CN101241952A - Solar battery slice technology for efficient and low-cost film crystal silicon - Google Patents
Solar battery slice technology for efficient and low-cost film crystal silicon Download PDFInfo
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- CN101241952A CN101241952A CNA2007100636430A CN200710063643A CN101241952A CN 101241952 A CN101241952 A CN 101241952A CN A2007100636430 A CNA2007100636430 A CN A2007100636430A CN 200710063643 A CN200710063643 A CN 200710063643A CN 101241952 A CN101241952 A CN 101241952A
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Abstract
The present invention is a technique for manufacturing a crystalline silicon solar cell piece, especially a technique for manufacturing a high-efficiency, low cost and thin-sheet solar cell piece, and the invention belongs to the solar energy application field. The technique aims at the thin-sheet crystal silicon chip with thickness less than 200 mu m, by adopting innovated technique and developing the original technique, combines the domestic cell whole equipment which is independently developed, settles the contradiction between the thin sheet and the fraction ratio, finished product rate and the electrical property, and satisfies the request of the cell piece product line to the high efficiency and low cost. The technique for manufacturing crystal silicon solar cell piece is subdivided to seven steps according to the process flow: eliminating the injury and coarsen the surface, diffusing to make a knot, plasma etching for eliminating the edge, PSG eliminating, PECVD depositing Si3N4 film, printing positive back electrode slurry and back field slurry on the silk screen, and co-baking to form an ohm contact. When the technique is adopted for the size 125*125mm<2>, the efficiency of the single crystalline silicon solar cell piece is up to 16.5, and the efficiency of the polycrystalline silicon solar cell is up to 15.0%.
Description
Technical field:
The present invention is a kind of crystalline silicon solar cell piece manufacturing process, and particularly a kind of manufacturing process of efficient, low-cost, wafer solar cell sheet belongs to the Application of Solar Energy field.
Background technology:
In the crystal-silicon solar cell commercialization process, never stopped with the work that reduces manufacturing cost over more than 20 year for improving efficiency of solar cell.In recent years along with the rapid expansion of solar energy industry, raw-material unbalanced supply-demand causes the price of solar level silicon materials to soar all the way, the thickness of silicon chip drops to below the 200 μ m from 320 μ m, 270 μ m, 230 μ m, 220 μ m always, sheet is a handle double-edged sword, thin slice can reduce cost, but fragment rate can increase, and adopts traditional handicraft, and the electrical property of battery sheet, appearance property all are difficult to guarantee.Therefore, technical processs such as matte preparation, diffusion, silk-screen printing technique must be reformed, innovate traditional handicraft, as control of the selection of the accurate control of making herbs into wool process loss of weight amount, slurry and modulation, battery sheet angularity etc.
In patent documentation, have a lot about the manufacturing process of crystal-silicon solar cell, but the thin slice solar cell piece is related to seldom, and be research basically single technical process, all be to be support, adaptability and the range of application of himself arranged with specific technical equipment.
My company relies on the whole line equipment of the solar battery sheet production of independent research, at the thin crystalline silicon sheet, works out battery sheet manufacture process, and a kind of high efficiency, low cost thin slice solar cell technology is provided, and success be applied to commercialization large-scale production.
Summary of the invention
The present invention be directed to thickness and be lower than 200 μ m thin slice crystal silicon chips, overcome the deficiencies in the prior art point, by adopt innovative technology, with original technological innovation, in conjunction with whole traditional thread binding being equipped with of homemade battery of independent development, development and Design each operation production technology of adapting of one cover and the specification of equipment of itself and requirement, solved the contradiction between thin slice and fragment rate, rate of finished products, the electrical property preferably, satisfied the battery slice assembly line to battery efficiency, cost requirement, characteristics such as the battery sheet of being produced has efficiently, low cost, electrical property is good, presentation quality is superior.Established technical foundation for the production domesticization of solar cell production equipment with it as crystal silicon cell sheet gauge modulus product that equipment supports.
The present invention is achieved through the following technical solutions:
It was seven steps that technology is subdivided into by public process flow: go damage and surperficial matteization, diffusion system knot, plasma etching trimming, PSG removal, PECVD to deposit Si
3N
4Film, the positive backplate slurry of silk screen printing and back-surface-field (BSF) paste, the common burning form ohmic contact.This technology is simplified with loss of weight the suede process and is accurately controlled, and adopts stopped pipe diffusion furnace diffusion system knot to guarantee diffusion uniformity and consistencyization, and PECVD deposits Si
3N
4Film carries out passivation to defective in interface and the body, to printed pattern optimization, mixes use with different slurries and improves electrical property and presentation quality, and the utility model also is optimized sintering temperature.
Below be described in detail as follows to each technical process of the present invention:
1. damage and surperficial matteization
The most of mixed solution that adopts alkali and isopropyl alcohol of monocrystalline silicon process for etching in research at home and abroad and the production, this technology and the different of traditional handicraft are, use the relatively low ethanol of price to replace isopropyl alcohol, form Woolen-making liquid, reduced cost with the aqueous solution of NaOH.Adopt 0.5-3 Ω .cm, P type (100) crystal orientation, concentration sodium hydroxide: 10g/L, concentration of ethanol 5%-10% reacted 25 minutes down at 85 ℃, just can be formed into cuclear density height, matte of uniform size at monocrystalline silicon surface.In addition, this technology with the traditional handicraft process go damage and two of making herbs into wool independently process and go on foot one finish, the process of having simplified has reduced cost.Use by titration technique realizes chatting in the scope in the more accurate control of solution concentration, guarantee to go to damage with making herbs into wool after wafer thinning at 20um-25um, taken into account many-sided problems such as production efficiency, reflectivity and following process process.
2. diffusion system knot
Adopt the POCl of 7N
3Liquid source is by N
2The mode of carrying enters diffusion furnace; diffusion furnace adopts independent development M5111-4W/UMX type stopped pipe diffusion furnace; the effective internal diameter φ of burner hearth 300mm; " silicon chip technology; the high-grade temperature controller of import that has from adjusting PID regulating system, 0.1 class precision and having multinomial defencive function is partly selected in temperature control for use, thereby the temperature-controlled precision height, and temperature stability is good; the heating-cooling response speed is fast is controlled automatically with computer communication realization temperature rate simultaneously to be applicable to 4-8.Technological parameter: 840 ℃-890 ℃ of diffusion temperatures, advance stove: 5-8min, big nitrogen 18L/min; Rise again: 10-20min, big nitrogen 18L/min, dried oxygen 0.8-1.8L/min; Diffusion: 30-40min, big nitrogen 18L/min, dried oxygen 0.5-1.5L/min, little nitrogen 0.5-1.5L/min; Advance: 8-10min, big nitrogen 18L/min, dried oxygen 0.5-1.5L/min; Come out of the stove: 5-8min, big nitrogen 18L/min.
Every groove is put two silicon chips during diffusion, and 400/pipe, compare with traditional open pipe diffusion, reduced POCl greatly
3Liquid source, N
2, dried oxygen consumption, improved production efficiency, effectively reduced the exhaust gas discharging amount, saved cost, reduced energy consumption, and environmental protection more.
2. ion etching trimming
With carbon tetrafluoride and oxygen is working gas, adopts independently the M42200-1/UM of the exploitation " plasma etching machine of silicon chip technology that is applicable to 4-8.The volume ratio of carbon tetrafluoride and oxygen 1: 10, the high frequency power of 500W, the PN junction of 10 minutes removal silicon chips periphery.
3.PSG remove
The secondary cleaning purpose is to remove the phosphorosilicate glass that is produced in the diffusion process, for subsequent P ECVD silicon nitride film, silk screen printing, sintering are got ready.
4.PECVD deposition Si
3N
4The passivation of film surface of silicon solar cell is to improve one of efficient ways of its conversion efficiency, because the silicon nitride film that generates contains a large amount of hydrogen, dislocation, surperficial dangling bonds in can well passivation silicon, thereby improved carrier mobility in the silicon chip, improve about 20%, simultaneously because the SiN film has very obviously passivation to monocrystalline silicon surface.Be higher than traditional as the single crystal silicon solar cell efficient of antireflective film with PECVD SiN by APCVD TiO
2As the antireflective film single crystal silicon solar cell.Adopt two pipe PECVD of independent research, the passivation of 168/pipe: the silicon chip after will cleaning is put into the PECVD vacuum chamber after inserting graphite boat, vacuumize, and begin to be warming up to 400 ℃, after the reative cell vacuum reaches 15Pa, temperature and reaches 400 ℃, in reative cell, feed flow 3500ml/min NH
3Gas remains on about 200Pa the reative cell vacuum, is 1400W and unlatching with the high frequency electric source power setting, allows silicon chip close high frequency electric source after the clock time in 5 minutes in the reative cell discharge, cuts off NH
3Gas.This process realizes defective in crystal boundary, point defect material surfaces such as (room, interstitial atom, metal impurities, oxygen, nitrogen and their compounds) and the body is carried out passivation, dangling bonds in saturated surface and the body, the minority carrier that reduces in surface and the body is caught probability, thereby improves its life-span.
Deposition: after the passivation, in reative cell, feed the SiH of flow 245ml/min
4The NH of gas and 2800ml/min
3Gas, and make the reative cell vacuum remain on 1～2 fen clock time about 265pa, and purpose is to allow gas be consistent in reative cell everywhere, high frequency electric source is set to 1500W and opens then, allow silicon chip after reative cell discharged 2 minutes, stop high-frequency discharge, cut off gas and feed, residual gas in reaction chamber is drained only, find time after charging into nitrogen again, after 3 times, just silicon chip can be taken out from reative cell repeatedly, deposition step is finished.
Gas flow ratio, sedimentation time, high frequency electric source power, reaction chamber temperature, chamber pressure are important parameter, are used, and prepare optimum SiN antireflective coating.
5. silk screen printing
For the ohmic contact that electrode and silicon face are formed, by the formed surface n of phosphorous diffusion-section bar material doping content is higher.High-concentration dopant reduces the minority carrier lifetime in the material, makes photo-generated carrier not collected effectively.And short wavelength's sunlight is absorbed by this layer of material, so the energy of these sunlights can not well be utilized, and forms so-called " dead layer ".
Starch the top electrode printing for the phosphorous silver of this this process using, cooperate the shallow junction diffusion, so both guaranteed good Ohmic contact, improve carrier lifetime simultaneously, the shortwave effect is good, thereby has improved efficient.
Be subjected to the silk screen technology limitation, it is very narrow that the metal electrode of front surface can not be done, thereby blocked the effective absorption of light in silicon chip.Because chat mixed slurry on adopting, the resistivity under the gate line electrode is starkly lower than white space, has reduced ohmic contact.
The resistivity that depends on silicon chip, design main grid line, thin grid line size and grating spacing make the theoretical coverage area 4-6% (actual printing area coverage is 6-8%) of front electrode, have reduced shielded area, have improved short circuit current.
Front electrode adopts phosphorous silver medal, back electrode to adopt silver-colored aluminium paste.
A back of the body employing mixes aluminium paste, has reduced cost.Burn till the about 25 μ m of thickness, by the thickness of accurate control silk screen printing, the angularity index when making thin slice is in diagonal 1%.
The conversion efficiency of the monocrystaline silicon solar cell of this explained hereafter is between 15.5%-16.5%, and the conversion efficiency of polycrystal silicon cell is between 14%-15.0%.
6. burn altogether and form ohmic contact
Adopt the spike net strip sintering furnace of independent research, the heating of infrared heating fluorescent tube, 0.1 class precision and the high-grade temperature controller temperature control of import with multinomial defencive function.Each warm area is accurately controlled, and response speed is fast.
Traditional handicraft will could form the good metal electrode ohmic contact that has with double sintering, co-firing technology only needs once sintered, form the ohmic contact of upper/lower electrode simultaneously, be an important critical process of high-efficiency crystal silicon solar cell, the external famous metal paste manufacturer co-firing technology of exerting all one's strength very much to promote.Electrode metal material and single crystal silicon semiconductor are when temperature reaches eutectic temperature, and the monocrystalline silicon atom is measured in certain proportion in the alloy electrode material that is added to fusion by phasor and gone.The monocrystalline silicon atom number that dissolves in is decided by the volume of alloy temperature and electrode material, and the sintered alloy temperature is higher, and the electrode metal material volume is bigger, the silicon atom number that then dissolves in also the more, at this moment state is called as the alloy system of crystalline electrode metal.If this moment, temperature reduced, system begins to cool down, and at this moment the silicon atom that originally was added in the electrode metal material crystallizes out with solid-state form again, just grows one deck epitaxial loayer on metal and crystal contact interface.Recrystallized layer contains q.s and impurity composition original crystalline material conduction type abnormal shape, this has just obtained to form the P-N knot with alloyage technology, the back side at battery forms electric field, improve the open-circuit voltage values of crystal silicon cell, a good aluminium back of the body gettering effect in addition, the defective of being introduced in the operation pyroprocess of front is eliminated, improved minority carrier life time.Printed the silicon chip of silver slurry, silver-colored aluminium paste, aluminium paste, and volatilized fully by the oven dry organic solvent, rete shrinks becomes the decorating film tight adhesion on silicon chip, at this moment, can be considered metal electrode material layer and silicon chip and contacts.Co-firing technology is the eutectic temperature that adopts silver-silicon, aluminium-silicon, and in seconds the monocrystalline silicon atom is added in the metal electrode material simultaneously, almost cools off simultaneously again afterwards to form recrystallized layer, and this recrystallized layer is the lattice lattice structure of more perfect monocrystalline silicon.Only through the hydrogen atom of once sintered passivated surface layer, it is limited that ease is lost, and burns altogether to have ensured that hydrogen atom exists in a large number, and the battery sheet fill factor, curve factor that institute's sintering comes out is higher.
Sintering temperature:
1 district: 300 ℃, 2 districts: 300 ℃, 3 districts: 300 ℃, 4 districts: 450 ℃, 5 districts: 460 ℃, 6 districts: 480 ℃, 7 districts: 620 ℃, 8 districts: 800 ℃, 9 districts: 910 ℃.Under this temperature, the monocrystalline silicon ohmic contact resistance is at 1-2m Ω, fill factor, curve factor 75%-78%
Specific embodiment:
125 * 125 silicon chips, chat technical process 1 in the employing and go damage and matte process, monocrystalline silicon: 0.5-3 Ω .cm, P type (100) crystal orientation, concentration sodium hydroxide: 10g/L, concentration of ethanol 5%-10% reacted 25 minutes down at 85 ℃, obtained monocrystalline silicon surface and was formed into cuclear density height, matte of uniform size.Polysilicon is put into the aqueous solution of nitric acid, hydrofluoric acid, and 0-15 ℃ was reacted 10 minutes, goes damage process to finish simultaneously in the process that matte is made.
Chat diffusion technology in the employing, technological parameter: monocrystalline: 840 ℃-890 ℃ of diffusion temperatures (830 ℃-880 ℃ of polycrystalline), advance stove: 5-8min, big nitrogen 18L/min; Rise again: 10-20min, big nitrogen 18L/min, dried oxygen 0.8-1.8L/min; Diffusion: 30-40min, big nitrogen 18L/min, dried oxygen 0.5-1.5L/min, little nitrogen 0.5-1.5L/min; Advance: 8-10min, big nitrogen 18L/min, dried oxygen 0.5-1.5L/min; Come out of the stove: 5-8min, big nitrogen 18L/min.Diffusion square resistance 20-60, junction depth 0.5um.
Plasma etching by on chat technology: 500w, pressure 100pa, time 10min
Secondary cleaning by on chat technology, hydrofluoric acid clean 2min, infra-red drying
PECVD by on chat technology, thickness 65-80nm, color is a navy blue
Backplate printed silver aluminium paste and oven dry, a back of the body printing aluminium paste and oven dry, the phosphorous silver slurry of positive printing
Sintering temperature: 1 district: 300 ℃, 2 districts: 300 ℃, 3 districts: 300 ℃, 4 districts: 450 ℃, 5 districts: 460 ℃, 6 districts: 480 ℃, 7 districts: 620 ℃, 8 districts: 800 ℃, 9 districts: 910 ℃.Belt speed: 5.1m/min.
Efficiency test: the efficient of single crystal silicon solar cell sheet reaches 16.5%, and the efficient of polycrystalline silicon solar cell reaches 15.0%.
Claims (8)
1. a high efficiency, low cost thin slice crystalline silicon solar cell piece technology is characterized in that: make crystalline silicon solar cell piece by technological process and be subdivided into for seven steps: go damage and surperficial matteization, diffusion system knot, plasma etching trimming, PSG removal, PECVD to deposit Si
3N
4Film, the positive backplate slurry of silk screen printing and back-surface-field (BSF) paste, the common burning form ohmic contact.
2. a kind of high efficiency, low cost thin slice crystalline silicon solar cell piece technology as claimed in claim 1 is characterized in that: described damage and the surperficial matte of going.Use the relatively low ethanol of price to replace isopropyl alcohol, form Woolen-making liquid with the aqueous solution of NaOH,, with the traditional handicraft process go two of damage and making herbs into wool independently process and go on foot one finish, simplified process, reduced cost.
3. a kind of high efficiency, low cost thin slice crystalline silicon solar cell piece technology as claimed in claim 1 is characterized in that: diffusion system knot.Technological parameter: 840 ℃-890 ℃ of diffusion temperatures, advance stove: 5-8min, big nitrogen 18L/min; Rise again: 10-20min, big nitrogen 18L/min, dried oxygen 0.8-1.8L/min; Diffusion: 30-40min, big nitrogen 18L/min, dried oxygen 0.5-1.5L/min, little nitrogen 0.5-1.5L/min; Advance: 8-10min, big nitrogen 18L/min, dried oxygen 0.5-1.5L/min; Come out of the stove: 5-8min, big nitrogen 18L/min.Every groove is put two silicon chips during diffusion, and 400/pipe, compare with traditional open pipe diffusion, reduced POCl greatly
3Liquid source, N
2, dried oxygen consumption, improved production efficiency, effectively reduced the exhaust gas discharging amount, saved cost, reduced energy consumption.
4. a kind of high efficiency, low cost thin slice crystalline silicon solar cell piece technology as claimed in claim 1 is characterized in that: the plasma etching trimming.
5. a kind of high efficiency, low cost thin slice crystalline silicon solar cell piece technology as claimed in claim 1 is characterized in that: PSG removes.
6. a kind of high efficiency, low cost thin slice crystalline silicon solar cell piece technology as claimed in claim 1, it is characterized in that: PECVD deposits Si
xN
yFilm.
7. a kind of high efficiency, low cost thin slice crystalline silicon solar cell piece technology as claimed in claim 1 is characterized in that: positive backplate slurry of silk screen printing and back-surface-field (BSF) paste.
8. a kind of high efficiency, low cost thin slice crystalline silicon solar cell piece technology as claimed in claim 1 is characterized in that: burn the formation ohmic contact altogether.
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| CN101958367A (en) * | 2010-07-14 | 2011-01-26 | 江苏林洋太阳能电池及应用工程技术研究中心有限公司 | Surface microregion controllable modification process of monocrystalline silicon solar battery |
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