CN103021511A - Front electrode silver paste of crystalline silicon solar battery and preparation method for front electrode silver paste - Google Patents
Front electrode silver paste of crystalline silicon solar battery and preparation method for front electrode silver paste Download PDFInfo
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Abstract
The invention provides front electrode silver paste of a crystalline silicon solar battery and a preparation method for the front electrode silver paste. The silver paste comprises the following components in reference to the total weight of the silver paste: 75 to 90 percent of silver powder, 1 to 3 percent of first glass powder, 1 to 5 percent of second glass powder and 6 to 25 percent of organic component, wherein the softening point of the first glass powder is 350 to 550 DEG C; the softening point of the second glass powder is 550 to 650 DEG C; and a difference between the softening point of the first glass powder and the softening point of the second glass powder is at least 70 DEG C. The invention also provides the preparation method for the electrode silver paste. The electrode silver paste can be sintered at a relatively wide sintering temperature range; and the obtained solar battery is low in series resistance and high in photoelectric conversion rate.
Description
Technical field
The invention belongs to the crystal silicon solar energy battery field, relate to a kind of crystal silicon solar energy battery front electrode silver slurry and preparation method thereof.
Background technology
Crystal silicon solar energy battery is developed rapidly as main solar energy power generating unit.Solar battery front side is as the one side that directly receives solar energy, by sandwich construction in the hope of reaching the widest reception spectral line and minimum light reflection consumption.Conventional commercial crystal silicon solar cell sheet front comprises silver electrode grid line, nonconducting antireflection layer, N-shaped diffusion layer, p-n junction district four floor primary structure.Front electrode is as the important component part of crystal silicon solar energy battery, the ratio of width to height of contact resistance between electrode and N-shaped silicon, the conductivity of electrode itself and electrode has direct impact to its electricity conversion, becomes one of main direction of studying of the sector.
At present, the manufacture method of commercial crystal silicon solar energy battery front electrode, usually adopt printing and inkjet printing conductive silver paste to form the large as far as possible grid line structure of depth-width ratio, pass through subsequently near the Fast Sintering process the room temperature to 780 ℃, form and the conductive electrode of N-shaped diffusion layer close contact.In this sintering process, usually by contained corrosivity frit in the slurry, such as lead borosilicate glass material commonly used fusion sediment gradually in temperature-rise period, spread over the ARC(antireflective of dissolving N-shaped silicon face between silicon chip and the silver powder) Ag powder in film and the slurry.In temperature-fall period, the oversaturated frit of Ag is separated out Ag at the N-shaped silicon face subsequently, and the Ag island that forms reverse pyramid conducts to photogenerated current the Ag grid line on upper strata.This current conductive path is made of following components: N-shaped silicon-Ag island-glassy layer-Ag electrode.The real output of crystal silicon solar energy battery is subjected to the Resistance Influence of this current path larger, the low resistance of General Requirements Ag electrode self, glassy layer is thin and conductivity is relatively high, the quantity on Ag island is many and volume is unsuitable excessive, to reduce the series resistance in the whole loop, improve the whole electricity conversion of crystal silicon solar cell sheet.But the series resistance of existing front electrode of solar battery is larger, makes its electricity conversion low.
Summary of the invention
The present invention exists series resistance large for solving existing front electrode of solar battery silver slurry, the defective that electricity conversion is low, thus provide a kind of series resistance little, front electrode of solar battery silver slurry that electricity conversion is high and preparation method thereof.
The low resistance that reduces Ag electrode self requires the Ag electrode as far as possible fine and close in sintering process, but present commercial sintering process, effectively sintering time very short (＜10s), the Ag electrode needs the frit of melting to help sintering; Frit also needs to deposit the ARC film that spreads over dissolving N-shaped silicon face between silicon chip and the silver powder in addition.
The present inventor draws through a large amount of experiments, adopt single frit in the common front side silver paste, realize at the same time will occurring in the situation of above-mentioned two kinds of functions the phenomenon of contradiction, its main cause is, can not the efficient melting deposition spread over the ARC film that dissolves the N-shaped silicon face between silicon chip and the silver powder at (＜740 ℃) glass dust under the lower technological temperature, and Ag powder sintering activity at this moment is inadequate, is difficult to densified sintering product; Improve sintering temperature and improve more than 20 ℃ or increase sintering time, be used between the silver powder helping the frit of burning also can deposit, cause that Ag electrode sintering is not fine and close, glassy layer is blocked up and excessive to the corrosion of silicon chip, burn the problems such as p/n knot.
The invention provides a kind of crystal silicon solar energy battery front electrode silver slurry, described silver slurry comprises silver powder, the first glass dust, the second glass dust and organic components; Take the total weight of silver slurry as benchmark, the content of described silver powder is the 75-90 % by weight, and the content of described the first glass dust is the 1-3 % by weight, and the content of described the second glass dust is the 1-5 % by weight, and the content of described organic component is the 6-25 % by weight; The softening point of described the first glass dust is 350-550 ℃, and the softening point of described the second glass dust is 550-650 ℃, and differs at least 70 ℃ between the softening point of the first glass dust and the second glass dust.
The present invention also provides a kind of preparation method of electrode silver plasm, and the method comprises mixes silver powder, the first glass frit, the second glass dust and organic component and grinding.
Crystal silicon solar energy battery front electrode silver slurry of the present invention, by two kinds of glass frit powder of in the silver slurry, adding different softening point, wherein the first glass dust is used for the corrosion antireflective coating in sintering process, the second glass dust is used for helping the silver powder sintering in sintering process, thereby reach effective control the extent of corrosion of silicon chip surface is prevented from burning the p/n interface, control simultaneously the thickness of glassy layer between emitter and the silver electrode, be conducive to slurry and in more broad sintering temperature window, obtain stable and outstanding electrical performance indexes.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of crystal silicon solar energy battery front electrode silver slurry, described silver slurry comprises silver powder, the first glass dust, the second glass dust and organic components; Take the total weight of silver slurry as benchmark, the content of described silver powder is the 75-90 % by weight, and the content of described the first glass dust is the 1-3 % by weight, and the content of described the second glass dust is the 1-5 % by weight, and the content of described organic component is the 6-25 % by weight; The softening point of described the first glass dust is 350-550 ℃, and the softening point of described the second glass dust is 550-650 ℃, and differs at least 70 ℃ between the softening point of the first glass dust and the second glass dust.
Differ at least 70 ℃ between the softening point of the first glass dust and the second glass dust, to guarantee under suitable process conditions, particularly in the situation of high temperature or longer sintering time, the wetting polycrystalline silicon substrate surface of the abundant sedimentation of the first glass dust, the second glass dust is unlikely to a large amount of depositions simultaneously increases glassy layer thickness, affects series resistance.
The softening point of described first glass dust should not be lower than 350 ℃, otherwise in the slurry organic substance also undecomposed volatilization totally, its drain passageway just is melted glass and fills up, and will cause the problems such as carbon residue, internal void, internal stress.Softening point should not be higher than 550 ℃, and deposition spreads between silicon chip and the silver powder otherwise be difficult to effectively.
The softening point range of described second glass dust is 550-650 ℃.Softening point is lower than in 550 ℃ the situation, and the too early fusion sediment of glass dust causes between Si sheet and the Ag electrode glassy layer blocked up, and series resistance increases, and can not play the effect of burning Ag electrode sintering that helps.Softening point is higher than in 650 ℃ the situation, and silver powder is when sintering, and the frit viscosity is higher, does not have sintering aids role.
Preferably, differ 160-260 ℃ between the softening point of described the first glass dust and the second glass dust.
The consumption of described first glass dust should be less than 1wt%, otherwise can not effectively spread between silicon chip and the silver powder, can't corrode the ARC layer of 70-80nm thickness fully yet.The consumption of first glass dust should be greater than 3wt% yet, otherwise glassy layer is blocked up, increases series resistance; It is excessive perhaps to corrode, and burns the p/n knot, causes short circuit.Under the preferable case, the consumption of first glass dust is 1.2-2wt%.
The consumption of described second glass dust should be less than 1wt%, otherwise can not be scattered in effectively equably between the silver powder, the consumption of second glass dust should be greater than 5wt% yet, otherwise frit will form connection, isolate Ag crystal in the Ag electrode, seriously reduce the conductivity of Ag electrode.Under the preferable case, the consumption of second glass dust is 2.5-3.5wt%.
Preferably, the average grain diameter of described the first glass dust and the second glass dust is the 0.1-10 micron.When particle diameter during less than 0.1 micron, powder is reunited, and is difficult to disperse in slurry; When particle diameter during greater than 10 microns, be difficult to use in the preparation of thin gate line electrode.More preferably in the situation, the average grain diameter of first glass dust is the 0.3-1.5 micron, and less particle diameter is conducive to after first the glass dust melting fast by the passage between the silver powder, and deposition is tiled between Si sheet and the silver powder.More preferably in the situation, the average grain diameter of second glass dust is the 2-6 micron, relatively large particle diameter is conducive to single glass dust and contacts with the more silver powder of periphery, help sintering, but when particle diameter is excessive, in the situation of same amount, the sum of glass dust reduces, and also is unfavorable for being dispersed in uniformly and effectively between the Ag powder.
Preferably, described first glass dust contains the Pb of 65-90wt% or the compound of Bi, or the combination of compound.The lead borosilicate glass that more preferably contains 70-85wt%PbO.Wherein the compound of Pb or Bi is the main matter for corrosion ARC film.For example, the PbO in the frit generates SiO by with ARC redox reaction occuring
2And Pb, wherein SiO
2Dissolving enters in the frit.Bi in the glass
3+Same effect is also arranged.Pb in the glass or the compounds content of Bi be than needing to surpass more than the 65wt%, the guarantee reaction density, constantly effectively corrosion thickness at the ARC of 70-80nm thickness film.The compound that surpasses simultaneously the above Pb of 65wt% or Bi also plays the effect of strong reduction glass softening point in glass, also can be by adding B
2O
3Softening point with a certain amount of alkali metal reduction glass.Also can add other compounds and adjust the performances such as the thermal coefficient of expansion of glass, softening point, wetability, viscosity.
Preferably, described second glass dust is not strict with composition, can select SiO
2, B
2O
3, PbO, ZnO, Bi
2O
3, V
2O
5And alkali metal compound etc. is as the main body composition of glass.Also can add other compounds and adjust the performances such as the thermal coefficient of expansion of glass, softening point, wetability, viscosity.
Preferably, the pattern of described silver powder can be the composition of the arbitrary shapes such as sheet, granular, colloidal, amorphous state or different morphologies powder, and average grain diameter is the 0.1-15 micron, and the powder tap density is greater than 3g/cm
3More preferably in the situation, can select granularly, average grain diameter is the silver powder between the 0.5-2 micron.The powder sintered activity of the Ag of the type is the most suitable, in that be higher than all can basic densified sintering product under 740 ℃ the Fast Sintering condition.If select the less silver powder of particle diameter, its tap density is difficult to guarantee greater than 3g/cm
3, be easy to reunite, it is inhomogeneous to cause it to disperse at middle slurry, and affects the mobile performance of slurry.
Preferably, the content of described silver powder in slurry should not be lower than 75wt%, even otherwise have frit to help sintering, also be difficult to densified sintering product.More preferably in the situation, silver powder content is 78-85wt%.
According to electrode silver plasm provided by the present invention, described organic component comprises binding agent, organic solvent and additive.Described binding agent is ethyl cellulose; Described organic solvent is terpinol; Additive is wetting agent or auxiliary rheological agents.
The present invention also provides the preparation method of this anode silver paste, and the method comprises mixes silver powder, the first glass frit, the second glass dust and organic component and grinding.
Preparation method according to the solar cell front electrode of the specific embodiment of the invention, comprise the steps: and to be imprinted on the sensitive surface of semiconductor substrate with silk screen print method according to the front electrode slurry of the specific embodiment of the invention, oven dry, then Fast Sintering forms the solar cell front electrode; The peak temperature of described Fast Sintering process is 755-765 ℃, and the peak temperature time is 1-3 second.
The flash sintering method of front electrode is the metallization process of the maturation of current large-scale industrial production crystal-silicon solar cell, generally comprises 4 stages: combustion of organic matter stage, temperature rise period, interval, the temperature-fall period of peak temperature.
The combustion of organic matter stage is generally at 300 ℃, and excess Temperature can cause between metal-semiconductor contact resistance excessive, and temperature is crossed and lowly can be caused the organic substance volatilization not exclusively, also can cause same problem.
Temperature rise period is rapidly heated and slowly heats up 2 kinds.The technique that heats up rapidly generally is that front 80 seconds in sintering process maintain the temperature at about 350 ℃, during 80 seconds left and right sides in seconds (3-5 second) be warmed up to rapidly 780 ℃.Slowly heating process generally is that front 40 seconds temperature of sintering process remain on about 300 ℃, and 40 seconds left and right sides Shi Zaiyue were warmed up to more than 750 ℃ in 50 seconds.Concrete heating rate is by the sintering furnace control of using.
The peak temperature interval is relatively more crucial technical process, especially will note the setting of peak temperature.Peak temperature has determined in the sintering process concentration of metal ion in aerdentalloy, the alusil alloy, that is to say, sintering temperature is being controlled the diffusion length of metal ion in the alloying process, to the sintering of front electrode, backplate, and the series resistance of the solar cell behind the sintering and fill factor, curve factor all have considerable influence.Preparation method according to the solar cell front electrode of the specific embodiment of the invention, the peak temperature of described sintering process is 750-790 ℃, the peak temperature time is 1-3 second, the front electrode that obtains like this is improved to the adhesion strength of semiconductor crystalline silicon matrix, thickness of electrode is even, broken string occurs, fall the situation of material, and the fill factor, curve factor of battery, series resistance, electricity conversion all there are improvement.
The temperature-fall period General Requirements is at the uniform velocity continuous, does not have large temperature gradient to change.But also can between peak region, increase afterwards as required annealing process.The too high burning that causes has certain improvement to this technique to peak temperature.
Other techniques of crystalline silicon solar cell piece preparation, such as making herbs into wool, diffusion system knot, removal phosphorosilicate glass, the P-N knot of removing the silicon chip edge, depositing antireflection film, silk screen printing etc. all are not particularly limited, and all can adopt technique well known in the art.For example, with concentration about 1%, temperature 70-85 ℃ sodium hydroxide solution carries out chemical corrosion making herbs into wool to the polycrystalline silicon surface; Can also contain a certain amount of HNO with HF(
3And surfactant) chemical corrosion making herbs into wool is carried out on the polycrystalline silicon surface; Use liquid POCl
3For the P source (or with P
2O
5+ H
2O is the P source) expansion P system knot; Plasma enhanced chemical vapor deposition (PECVD) or electric glow discharge method deposited silicon nitride antireflective coating.Above-mentioned technique and inventive point of the present invention relation are little, and all are prior aries, so do not repeat them here.
Below in conjunction with technology embodiment, the present invention is further described in detail.
Embodiment 1
1, preparation electrode silver plasm
Silver powder 79%, 0.8 micron of average grain diameter; First glass frit powder 1.5% PbO-B
2O
3-SiO
2(PbO: 85wt%) average grain diameter is 1.5 microns, 360 ℃ of softening points; Second glass frit powder 3.5%, B
2O
3-ZnO-V
2O
5, 2.5 microns of average grain diameters, 620 ℃ of softening points; Oleyl alcohol 12% in the pine, ethyl cellulose 2%, wetting dispersing agent 2%.
Above-mentioned substance is mixed and grinding at three-roll grinder, and fineness reaches 13 microns, obtains electrode silver plasm A1.
2, polycrystalline silicon solar cell preparation
At first the P type polysilicon chip of 3 area 156mm * 156mm carried out surface wool manufacturing: polysilicon chip is immersed in 75 ℃, and the quality percentage composition of NaOH and ethanol is respectively 40min in the solution of 20wt%, 10wt%.Take out polysilicon chip, use washed with de-ionized water 10 times, with the residual Woolen-making liquid of flush away silicon chip surface, then dry.
Then use liquid POCl
3The polysilicon chip of doing the effects on surface making herbs into wool of phosphorus source expands phosphorus system knot, forms one deck N-type silicon on a surface of P type polysilicon, thereby makes the P-N knot.The emitter junction square resistance that expands the polycrystalline silicon solar cell after phosphorus system is tied is generally every square 65 Ω, the thickness 180 μ m of polysilicon chip.Afterwards it is carried out dephosphorization silex glass, edge passivation, the processing of PECVD antireflective coating.
The back side at polysilicon applies the formation negative electrode with commercial ferro53-102 and 3347 backplate slurries.
Be that (Dongguan excellent seal silk screen bat printing machinery plant UP-S7090) is imprinted on electrode silver plasm material A1 on the polysilicon sensitive surface that expands behind the phosphorus system knot every polysilicon sacrificial electrode silver slurry A1 0.18g for the screen process press of 280-320 with meshcount subsequently.250 ℃ of lower oven dry 5min, then in long 12 meters continuous tunnel furnace since 300 ℃ of sintering, the sintering final temperature is respectively 750 ℃, 770 ℃ and 790 ℃, silicon chip process of passing through tunnel stove at the uniform velocity in 2 minutes and 12 seconds, then the rate of temperature fall with 164 ℃/S cools to 100 ℃, forms the sensitive surface grid electrode.The peak temperature of sintering is 750 ℃, 770 ℃ and 790 ℃, and the peak temperature time is 2s.Under three kinds of sintering temperatures, obtain respectively polysilicon solar cell B1, C1 and D1.
Embodiment 2
Silver powder 83.5%, 1.2 microns of average grain diameters; First glass frit powder 2.5% Bi
2O
3-B
2O
3-SiO
2-K
2O(Bi
2O
3: 82wt%) average grain diameter is 0.6 micron, 420 ℃ of softening points; Second glass frit powder 2%, PbO-ZnO-SiO
2, 6 microns of average grain diameters, 580 ℃ of softening points; Terpinol 9.5%, ethyl cellulose 1.5%, wetting dispersing agent 1%.
Above-mentioned substance is mixed and grinding at three-roll grinder, and fineness reaches 15 microns, obtains electrode silver plasm A2.
Method according to embodiment 1 prepares polysilicon solar cell B2, C2 and D2.
Embodiment 3
Silver powder 83.5%, 1.2 microns of average grain diameters; First glass frit powder 2% PbO-B
2O
3-SiO
2-ZnO(PbO:78wt%) 0.8 micron of average grain diameter, 380 ℃ of softening points; Second glass frit powder 2.5%, PbO-ZnO-B
2O
3, 1.5 microns of average grain diameters, 550 ℃ of softening points; Terpinol 8.8%, ethyl cellulose 1.5%, wetting dispersing agent 1.7%.
Above-mentioned substance is mixed and grinding at three-roll grinder, and fineness reaches 14 microns, obtains electrode silver plasm A3.
Method according to embodiment 1 prepares polysilicon solar cell B3, C3 and D3.
Embodiment 4
Silver powder 75%, 0.1 micron of average grain diameter; First glass frit powder 3% PbO-B
2O
3-SiO
2-ZnO(PbO:78wt%) 0.3 micron of average grain diameter, 350 ℃ of softening points; Second glass frit powder 5%, PbO-ZnO-B
2O
3, 0.1 micron of average grain diameter, 600 ℃ of softening points; Terpinol 11%, ethyl cellulose 4%, wetting dispersing agent 2%.
Above-mentioned substance is mixed and grinding at three-roll grinder, and fineness reaches 13 microns, obtains electrode silver plasm A4.
Method according to embodiment 1 prepares polysilicon solar cell B4, C4 and D4.
Embodiment 5
Silver powder 90%, 2 microns of average grain diameters; First glass frit powder 1% PbO-B
2O
3-SiO
2-ZnO(PbO:78wt%) 0.1 micron of average grain diameter, 550 ℃ of softening points; Second glass frit powder 1%, PbO-ZnO-B
2O
3, 2 microns of average grain diameters, 620 ℃ of softening points; Terpinol 7%, ethyl cellulose 1%.
Above-mentioned substance is mixed and grinding at three-roll grinder, and fineness reaches 15 microns, obtains electrode silver plasm A5.
Method according to embodiment 1 prepares polysilicon solar cell B5, C5 and D5.
Embodiment 6
Silver powder 85%, 15 microns of average grain diameters; First glass frit powder 1.2% PbO-B
2O
3-SiO
2-ZnO(PbO:78wt%) 10 microns of average grain diameters, 400 ℃ of softening points; Second glass frit powder 4%, PbO-ZnO-B
2O
3, 10 microns of average grain diameters, 650 ℃ of softening points; Terpinol 7%, ethyl cellulose 2.8%.
Above-mentioned substance is mixed and grinding at three-roll grinder, and fineness reaches 12 microns, obtains electrode silver plasm A6.
Method according to embodiment 1 prepares polysilicon solar cell B6, C6 and D6.
Comparative Examples 1
The electrode slurry that is purchased (Ferro, 33-462 front side silver paste) CA1 prepares polysilicon solar cell CB1, CC1 and CD1 according to the method for embodiment 1.
Comparative Examples 2
Silver powder 83.5%, 1.2 microns of average grain diameters; Glass frit powder 4.5% Bi
2O
3-B
2O
3-SiO
2-K
2O(Bi
2O
3: 82wt%) average grain diameter is 0.6 micron, 420 ℃ of softening points; Terpinol 9.5%, ethyl cellulose 1.5%, wetting dispersing agent 1%.
Above-mentioned substance is mixed and grinding at three-roll grinder, and fineness reaches 15 microns, obtains electrode silver plasm CA2.
Method according to embodiment 1 prepares polysilicon solar cell CB2, CC2 and CD2.
Comparative Examples 3
Silver powder 83.5%, 1.2 microns of average grain diameters; Glass frit powder 4.5%, PbO-ZnO-B
2O
3, 1.5 microns of average grain diameters, 550 ℃ of softening points; Terpinol 8.8%, ethyl cellulose 1.5%, wetting dispersing agent 1.7%.
Above-mentioned substance is mixed and grinding at three-roll grinder, and fineness reaches 14 microns, obtains electrode silver plasm CA3.
Method according to embodiment 1 prepares polysilicon solar cell CB3, CC3 and CD3.
Comparative Examples 4
Silver powder 83.5%, 1.2 microns of average grain diameters; Glass frit powder is respectively 2.5% Bi
2O
3-B
2O
3-SiO
2-K
2O(Bi
2O
3: 82wt%) with 2% PbO-B
2O
3-SiO
2-ZnO(PbO:78wt%), average grain diameter all is 0.6 micron, softening point is respectively 420 ℃, 380 ℃; Terpinol 9.5%, ethyl cellulose 1.5%, wetting dispersing agent 1%.
Above-mentioned substance is mixed and grinding at three-roll grinder, and fineness reaches 14 microns, obtains electrode silver plasm CA4.
Method according to embodiment 1 prepares polysilicon solar cell CB4, CC4 and CD4.
Comparative Examples 5
Silver powder 83.5%, 1.2 microns of average grain diameters; Glass frit powder is respectively 2.5% PbO-ZnO-B
2O
3With 2% PbO-ZnO-SiO
2, average grain diameter all is 1.5 microns, softening point is respectively 550 ℃ and 580 ℃; Terpinol 8.8%, ethyl cellulose 1.5%, wetting dispersing agent 1.7%.
Above-mentioned substance is mixed and grinding at three-roll grinder, and fineness reaches 14 microns, obtains electrode silver plasm CA5.
Method according to embodiment 1 prepares polysilicon solar cell CB5, CC5 and CD5.
Method of testing and result
The fill factor, curve factor of solar cell, series resistance, electricity conversion
With the solar battery sheet special test equipment (Shang Haiju receives Science and Technology Ltd., NELC-140A), the above-mentioned performance of the polycrystalline silicon solar cell that obtains by the method for embodiment and Comparative Examples in the lower test of standard test condition (STC).The test result sintering temperature is 750 ℃ as shown in table 1 below, sintering temperature is 770 ℃ as shown in table 2, and sintering temperature is 79 ℃ 0, and is as shown in table 3.(STC) is as follows for standard test condition: light intensity: 1000W/m
2Spectrum: AM1.5; Temperature: 25
oC.
Table 1
| ? | Optoelectronic transformation efficiency % | Series resistance m Ω | Parallel resistance Ω |
| B1 | 16.35 | 3.6 | >100 |
| B2 | 16.4 | 3.45 | >100 |
| B3 | 16.5 | 3.3 | >100 |
| B4 | 16.3 | 3.8 | >100 |
| B5 | 15.9 | 6.2 | >100 |
| B6 | 16.3 | 3.7 | >100 |
| CB1 | 16.05 | 4.3 | >100 |
| CB2 | 16.1 | 4.0 | >100 |
| CB3 | 16.05 | 4.4 | >100 |
| CB4 | 16.3 | 3.8 | >100 |
| CB5 | 16.0 | 4.6 | >100 |
Table 2
| ? | Optoelectronic transformation efficiency % | Series resistance m Ω | Parallel resistance Ω |
| C1 | 16.42 | 3.4 | >100 |
| C2 | 16.5 | 3.2 | 88 |
| C3 | 16.5 | 3.2 | 91 |
| C4 | 16.4 | 3.5 | 76 |
| C5 | 16.1 | 3.9 | >100 |
| C6 | 16.5 | 3.3 | 80 |
| CC1 | 16.4 | 3.5 | 86 |
| CC2 | 16.4 | 3.4 | 82 |
| CC3 | 16.35 | 3.6 | 95 |
| CC4 | 16.5 | 3.1 | 89 |
| CC5 | 16.3 | 3.6 | >100 |
Table 3
| ? | Optoelectronic transformation efficiency % | Series resistance m Ω | Parallel resistance Ω |
| D1 | 16.6 | 3.2 | 95 |
| D2 | 16.45 | 3.4 | 89 |
| D3 | 16.4 | 3.45 | 90 |
| D4 | 16.3 | 3.7 | 82 |
| D5 | 16.4 | 3.4 | 92 |
| D6 | 16.3 | 3.6 | 83 |
| CD1 | 15.7 | 5.1 | 31 |
| CD2 | 15.8 | 5.3 | 28 |
| CD3 | 16.0 | 4.8 | 34 |
| CD4 | 15.8 | 5.2 | 29 |
| CD5 | 16.2 | 3.9 | 75 |
Can find out from experimental result, adopt the present invention under 750-790 ℃ different sintering temperature conditions, all can obtain low series resistance and very high parallel resistance, guaranteed in the situation of process conditions than great fluctuation process that the electricity conversion of crystal silicon solar cell sheet is more than 16.0%, but the solar cell of Comparative Examples can only satisfy narrower sintering range, surpass this temperature range, its optoelectronic transformation efficiency is very low.
Claims (11)
1. a crystal silicon solar energy battery front electrode silver slurry is characterized in that, described silver slurry comprises silver powder, the first glass dust, the second glass dust and organic components; Take the total weight of silver slurry as benchmark, the content of described silver powder is the 75-90 % by weight, and the content of described the first glass dust is the 1-3 % by weight, and the content of described the second glass dust is the 1-5 % by weight, and the content of described organic component is the 6-25 % by weight; The softening point of described the first glass dust is 350-550 ℃, and the softening point of described the second glass dust is 550-650 ℃, and differs at least 70 ℃ between the softening point of the first glass dust and the second glass dust.
2. electrode silver plasm according to claim 1 is characterized in that, differs 160-260 ℃ between the softening point of described the first glass dust and the second glass dust.
3. electrode silver plasm according to claim 1 is characterized in that, the content of described silver powder is 78-85wt%, and the content of described the first glass dust is 1.2-2wt%, and the content of described the second glass dust is 2.5-3.5wt%, and the content of described organic components is 8-18wt%.
4. electrode silver plasm according to claim 1 is characterized in that, described the first glass dust average grain diameter is the 0.1-10 micron, and the average grain diameter of described the second glass dust is the 0.1-10 micron.
5. electrode silver plasm according to claim 4 is characterized in that, described the first glass dust average grain diameter is the 0.3-1.5 micron.
6. electrode silver plasm according to claim 4 is characterized in that, the average grain diameter of described the second glass dust is the 2-6 micron.
7. electrode silver plasm according to claim 1 is characterized in that, described first glass dust contains the Pb of 65-90wt% or the compound of Bi.
8. electrode silver plasm according to claim 7 is characterized in that, described first glass dust is the lead borosilicate glass that contains 70-85wt%PbO.
9. electrode silver plasm according to claim 1 is characterized in that, described second glass dust contains SiO
2, B
2O
3, PbO, ZnO, Bi
2O
3, V
2O
5And alkali metal compound at least a.
10. electrode silver plasm according to claim 1 is characterized in that, the particle mean size of described silver powder is the 0.1-15 micron.
11. the preparation method of a front electrode silver slurry claimed in claim 1 is characterized in that, the method comprises mixes silver powder, the first glass frit, the second glass dust and organic component and grinding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110282715.7A CN103021511B (en) | 2011-09-22 | 2011-09-22 | A kind of crystal silicon solar energy battery front electrode silver slurry and preparation method thereof |
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Cited By (14)
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| CN103337277A (en) * | 2013-07-11 | 2013-10-02 | 中国工程物理研究院化工材料研究所 | Conductive silver paste for front electrode of solar battery and preparation method of conductive silver paste |
| CN103545016A (en) * | 2013-10-21 | 2014-01-29 | 深圳首创光伏有限公司 | Crystalline silicon solar cell front electrode electrocondution slurry and preparation method thereof |
| CN103545015A (en) * | 2013-10-21 | 2014-01-29 | 深圳首创光伏有限公司 | Crystalline silicon solar cell front electrode electrocondution slurry and preparation method thereof |
| CN103760055A (en) * | 2013-11-30 | 2014-04-30 | 彩虹集团电子股份有限公司 | Method for measuring silver content in silver slurry |
| CN104505139A (en) * | 2014-12-11 | 2015-04-08 | 乐凯胶片股份有限公司 | Low-resistance high-efficiency lead-free back silver pulp for amorphous silicon solar battery |
| CN105097070A (en) * | 2015-07-22 | 2015-11-25 | 深圳市春仰科技有限公司 | Positive conductive silver pulp of solar cell and preparation method of positive conductive silver pulp |
| CN107293349A (en) * | 2016-04-13 | 2017-10-24 | E.I.内穆尔杜邦公司 | Conducting paste composition and the semiconductor device being made of it |
| CN110289121A (en) * | 2019-06-19 | 2019-09-27 | 南通天盛新能源股份有限公司 | A kind of alloy aluminium paste for PERC rear surface of solar cell |
| CN110634618A (en) * | 2018-06-25 | 2019-12-31 | 优阳材料科技股份有限公司 | Method for manufacturing solar cell electrode, conductive paste and method for manufacturing conductive paste |
| CN111499208A (en) * | 2020-04-23 | 2020-08-07 | 常州聚和新材料股份有限公司 | Glass material for front silver paste of monocrystalline silicon solar cell and preparation method and application thereof |
| CN111557036A (en) * | 2017-11-06 | 2020-08-18 | LS-Nikko铜制炼株式会社 | Conductive paste for solar cell electrode and solar cell manufactured using same |
| CN115466057A (en) * | 2021-06-11 | 2022-12-13 | 厦门市敬微精密科技有限公司 | Composite glass slurry and preparation method thereof |
| CN116444164A (en) * | 2023-04-14 | 2023-07-18 | 西北大学 | Glass powder for TOPCON battery fine grid silver aluminum paste |
| CN116444164B (en) * | 2023-04-14 | 2024-04-19 | 西北大学 | Glass powder for TOPCon battery fine grid silver aluminum paste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103337277A (en) * | 2013-07-11 | 2013-10-02 | 中国工程物理研究院化工材料研究所 | Conductive silver paste for front electrode of solar battery and preparation method of conductive silver paste |
| CN103545016A (en) * | 2013-10-21 | 2014-01-29 | 深圳首创光伏有限公司 | Crystalline silicon solar cell front electrode electrocondution slurry and preparation method thereof |
| CN103545015A (en) * | 2013-10-21 | 2014-01-29 | 深圳首创光伏有限公司 | Crystalline silicon solar cell front electrode electrocondution slurry and preparation method thereof |
| CN103545016B (en) * | 2013-10-21 | 2016-06-29 | 深圳市首骋新材料科技有限公司 | Crystal silicon solar energy battery front electrode electrocondution slurry and preparation method thereof |
| CN103545015B (en) * | 2013-10-21 | 2016-08-24 | 深圳市首骋新材料科技有限公司 | Crystal silicon solar energy battery front electrode electrocondution slurry and preparation method thereof |
| CN103760055A (en) * | 2013-11-30 | 2014-04-30 | 彩虹集团电子股份有限公司 | Method for measuring silver content in silver slurry |
| CN103760055B (en) * | 2013-11-30 | 2016-02-10 | 彩虹集团电子股份有限公司 | The method of testing of silver content in a kind of silver paste |
| CN104505139B (en) * | 2014-12-11 | 2017-02-22 | 乐凯胶片股份有限公司 | Low-resistance high-efficiency lead-free back silver pulp for amorphous silicon solar battery |
| CN104505139A (en) * | 2014-12-11 | 2015-04-08 | 乐凯胶片股份有限公司 | Low-resistance high-efficiency lead-free back silver pulp for amorphous silicon solar battery |
| CN105097070B (en) * | 2015-07-22 | 2017-05-31 | 深圳市春仰科技有限公司 | Solar battery front side conductive silver paste and preparation method thereof |
| CN105097070A (en) * | 2015-07-22 | 2015-11-25 | 深圳市春仰科技有限公司 | Positive conductive silver pulp of solar cell and preparation method of positive conductive silver pulp |
| CN107293349A (en) * | 2016-04-13 | 2017-10-24 | E.I.内穆尔杜邦公司 | Conducting paste composition and the semiconductor device being made of it |
| CN107293349B (en) * | 2016-04-13 | 2020-12-25 | E.I.内穆尔杜邦公司 | Conductive paste composition and semiconductor device using the same |
| CN111557036A (en) * | 2017-11-06 | 2020-08-18 | LS-Nikko铜制炼株式会社 | Conductive paste for solar cell electrode and solar cell manufactured using same |
| CN111557036B (en) * | 2017-11-06 | 2022-03-25 | LS-Nikko铜制炼株式会社 | Conductive paste for solar cell electrode and solar cell manufactured using same |
| CN110634618A (en) * | 2018-06-25 | 2019-12-31 | 优阳材料科技股份有限公司 | Method for manufacturing solar cell electrode, conductive paste and method for manufacturing conductive paste |
| CN110289121A (en) * | 2019-06-19 | 2019-09-27 | 南通天盛新能源股份有限公司 | A kind of alloy aluminium paste for PERC rear surface of solar cell |
| CN111499208A (en) * | 2020-04-23 | 2020-08-07 | 常州聚和新材料股份有限公司 | Glass material for front silver paste of monocrystalline silicon solar cell and preparation method and application thereof |
| CN115466057A (en) * | 2021-06-11 | 2022-12-13 | 厦门市敬微精密科技有限公司 | Composite glass slurry and preparation method thereof |
| CN115466057B (en) * | 2021-06-11 | 2023-11-21 | 厦门市敬微精密科技有限公司 | Composite glass slurry and preparation method thereof |
| CN116444164A (en) * | 2023-04-14 | 2023-07-18 | 西北大学 | Glass powder for TOPCON battery fine grid silver aluminum paste |
| CN116444164B (en) * | 2023-04-14 | 2024-04-19 | 西北大学 | Glass powder for TOPCon battery fine grid silver aluminum paste |
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