CN1744331A - Method for manufacturing solar cell - Google Patents
Method for manufacturing solar cell Download PDFInfo
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- CN1744331A CN1744331A CNA2005100430320A CN200510043032A CN1744331A CN 1744331 A CN1744331 A CN 1744331A CN A2005100430320 A CNA2005100430320 A CN A2005100430320A CN 200510043032 A CN200510043032 A CN 200510043032A CN 1744331 A CN1744331 A CN 1744331A
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- solar cell
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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
Abstract
According to production process, the invention includes following six steps: preceding chemical pretreatment; preparing semiconductor PN junction; etching periphery through inductance coupling plasma (ICP); depositing film of silicon nitride; screen printing front electrode and back electrode; metallizing front electrode and back electrode and burning through film of silicon nitride. Silver- aluminum paste is adopted for printing small window of aluminum paste in order to guarantee that the small window also obtains structure of aluminum backfield as well as realizes compensation from trivalent aluminum for quinquevalent phosphor at the small window. The invention optimum designs depth of frontal PN junction of silicon cell in technique for burning through film of silicon nitride. Effect of the invention is that efficiency of solar cell in single crystal silicon reaches to 14.6%, and efficiency of solar cell in polysilicon to 14.0%.
Description
Technical field
The present invention relates to the solar cell manufacturing technology, relate in particular to a kind of low cost, high efficiency, high-power, large-area a kind of method for manufacturing solar battery belongs to the Application of Solar Energy field.
Background technology
Crystal silicon chip solar cell yield and sales volume, the basis that the index access formula increases in the time is the lasting reduction of the improvement of crystal silicon chip manufacture of solar cells technology and development, production cost in the past twenty years.
In the patent documentation of existing scientific and technological magazine and countries in the world, the technology report of relevant crystal solar cell is a lot, anatomize, be not quite similar, every kind of special technical process all has the characteristics of self and the technical equipment background and the scope of application that is supported, and what the overwhelming majority was reported is the research of individual event technical process.Find by literature search, James Amick, Princeton, N.J. wait the United States Patent (USP) " solar cell and manufacture method " of application, number of patent application: US005320684A, back electrode is made with the aluminium paste of silk screen seal band wicket in this patent back side, aluminium paste wicket place stamps the silver slurry leg slightly bigger than aluminium paste wicket earlier, near positive PN junction junction depth is 0.5 μ m, and this patent has solved Ohmic electrode contact, aluminium back of the body field and the leg design of suitable extraction electrode weldering knot at the back side and concrete technology realizes.This technology is not considered the influence to aluminium back of the body field that aluminium paste wicket place printing fine silver slurry is brought.Aluminium paste wicket place does not realize that back side trivalent aluminium is to phosphoric compensating action yet.In addition, this technology does not consider that in burning silicon nitride film technology, positive PN junction needs further design yet.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of high efficiency, low cost large tracts of land a kind of method for manufacturing solar battery, it organically is together in series every technology, obtained to be fit to the method for the production process of the specification of homemade technological equipment and requirement, simplified solar cell technology, reduced cost, established technical foundation for the production domesticization of silicon chip solar battery production and silicon solar cell product go to the world.
The present invention is achieved by the following technical solutions, and a kind of method for manufacturing solar battery of the present invention is divided into following six steps in proper order by the production of processing line: preceding Dow Chemical preliminary treatment; The making of semiconductor PN; Inductance coupling plasma (ICP) etching periphery; Deposition silicon nitride film; Silk screen printing just, backplate: just, backplate metallization and silicon nitride film burn.Silver-colored aluminium paste is adopted in aluminium paste wicket place printing, has guaranteed that wicket obtains aluminium back of the body field structure too, and the trivalent aluminium that has realized aluminium paste wicket place is to phosphoric compensating action.The present invention has simultaneously also made further optimal design to the silion cell front PN junction junction depth that burns in the silicon nitride film technology.
Below step of the present invention is described in further detail, particular content is as follows:
One, preceding Dow Chemical preliminary treatment
Select the silicon wafer of resistivity at 0.6～2 Ω cm, adopt semi-conductive conventional cleaning, remove the affected layer that slicing processes is brought with the aqueous slkali reduction process, silicon wafer thickness behind the attenuate reaches 300 μ m, carry out the surface-texturing of silicon chip with the dilute hydrogen sodium hydroxide solution of percentage by weight 1.25% and handle, (volume ratio is H with aqueous hydrochloric acid solution
2O: HCl: H
2O
2=6: 1: 1) boil 10 minutes twice, float surface silicon layer, after the per pass chemical treatment operation,, use hot and cold washed with de-ionized water number time, infrared lamp dry for standby at last with washed with de-ionized water number time with the diluted hydrofluoric acid aqueous solution of percent by volume 5%.
Two, semiconductor PN is made
Adopt semiconductor liquid source diffusion technology, POCI
3Be the phosphorus gaseous source, the conventional diffusion facilities of semi-conductor industry, platinum rhodium thermocouple is surveyed the temperature of diffusion furnace, semiconductor is temperature automatically controlled, the temperature of the flat-temperature zone that the single crystal silicon solar cell PN junction is made is 900～950 ℃, the temperature of the flat-temperature zone that the polycrystalline silicon solar cell PN junction is made is made temperature a little less than the single crystal silicon solar cell PN junction, is 850～900 ℃, and the length of flat-temperature zone is 110cm.Preheated in 5 minutes: logical nitrogen 300ml/min, oxygen 85ml/min, 10～20 minutes Heng Yuan diffusion: logical nitrogen 300ml/min, oxygen 85ml/min, take source nitrogen 70ml/min, 20～40 minutes the source of deciding advances: logical nitrogen 300ml/min, oxygen 85ml/min.During diffusion, silicon chip is placed in quartz ampoule in twos back-to-back, can reduce the N at the back side
+The concentration of the phosphorus impurities of layer.
Three, ICP plasma etching periphery
Adopt carbon tetrafluoride (CF
4) and oxygen (O
2) working gas, inductance coupling plasma (ICP) generator produces the plasma that silicon chip is had corrasion, makes peripheral etching to building the silicon chip of putting well in advance in reative cell, has removed the positive back side short circuit PN junction of silicon chips periphery.
Four, deposition silicon nitride film
Silicon nitride film is concealment diffusion and the purifying film of using always in semiconductor device technology, in crystal-silicon solar cell technology, also select for use silicon nitride film that the front surface of solar cell is carried out purifying, to reduce the recombination velocity of surperficial photoproduction minority carrier, simultaneously, the light refractive index and the thickness of control silicon nitride film, make it reach best optics antireflective effect, match with textured silicon face, form the light trapping of incident light, strengthened the light amount of incident that enters silicon chip.
The present invention adopts plasma-reinforced chemical phase depositing operation deposited silicon nitride purifying, antireflection film, also available reaction radio frequency sputtering technology.Adopt high frequency plasma (13.Plasma-enhanced chemical vapor deposition technology (PECVD) 56MHz), the process conditions of preparation silicon nitride film are as follows: high frequency power is 100W, base vacuum 0.5Pa, the flow 400ml/min (SiH of silicon source gas
45%+N
295%) nitrogen source gas flow 40ml/min (high-purity ammonia NH,
3), reacting gas pressure 10Pa.Deposition time decide by the speed of heavy film, and underlayer temperature is 350 ℃, and the thickness of controlling silicon nitride film usually is at 70～80nm, and this thickness is 1/4th a wavelength light path with blue light (480nm) calculating.The existing navy blue in the surface of solar cell.
Five, silk screen printing just, backplate
The front of silicon solar cell is for being subjected to plane of illumination, and front electrode should be drawn photogenerated current, is unlikely to the area that blocks too many sunlight, reduced illumination again.Adopt grid line to add bus-bar structure, the width of grid line is 0.4～0.1mm, and the width of busbar is 2～3mm, and the used material of front gate line is the silver slurry.The backplate of silicon solar cell prepares with aluminium paste, for the welding sequence in road, back, makes the leg bar with the silver slurry, and the silver-colored aluminium paste of leg bar should be printed on the back side of battery prior to the aluminium paste of aluminium electrode.The aluminium lamination electrode at the back side has a plurality of effects: the first, and the PP at the formation back side
+The height knot, promptly aluminium is carried on the back the field, improves the open circuit voltage of battery; The second, the forming process of alusil alloy layer has surperficial purifying and rich phosphorus N
+The compensating action of layer, consider that aluminium paste is different with silver-colored aluminium paste thermal coefficient of expansion in the sintering forming process under the high temperature, with the silver-colored aluminium paste leg bar at the back side be imprinted on aluminium paste below, the back side aluminium electrode that aluminium paste forms is opened a strip window at the place, seat of every leg bar, width is 3～5mm, the width of leg bar is 4～6mm, the width outline of this window is less than the width of silver-colored aluminium paste leg bar, window place at the aluminium electrode, expose the leg bar, aluminium electrode and leg bar have having a common boundary of 0.5～2mm width, to improve the conductivity at the back side.
Six, just, backplate metallization and silicon nitride film burn
Just, the metallized disposable sintering of backplate; simplified the manufacture craft process of crystal-silicon solar cell; energy consumption and production cycle have been reduced; carry out silicon nitride film simultaneously and burn technology, burn silicon nitride film technology, both can be when metallization; the protection surface is not contaminated; realize the structure optimization of crystal-silicon solar cell again, and the purifying of front surface, improved the power output of solar cell.Adopt homemade chain-type sintering furnace equipment, preferred processing condition is: 850 ℃ of sintering single crystal silicon solar cell electrode high-temperature region maximum temperatures, sintering polycrystalline silicon solar cell electrode high-temperature region maximum temperature is a little less than the sintering temperature of single crystal silicon solar cell, it is 750～800 ℃, rotating speed is 1250 rev/mins, cover whole process and need 4 minutes, the high-temperature region residence time is less than 30 seconds.
The present invention just, the once sintered metallization technology of backplate, reach and burn silicon nitride purifying thin film technique simultaneously, below silicon nitride film, having formed good silver---the front electrode of silicon ohmic contact has formed the alusil alloy back electrode that back of the body field effect is arranged again.The metallization sintering process of back side aluminium electrode has been carried out purifying to the back side, has simultaneously rich phosphorus N
+The compensating action of layer.
The present invention has substantive distinguishing features and marked improvement.It is the anti-reflection purification membrane of front surface that the present invention adopts silicon nitride film, the back side adopts the aluminium paste of silk screen seal band wicket to make back electrode, aluminium paste wicket place stamps the silver-colored aluminium mixed pulp leg slightly bigger than aluminium paste wicket earlier, just, backplate is once sintered and simultaneously silicon nitride film burn technology, and can accomplish 0.3 μ m～0.5 μ m near positive PN junction junction depth.Obtain best optimization effect like this, simplified solar cell technology, two to three times original electrode has been burnt sintering process, be simplified to once and finish, reduced cost, improved efficiency of solar cell.Silver-colored aluminium paste is adopted in aluminium paste wicket place printing, guarantees that wicket obtains aluminium back of the body field structure too, and the trivalent aluminium that has realized aluminium paste wicket place is to phosphoric compensating action, and open circuit voltage can reach more than the 610mV.Patent of the present invention has also been made further optimal design to the silion cell front PN junction junction depth that burns in the silicon nitride film technology simultaneously.Adopt this technology, can obtain commercialization large tracts of land (103*103mm
2) efficient of single crystal silicon solar cell reaches 15.7%, this technology also is applicable to polycrystalline silicon solar cell, polycrystalline silicon solar cell efficient can reach more than 14.0%, (AM1.5, intensity of illumination 100mW/cm
2, 25 ℃).
Embodiment
Content statement specific embodiments below in conjunction with technology of the present invention is described further a kind of method for manufacturing solar battery of the present invention.
Dow Chemical preliminary treatment before adopting above-mentioned step 1 to carry out: the semiconductor PN manufacture craft is: the temperature of flat-temperature zone is 900 ℃, the temperature of the flat-temperature zone that the polycrystalline silicon solar cell PN junction is made is made temperature a little less than the single crystal silicon solar cell PN junction, it is 850 ℃, preheated in 5 minutes: logical nitrogen 300ml/min, oxygen 85ml/min, 10 minutes Heng Yuan diffusion: logical nitrogen 300ml/min, oxygen 85ml/min, take source nitrogen 70ml/min, 20 minutes the source of deciding advances: logical nitrogen 300ml/min, oxygen 85ml/min.
Adopt above-mentioned step 3 and step 4 to carry out the deposition of inductance coupling plasma periphery etching and silicon nitride film; Adopt above-mentioned step 5 carry out silk screen printing just, backplate, the width of grid line is 0.15mm, the width of busbar is 2mm, the used material of front gate line is a silver slurry.The backplate of silicon solar cell prepares with aluminium paste, make the leg bar with silver-colored aluminium paste, the silver-colored aluminium paste of leg bar is printed on the back side of battery prior to the aluminium paste of aluminium electrode, with the silver-colored aluminium paste leg bar at the back side be imprinted on aluminium paste below, back side aluminium electrode is 3mm at leg bar place window width, the width of leg bar is 4mm, the width outline of this window is less than the width of silver-colored aluminium paste leg bar, at the window place of aluminium electrode, expose the leg bar, aluminium electrode and leg bar have having a common boundary of 0.5mm width; Just, metallize disposable sintering and silicon nitride film of backplate burns technical process, 850 ℃ of high-temperature region maximum temperatures, sintering polycrystalline silicon solar cell electrode high-temperature region maximum temperature is a little less than the sintering temperature of single crystal silicon solar cell, it is 750 ℃, rotating speed is 1100 rev/mins, cover whole process and need 4.5 minutes, the high-temperature region residence time is less than 30 seconds.
Implementation result: the efficient of single crystal silicon solar cell reaches 14.6%, and the efficient of polycrystalline silicon solar cell reaches 14.0%.
Claims (7)
1, a kind of method for manufacturing solar battery is characterized in that: be divided into following six steps in proper order by manufacture method production: preceding Dow Chemical preliminary treatment; Semiconductor PN is made; Inductance coupling plasma etching periphery; Deposition silicon nitride film; Silk screen printing just, backplate; Just, backplate metallization and silicon nitride film burn.
2, follow according to the described a kind of method for manufacturing solar battery of claim 1, it is characterized in that described preceding Dow Chemical preliminary treatment is specific as follows:
Select the silicon wafer of resistivity at 0.6～2 Ω cm, adopt semi-conductive conventional cleaning, remove the affected layer that slicing processes is brought with the aqueous slkali reduction process, silicon wafer thickness behind the attenuate reaches 300 μ m, carrying out the surface-texturing of silicon chip with the dilute hydrogen sodium hydroxide solution of percentage by weight 1.25% and handle, is H with volume ratio
2O: HCl: H
2O
2=6: aqueous hydrochloric acid solution boiled 10 minutes twice in 1: 1, the diluted hydrofluoric acid aqueous solution with percent by volume 5% floats the surface oxidation silicon layer, after the per pass chemical treatment operation, with washed with de-ionized water number time, use hot and cold washed with de-ionized water number time, infrared lamp dry for standby at last.
3, follow according to the described a kind of method for manufacturing solar battery of claim 1, it is characterized in that: described semiconductor PN is made specific as follows:
Adopt semiconductor liquid source diffusion technology, POCI
3Be the phosphorus gaseous source, the conventional diffusion facilities of semi-conductor industry, platinum rhodium thermocouple is surveyed the temperature of diffusion furnace, semiconductor is temperature automatically controlled, the temperature of the flat-temperature zone that the single crystal silicon solar cell PN junction is made is 900～950 ℃, the temperature of the flat-temperature zone that the polycrystalline silicon solar cell PN junction is made is 850～900 ℃, and the length of flat-temperature zone is 110cm; Preheated in 5 minutes: logical nitrogen 300ml/min, oxygen 85ml/min, 10～20 minutes Heng Yuan diffusion: logical nitrogen 300ml/min, oxygen 85ml/min, take source nitrogen 70ml/min, 20～40 minutes the source of deciding advances: logical nitrogen 300ml/min, oxygen 85ml/min; During diffusion, silicon chip is placed in quartz ampoule in twos back-to-back, reduces the N at the back side
+The concentration of the phosphorus impurities of layer.
4, follow according to the described crystal silicon chip solar module of claim 3, it is characterized in that: described inductance coupling plasma etching periphery is specific as follows:
Adopt carbon tetrafluoride and oxygen working gas, inductance coupling plasma generator produces the plasma that silicon chip is had corrasion, makes peripheral etching to building the silicon chip of putting well in advance in reative cell, has removed the positive back side short circuit PN junction of silicon chips periphery.
5, follow according to the described a kind of method for manufacturing solar battery of claim 1, it is characterized in that: described deposition silicon nitride film is specific as follows:
Adopt plasma-reinforced chemical phase depositing operation deposited silicon nitride purifying, antireflection film, adopt the plasma-enhanced chemical vapor deposition technology of high frequency plasma, the process conditions of preparation silicon nitride film are as follows: high frequency power is 100W, base vacuum 0.5Pa, the flow 400ml/min of silicon source gas, wherein SiH
45%+N
295%, nitrogen source gas flow 40ml/min adopts high-purity ammonia NH
3, reacting gas pressure 10Pa.Deposition time decide by the speed of heavy film, and underlayer temperature is 350 ℃, and the thickness of controlling silicon nitride film usually is at 70～80nm, and this thickness is 1/4th a wavelength light path with blue light calculating.The existing navy blue in the surface of solar cell.
6, follow according to the described a kind of method for manufacturing solar battery of claim 1, it is characterized in that: silk screen printing just, backplate, concrete feature is as follows:
The positive grid line that adopts adds bus-bar structure, and the width of grid line is 0.4～0.1mm, and the width of busbar is 2～3mm, and the used material of front gate line is the silver slurry; The backplate of silicon solar cell prepares with aluminium paste, makes the leg bar with silver slurry, and the silver-colored aluminium paste of leg bar is printed on the back side of battery prior to the aluminium paste of aluminium electrode, and the aluminium lamination electrode at the back side can form the PP at the back side
+The height knot, the forming process of alusil alloy layer is to carrying on the back surperficial purifying and rich phosphorus N
+The compensation of layer, with the silver-colored aluminium paste leg bar at the back side be imprinted on aluminium paste below, the back side aluminium electrode that aluminium paste forms is opened a strip window at the place, seat of every leg bar, 3～5mm, the width of leg bar is 4～6mm, and the width outline of this window is less than the width of silver-colored aluminium paste leg bar, at the window place of aluminium electrode, expose the leg bar, aluminium electrode and leg bar have having a common boundary of 0.5～2mm width.
7, a kind of method for manufacturing solar battery according to claim 1 is characterized in that: described just, backplate metallization and silicon nitride film burn specific as follows:
Just, the metallized disposable sintering of backplate, carry out silicon nitride film simultaneously and burn technology, burn the homemade chain-type sintering furnace equipment of silicon nitride film process using, preferred processing condition is: 850 ℃ of sintering single crystal silicon solar cell electrode high-temperature region maximum temperatures, sintering polycrystalline silicon solar cell electrode high-temperature region maximum temperature is 750～800 ℃, rotating speed is 1250 rev/mins, covers whole process and needs 4 minutes, and the high-temperature region residence time is less than 30 seconds.
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|---|---|---|---|
| CNA2005100430320A CN1744331A (en) | 2005-08-01 | 2005-08-01 | Method for manufacturing solar cell |
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|---|---|---|---|
| CNA2005100430320A CN1744331A (en) | 2005-08-01 | 2005-08-01 | Method for manufacturing solar cell |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101859720A (en) * | 2010-04-15 | 2010-10-13 | 中山大学 | Method for measuring surface contact resistivity of crystalline silicon solar battery |
| CN102044575A (en) * | 2010-12-02 | 2011-05-04 | 江苏大学 | Surface plasma silicon hydride film solar cell |
| CN101783374B (en) * | 2010-01-25 | 2011-09-28 | 日地太阳能电力股份有限公司 | Method for manufacturing silicon solar cell |
| CN102290494A (en) * | 2011-09-14 | 2011-12-21 | 江阴鑫辉太阳能有限公司 | Dry etching technology for solar cell |
| CN103618009A (en) * | 2013-10-18 | 2014-03-05 | 浙江晶科能源有限公司 | Silk-screen printing back passivation battery and preparation method thereof |
| CN103646991A (en) * | 2013-11-28 | 2014-03-19 | 奥特斯维能源（太仓）有限公司 | Preparation method of P-type crystal silicon double-sided cell |
-
2005
- 2005-08-01 CN CNA2005100430320A patent/CN1744331A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101783374B (en) * | 2010-01-25 | 2011-09-28 | 日地太阳能电力股份有限公司 | Method for manufacturing silicon solar cell |
| CN101859720A (en) * | 2010-04-15 | 2010-10-13 | 中山大学 | Method for measuring surface contact resistivity of crystalline silicon solar battery |
| CN101859720B (en) * | 2010-04-15 | 2012-02-29 | 中山大学 | Method for measuring surface contact resistivity of crystalline silicon solar battery |
| CN102044575A (en) * | 2010-12-02 | 2011-05-04 | 江苏大学 | Surface plasma silicon hydride film solar cell |
| CN102044575B (en) * | 2010-12-02 | 2012-08-29 | 江苏大学 | Surface plasma silicon hydride film solar cell |
| CN102290494A (en) * | 2011-09-14 | 2011-12-21 | 江阴鑫辉太阳能有限公司 | Dry etching technology for solar cell |
| CN102290494B (en) * | 2011-09-14 | 2013-09-18 | 江阴鑫辉太阳能有限公司 | Dry etching technology for solar cell |
| CN103618009A (en) * | 2013-10-18 | 2014-03-05 | 浙江晶科能源有限公司 | Silk-screen printing back passivation battery and preparation method thereof |
| CN103646991A (en) * | 2013-11-28 | 2014-03-19 | 奥特斯维能源（太仓）有限公司 | Preparation method of P-type crystal silicon double-sided cell |
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