser sintering is influenced by the microwave skin effect, so that micro-melting of the surface layer in the metal electrode can be promoted, the pores in the metal electrode can be reduced, and the skin effect is shallower as the microwave frequency is higher.
The thickness of the conventional metal electrode is 8 mu m, and the surface layer in the metal electrode is subjected to heat treatment by adopting high-frequency microwaves, so that the whole metal electrode is prevented from being overhigh in temperature, and the metal electrode is prevented from continuing to diffuse to the PN junction or the silicon substrate of the battery. Alternatively, the surface layer thickness in the metal electrode may range from 1 μm to 2 μm, such as 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, or 2.0 μm.
In an alternative embodiment, the conditions for microwave sintering are: the microwave frequency ranges from 2GHz to 20GHz, and the microwave power ranges from 2KW to 20KW.
Specifically, when the microwave frequency is lower than 2GHz, the penetration depth of the metal electrode is too deep, so that the temperature rise of the metal electrode in a short time is not facilitated, the diffusion of the metal electrode and the PN junction region is possibly increased, and if the metal electrode is continuously diffused, the risk of overburning is brought; when the microwave power is higher than 20GHz, the frequency is too high, the penetration depth of the metal electrode becomes shallow, only the surface layer of the metal electrode can be processed, so that heat is easy to concentrate on the surface of the metal electrode, and the risk of oxidization of the metal electrode is caused, therefore, the microwave frequency range is limited to 2GHz-20GHz, the penetration depth of the metal electrode can be prevented from being too deep, the temperature rise of the metal electrode in a short time is facilitated, the diffusion of the metal electrode and a PN junction region can be reduced, and meanwhile, the risk of overheating caused by continuous diffusion of the metal electrode is avoided. Specifically, the microwave frequency may be 2GHz, 4GHz, 8GHz, 12GHz, 16GHz or 20GHz.
The microwave power is too low or too high, so that the internal temperature rising phenomenon of the metal electrode can be influenced, and the risk of overburning of the metal electrode exists, so that the PN junction of the battery is damaged, and therefore the microwave power is in the range of 2KW-20KW, the temperature rising of the metal electrode in a short time is facilitated, the risk of overburning of the metal electrode is avoided, and the PN junction of the battery is prevented from being damaged. In particular, the microwave power may be 2KW, 5KW, 10KW, 15KW or 20KW.
The microwave power and the microwave frequency are related to the heating time in microwave sintering.
In an alternative embodiment, the microwave temperature range in the microwave sintering is 700-900 ℃ and the time in the microwave sintering is not more than 20s.
Specifically, the sintering temperature of the metal powder is usually 1000-1200 ℃, and the metal powder is not suitable for densification of the metal electrode in the photovoltaic cell, and the metal electrode can be controlled to 700-900 ℃ by utilizing microwave radiation heating, so that the densification of the metal electrode in the photovoltaic cell is facilitated. When the time in microwave sintering exceeds 20s, the time is long, which means that the productivity is reduced, and the temperature is raised integrally to influence the cooling rate, so that the time in microwave sintering is not more than 20s, the productivity can be improved, and the excessive interference to the cooling curve is avoided.
In an alternative embodiment, the deflection voltage is applied while laser sintering is performed.
Specifically, first, a battery piece is irradiated by a low-power picosecond laser beam to form an induction carrier, and a local current is formed by combining deflection voltage; the preferential path of the local current is positioned between the emitter below the metal electrode and the metal electrode (such as a silver electrode) and forms high current density; secondly, the high current density causes heating points, sintering occurs at the corresponding positions, and interdiffusion of silver and silicon is caused; finally, the cooling process. The heating time caused by the current is between microseconds and milliseconds, and mainly depends on the service life of the carriers, the temperature near the melting point is rapidly reduced, and the metal electrode (silver electrode) and the silicon form a silver-silicon alloy.
In an alternative embodiment, the deflection voltage is in the range of-10V to-16V.
Specifically, the deflection voltage determines the temperature of local contact between the metal electrode and silicon, when the voltage in the deflection voltage is greater than-10V, the higher the negative bias voltage is, the more local heating between the metal electrode and silicon (polysilicon) is, so that the diffusion depth of the metal electrode is increased, the deeper the metal electrode enters a PN junction or a silicon substrate, and the open-circuit voltage of a photovoltaic cell is further reduced; when the voltage in the deflection voltage is smaller than-16V, the local temperature is lower, and effective silver-silicon alloy is difficult to form, so that the voltage range in the deflection voltage is designed to be-10V to-16V, the negative bias voltage is prevented from being too high, the local heating between the metal electrode and silicon is prevented from being serious, the diffusion depth of the metal electrode is reduced, the open-circuit voltage of a photovoltaic cell is reduced, the local temperature between the metal electrode and silicon can be increased, and the effective silver-silicon alloy is formed. Specifically, the voltage in the deflection voltage may be-10V, -11V, -12V, -13V, -14V, -15V or-16V.
In an alternative embodiment, the conditions for laser sintering are: the laser wavelength range is 310 nm-1064 nm, the laser spot range is 30-200 mu m, and the laser power range is 20-100w.
Specifically, the size of the laser spot is usually designed by combining the metal electrode interval in the pre-sintered silicon wafer, and when the laser spot is smaller than 30 mu m and the laser power is lower than 20w, the productivity can be influenced; when the laser light spot is larger than 200 μm and the laser power is larger than 100w, the metal electrode may burn through the pre-sintered silicon wafer, so that the laser light spot range is designed to be 30-200 μm and the laser power range is designed to be 20-100w, not only can the productivity be improved, but also the metal electrode is prevented from burning through the pre-sintered silicon wafer, specifically, the laser light spot can be 30 μm, 60 μm, 90 μm, 120 μm, 150 μm, 180 μm or 200 μm, and the laser power can be 20w, 40w, 60w, 80w or 100w.
By way of example, assuming a laser power of 40W if the laser spot is 120 μm, 6000 pre-sintered battery plates can be processed per hour; if the laser spot is 200 micrometers and the laser power is 100W, 9000 pre-sintered battery plates can be processed per hour.
It should be noted that: the laser energy does not damage the passivation dielectric layers on the surface of the presintered battery piece, such as dielectric layers of silicon oxide, aluminum oxide and the like.
Table 1 conditions and corresponding photovoltaic cell electrical parameters are referred to in comparative examples and examples
It should be noted that: (1) In table 1, the corresponding example 1 is only conventional sintering, and the comparative example 2 is conventional sintering and laser-assisted sintering; the examples are conventional sintering, laser-assisted sintering and microwave-assisted sintering in this example; (2) Condition 1 is deflection voltage, condition 2 is laser condition, condition 3 is microwave power, condition 4 is microwave frequency, condition 5 is microwave temperature; (3) U (U) oc Is open circuit voltage, I sc Is short-circuit current, FF is fill factor, E ta Is photoelectric conversion efficiency.
From the results in Table 1, it can be derived that: compared with the sintering condition provided in comparative example 2, the sintering condition provided in this example has the advantages that the laser wavelength is 355nm, the spot size is equal to the main grid line spacing, the laser power is 20W, the microwave power is 2kW, the microwave frequency is 2GHz, the microwave temperature is 700 ℃, the corresponding filling factor FF is improved by 0.2-0.4 compared with that of comparative example 2, and the corresponding photoelectric conversion effect is achievedRate E ta Lifting by 0.06-0.162 compared with comparative example 2; aiming at the laser wavelength of 960nm, the spot size and the main grid line distance, the laser power is 100W, the microwave power is 20kW, the microwave frequency is 20GHz, the microwave temperature is 900 ℃, the corresponding filling factor FF is improved by 0.2-0.4 compared with that of comparative example 2, and the corresponding photoelectric conversion efficiency E is improved ta The improvement is 0.202-0.381 compared with the comparison example 2; aiming at the laser wavelength of 532nm, the spot size and the main grid line distance, the laser power is 60W, the microwave power is 11kW, the microwave frequency is 11GHz, and the filling factor and the photoelectric conversion efficiency are obviously improved when the microwave temperature is 800 ℃, which is not listed here.
It should be noted that: the wavelength of the current mass production common laser can be 355nm, 532nm or 1064nm.
In an alternative embodiment, fig. 2 is a second schematic flow chart of the method for manufacturing a photovoltaic cell according to the present invention; referring to fig. 2, a laser-sintered silicon wafer is subjected to microwave sintering and then to photo-thermal annealing.
Specifically, as shown in fig. 2, the surface defects of the photovoltaic cell, the defects inside the photovoltaic cell and the metallized ohmic contact portions after microwave sintering are repaired by exciting hydrogen in combination with a photo-thermal annealing process. Specifically, the anti-reflection layer (such as silicon nitride) in the photovoltaic cell comprises a silicon hydrogen bond and a nitrogen hydrogen bond. Under the high temperature condition, the silicon hydrogen bond and the nitrogen hydrogen bond are broken, and hydrogen is rapidly diffused in silicon. By adjusting irradiance and raising temperature, hydrogen permeated into the silicon body is combined with the unbalanced carrier to generate hydrogen with different charge states, so that passivation of the hydrogen and most impurities or defects is realized. For example, ag-H bonds are formed, so that not only can the metal-semiconductor contact be improved, but also the contact resistance can be reduced, the filling factor of the photovoltaic cell can be improved, and the conversion efficiency of the cell can be further improved.
In an alternative embodiment, providing a silicon wafer having a metal electrode includes:
preparing a metal electrode on the surface of a silicon wafer by utilizing a screen printing technology; or preparing a metal electrode on the surface of the silicon wafer by utilizing a laser transfer printing technology.
Specifically, printing slurry on the surface of the silicon wafer by utilizing a screen printing technology to obtain a metal electrode, specifically, printing metal slurry on the front surface and the back surface of the silicon wafer by utilizing the screen printing technology to prepare a silicon wafer metal electrode, sintering the metal slurry to form a front electrode on the front surface of the silicon wafer and a back electrode on the back surface of the silicon wafer, wherein the front electrode and the back electrode are used for collecting and conveying current of a photovoltaic cell.
And (3) printing slurry on the surface of the silicon wafer by using a laser transfer printing technology to obtain the metal electrode. Specifically, laser grooving can be performed on the front and back surfaces of the silicon wafer by using a laser device; and printing sizing agent on the front surface and/or the back surface by utilizing a laser transfer printing technology to form a front electrode and/or a back electrode, wherein the front electrode and the back electrode are used for collecting and conveying current of the photovoltaic cell.
Fig. 3 is a schematic structural diagram of a photovoltaic cell provided by the present invention, and referring to fig. 3, this embodiment provides a photovoltaic cell including a photovoltaic cell prepared by the above photovoltaic cell preparation method.
Specifically, the photovoltaic cell comprises the photovoltaic cell prepared by the photovoltaic cell preparation method, the photovoltaic cell can be a TOPCon cell, the TOPCon cell comprises a silicon substrate 1, a front electrode 2 and a back electrode 3, the silicon substrate 1 can be an N-type silicon substrate, and the front electrode 2 and the back electrode 3 can be metals such as silver, aluminum, copper or nickel;
one surface of the silicon substrate 1 is sequentially laminated with a tunneling oxide layer 4, a polycrystalline silicon layer 5 and a first passivation layer 6 along the direction far away from the silicon substrate 1, and the back electrode 3 penetrates through the first passivation layer 6 and is electrically connected with the polycrystalline silicon layer 5; the tunneling oxide layer 4 can enable multi-electron tunneling to enter the polycrystalline silicon layer 5, meanwhile, minority carrier hole recombination is blocked, electrons are further transmitted transversely in the polycrystalline silicon layer 5 and are collected by metal, the recombination rate is greatly reduced, the open-circuit voltage and the short-circuit current of the battery are improved, and therefore the conversion efficiency of the battery is improved;
the silicon substrate 1 comprises a base region 11 and an emitter electrode 12, the emitter electrode 12 is positioned on one side of the base region 11 far away from the tunneling oxide layer 4, and a second passivation layer 7 is arranged on one side of the emitter electrode 12 far away from the base region 11; the front electrode 2 is electrically connected to the emitter electrode 12 through the second passivation layer 7.
According to the embodiment, the photovoltaic cell preparation method and the photovoltaic cell provided by the invention have the following beneficial effects:
the invention provides a photovoltaic cell preparation method and a photovoltaic cell, wherein the photovoltaic cell preparation method comprises the following steps: firstly, providing a silicon wafer with a metal electrode; and finally, the silicon wafer after laser sintering is subjected to microwave sintering by utilizing a microwave technology, so that the porosity of the metal electrode can be reduced, the metal electrode is denser, the presintering time of the silicon wafer with the metal electrode is shortened, the metal electrode is prevented from diffusing to a relatively deep depth at a PN junction, the recombination between the metal electrode and silicon is reduced, and the energy consumption is reduced.
While certain specific embodiments of the invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (7)
1. A method of manufacturing a photovoltaic cell, comprising the steps of:
providing a silicon wafer with a metal electrode;
pre-sintering the silicon wafer with the metal electrode, removing impurities in the metal electrode, and obtaining a pre-sintered silicon wafer, wherein the peak temperature in the pre-sintering is lower than that in a common sintering furnace;
carrying out laser sintering on the pre-sintered silicon wafer to obtain a laser sintered silicon wafer;
and carrying out microwave sintering on the silicon wafer after laser sintering, wherein the microwave sintering comprises the following steps: treating the surface layer of a metal electrode in the laser sintered silicon wafer by utilizing a microwave technology to obtain a photovoltaic cell, wherein the photovoltaic cell is TOPCO;
the conditions of the microwave sintering are as follows: the microwave frequency range is 2-20GHz, the microwave power range is 2-20KW, the microwave temperature range in microwave sintering is 700-900 ℃, and the time in microwave sintering is not more than 20s.
2. The method of manufacturing a photovoltaic cell according to claim 1, characterized in that a deflection voltage is applied at the same time as the laser sintering.
3. The method for manufacturing a photovoltaic cell according to claim 2, wherein the deflection voltage is in a voltage range of-10V to-16V.
4. The method of claim 1, wherein the laser sintering conditions are: the laser wavelength range is 310-1064 nm, the laser spot range is 30-200 mu m, and the laser power range is 20-100w.
5. The method of claim 1, wherein the laser sintered silicon wafer is subjected to a microwave sintering followed by a photo-thermal annealing.
6. The method of claim 1, wherein providing a silicon wafer having a metal electrode comprises:
preparing the metal electrode on the surface of the silicon wafer by utilizing a screen printing technology; or,
and preparing the metal electrode on the surface of the silicon wafer by utilizing a laser transfer printing technology.
7. A photovoltaic cell comprising a photovoltaic cell prepared by the photovoltaic cell preparation method of any of claims 1-6.
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