CN104810076A - Silver-aluminum paste used for positive electrode of high-performance N type solar cell - Google Patents
Silver-aluminum paste used for positive electrode of high-performance N type solar cell Download PDFInfo
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- CN104810076A CN104810076A CN201510207047.XA CN201510207047A CN104810076A CN 104810076 A CN104810076 A CN 104810076A CN 201510207047 A CN201510207047 A CN 201510207047A CN 104810076 A CN104810076 A CN 104810076A
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Abstract
The invention provides silver-aluminum paste used for a positive electrode of a high-performance N type solar cell. The silver-aluminum paste aims at solving the problems that when homojunction metal aluminum powder serves as additives in silk-screen printing silver-aluminum paste of n type crystalline silicon solar cells, due to the fact that aluminum powder is prone to oxidation, aluminum is prevented from conducting further diffusion and alloying on p+ transmitter layers. The silver-aluminum paste is composed of electric conduction silver powder, glass powder, organic carrier phases and additive aluminum and silicon doped alloy powder, and is characterized in that the aluminum-silicone alloy powder serves as additives and the content of silicone in the aluminum-silicon alloy powder ranges from 1 wt% to 20 wt%. The aluminum-silicone alloy powder is heavily doped in p+ transmitters through diffusion, and therefore highly electrically-conductive loops are formed by silver-silicon transmitters, and the contact resistance is reduced. Due to the silicone in the aluminum-silicone alloy, it is avoided that the silicone in the p+ transmitters is diffused to the electrode due to mutual aluminum and silicone diffusion in the position of interfaces of the silver-silicone transmitters at a high temperature, surface defects of the transmitters can be avoided, electric leakage is reduced, and the open pressure is improved.
Description
Technical field
The invention belongs to area of solar cell, particularly relate to a kind of front electrode silver-aluminum slurry material.
Background technology
Improving conversion efficiency and reducing costs is the target that photovoltaic is chased always.Because the common metal impurity such as iron are large to the capture cross in the capture cross comparison hole of electronics, so under low injection condition, N-shaped silicon has higher minority carrier life time than p-type silicon.In solar level silicon materials, the effective minority carrier life time of N-shaped Cz silicon is at more than 1ms, even if the minority carrier life time of N-shaped polysilicon also can reach 100 μ s, far above p-type crystalline silicon.Therefore relative to p-type silicon, N-shaped crystalline silicon more satisfies the requirements and improves the conversion efficiency, particularly high performance solar batteries of solar cell, as IBC, HIT, double-side cell etc., requires higher, only have N-shaped crystalline silicon just can meet the demands to minority carrier life time.In addition, the decay of battery component in recent years more and more causes the attention of people, and particularly in dust storm, saline and alkaline, wet environment, p-type crystal silicon cell photo attenuation effect is particularly serious.As far back as 1973, H.Fischer and W.Pschunder(Fischer, H. and W.Pschunder. Investigation of photon and thermal induced changes in silicon solar cells. In 10
thiEEE Photovoltaic Specialists Conference. 1973. Palo Alto, CA, USA.) just find that the boron doped p type Cz monocrystalline solar cell just made there will be obvious decay under light illumination.1997, (Schmidt, J., A.G. Aberle, the and R. Hezel. Investigation of carrier lifetime instabilities in Cz-grown silicon. In 26 such as J.Schmidt
thiEEE PVSC.1997. New York, USA.) people confirms that the photo attenuation phenomenon that boron doping Cz silicon occurs is because boron oxygen is to caused, because in phosphorus doping N-shaped Cz silicon, Boron contents is extremely low, boron oxygen is not obvious to caused photo attenuation.Therefore, from the viewpoint of improving battery conversion efficiency and anti-induced attenuation further, N-shaped crystal silicon cell is studied and market-oriented Main way after being.
Continuing to reduce costs and improve constantly conversion efficiency is the inevitable requirement that photovoltaic can be widely used.Silk screen printing is the most important metallization process of current commercialization silica-based solar cell, is also the metallization mode that cost is minimum simultaneously.If but current business-like p-type silver slurry is directly used on N-shaped battery, contact resistance is too large, greatly lowers efficiency.Consider that aluminium paste is successfully used in the p-type silicon back side, therefore think that aluminium forms good ohmic to silver slurry and p+ emitter and contacts and play a key effect.In fact, experiment shows when aluminium joins in silver slurry as additive, along with the increase contact resistance of aluminium content obviously declines, but also cause remarkable increase (H. Kerp et al. " Development of screen printable contacts for p+ emitters in bifacial solar cells " the Proceedings 21st European Photovoltaic Solar Energy Conference of electric leakage and volume resistance simultaneously, Dresden Germany, 2006).The resistivity of pure metallic aluminum is 2.65X10
-8Ω m, the resistivity of pure metallic silver is 1.586X10
-8Ω m, therefore, along with aluminium content increases, volume resistance also can increase.And be very easily oxidized due to pure aluminum, form the protective layer of alumina of one deck insulation on superfine aluminium power surface, prevent aluminium to the further diffusion of p+ layer and alloying process.
In order to solve the silk screen printing of n-type crystalline silicon solar cell silver aluminium paste in elemental metals aluminium powder as additive, the oxidizable prevention aluminium of aluminium powder spreads and alloying problem further to p+ emitter layer, the invention provides the silver-colored aluminium paste of a kind of N-type solar cell front electrode, substitute simple metal aluminium powder by alusil alloy powder, the p+ for n-type crystalline silicon solar cell contacts.Silver-colored aluminium paste silk screen printing will be the invention provides on N-shaped crystal silicon cell, sinter at moderate temperatures through infrared sintering furnace, cell contact resistance will be low, open pressure high, leak electricity little, conversion efficiency is high.This thick film ink consist of conductive silver powder, glass dust, organic carrier phase, additive be alusil alloy powder.
Summary of the invention
The silver-colored aluminium paste composition of N-type solar cell front electrode comprises: conductive silver powder, glass dust, organic carrier phase and additive mix alusil alloy powder.Additive-aluminium silicon alloy powder is formed heavily doped by being diffused in p+ emitter, makes silver-colored silicon emitter form high connductivity path, reduces contact resistance.Under the existence of silicon from aluminum-silicon alloy avoids high temperature simultaneously, silver-colored silicon emitter interface makes the silicon in p+ emitter be diffused in electrode because aluminium silicon expands mutually, therefore can avoid causing emitter surface defect, reduces electric leakage, improves and opens pressure.Slurry of the present invention is applicable to N-shaped polycrystalline and single crystal silicon solar cell screen printing electrode.
1 conductive silver powder
Silver powder is the conductive phase in silver paste.Conductive silver powder can be elemental silver can be also silver alloy, comprises Ag-Cu, Ag-Ni, Ag-Pd, Ag-Mg alloy etc.Conductive silver powder can be spherical, sheet, near-spherical, bulk, dendroid etc.The diameter of conductive silver powder is 0.2--10 μm.If silver powder particles is less than 0.2 μm, silver powder surface energy is large, and sintering temperature is low, and silver-silicon interface place contact point is few, and contact resistance is large.If silver powder particles is greater than 10 μm, sintering temperature is high, and silver is easily diffused into silicon emitter inside, forms complex centre, causes electric leakage, even can puncture emitter, cause battery failure.The suitable size of conductive silver powder particle of the present invention is 1-5 μm, and the ratio of conductive silver powder in silver slurry is 75-95wt%, and suitable ratio is 80-90wt%.
2 additives
Alusil alloy has excellent chemical stability at normal temperatures, not oxidizable.Alusil alloy is in silicone content 12.2%(molar content) time eutectic temperature be 577 DEG C, during as N-shaped contact material high temperature sintering, alusil alloy melts, alusil alloy is made more easily to flow to silver-colored silicon contact interface, be convenient to aluminium be diffused in p+ emitter, improve the concentration of emitter charge carrier under electrode, reduce the contact resistance of silver-silicon interface, decrease body middle aluminium content mutually simultaneously, reduce volume resistance.In addition, under the existence of silicon from aluminum-silicon alloy prevents high temperature, silver-colored silicon emitter interface makes the silicon in p+ emitter be diffused in electrode because aluminium silicon expands mutually, therefore can avoid causing emitter surface defect, reduces electric leakage, improves and opens pressure.
Silicon from aluminum-silicon alloy content is 1-20wt%, and suitable content is in 5-15wt% scope.The too low silver-colored silicon interface place aluminium silicon that can not effectively suppress of silicone content expands mutually.Silicone content is too high, and the fusion temperature of alusil alloy is higher, not easily melts during sintering, makes aluminium silicon not play useful effect, causes volume resistance to increase simultaneously.The granular size of alusil alloy powder is 0.5-10 μm of scope.Addition is between 1-10wt%, if addition is lower than 1wt%, silver-colored silicon interface emitter can not form effective aluminium heavy doping; If addition is greater than 10%, electrode body resistance is increased, conversion efficiency reduces, and the welding performance of battery also can be made to decline simultaneously.The OK range of alusil alloy powder addition is between 1-6wt%.
3 glass dust
Glass dust is in the slurry as high temperature bond phase.Low melting point and glass transition temperature to be had for the glass in solar cell size, to silicon emitter surface and silver, there is good wetability under high temperature, SiNx antireflection layer can be penetrated, form good ohmic contact.In addition the composition of frit and sintering process also can have influence on solderability and the soldering resistance of electrode.Therefore, glass involved in the present invention is PbO-B
2o
3-SiO
2, TeO
2-B
2o
3– PbO, Bi
2o
3-B
2o
3-SiO
2, TeO
2-PbO system glass.The softening temperature of glass is 280-550 DEG C, and glass powder particles size is 1-10 μm.The ratio that glass dust accounts in the slurry is 1-10wt%, if glass content is lower than 1wt%, electrode adhesion intensity is little, molten silver and poor to SiNx opening capability, and contact resistance is large.If glass content is higher than 10wt%, silver-colored silicon contact interface place glassy layer is thicker, affects photoelectronic transmission and collection, meanwhile, body mutually in glass more, volume resistance can be caused to increase, conversion efficiency is reduced.
4 organic carrier phases
The effect of organic carrier is that conductive phase silver powder, glass dust, the mixing of additive-aluminium silicon alloy powder are dispersed into paste, forms the slurry with special flow sex change, thixotropic property.Make slurry under the effect of silk screen printing shearing force, accurately print off the electrode pattern of design, and make between electrode and silicon, to form good physical contact, make electrode have certain depth-width ratio.Organic carrier mainly contains solvent, thickener, plasticizer, surfactant, thixotropic agent composition mutually.Solvent mainly contains one or more compositions in turpentine oil, terpinol, butyl carbitol, butyl carbitol acetate, tributyl citrate, thickener is mainly ethyl cellulose, butyl cellulose, plasticizer is mainly phthalic acid ester, table activating agent is mainly caprylic acid, lecithin, class of department 85, and thixotropic agent is mainly rilanit special.
In silver slurry, the content of organic carrier phase is 3-10%.When organic carrier phase content lower than 3% time, organic carrier be mutually difficult to by silver powder, glass dust, the abundant wetting and dispersing of additive-aluminium silicon alloy powder; And when organic carrier phase content is greater than 10%, sintered density is too little after the electrode sintering printed, cause cell series resistance larger.
The preparation method of slurry: accurate weighing silver powder (granularity 1-3 μm of ball shape silver powder), tellurate system glass dust (granularity 3-5 μm), alusil alloy powder (silicone content 15wt%, granularity 1-3 μm), above-mentioned three kinds of powders total content 90wt% in the slurry, glass dust and organic phase remain unchanged, and change the ratio of silver powder and alusil alloy powder.After three kinds of pressed powders proportionally accurate weighing, these three kinds of powder are fully mixed, make it dispersed, then add organic phase fully stir carry out pre-dispersed, roll with three-roller again and be less than 14 μm to Hegman fineness grind, obtain the silver-colored aluminum slurry of N-shaped crystal silicon solar energy battery front electrode.
By the silk screen printing of obtained N-shaped silver aluminum slurry in n-type silicon chip, at a proper temperature through infrared sintering furnace sintering, obtained solar battery sheet, tests its electrical property.Silicon chip used is N-shaped monocrystalline silicon or polysilicon, through chemical surface making herbs into wool, expands after boron and forms p-n junction, sheet resistance 80-90/, and after removing Pyrex, carving limit, PECVD deposits SiNx antireflection layer, thickness 80-90nm.
Embodiment
Embodiment
According to formula preparation silver slurry S1, S2, S3 of table 1, be printed on monocrystalline (156mm × 156mm respectively, sheet resistance 80/), polycrystalline (156mm × 156mm, sheet resistance 90/) two kinds of specifications silicon chip on, obtained solar cell after sintering, test electrical property, certificate of taking the mean, the results are shown in table 3 and table 4.
Comparative example
By the technique identical with embodiment prepare solid content be 90wt%, add pure metallic aluminium powder 0, the conductive silver paste of 5wt, 10wt% is designated as A1, A2, A3.Printed electrode on the silicon chip of monocrystalline (156mm × 156mm, sheet resistance 80/), polycrystalline (156mm × 156mm, sheet resistance 90/) two kinds of specifications respectively, forms silicon solar cell through sintering, test electrical property, certificate of taking the mean.Obtained by embodiment and comparative example, the electrical property of solar cell is with S1 slurry battery for benchmark, and comparative result lists in table 3 and table 4.
The formula composition table of table 1 embodiment
| Silver slurry numbering | Silver powder | Alusil alloy powder | Glass dust | Organic phase | Silicon substrate |
| S1 | 86% | 1% | 3% | 10% | Monocrystalline silicon (80 Ω/) |
| S2 | 82% | 5% | 3% | 10% | Monocrystalline silicon (80 Ω/) |
| S3 | 77% | 10% | 3% | 10% | Monocrystalline silicon (80 Ω/) |
| S1 | 86% | 1% | 3% | 10% | Polysilicon (90 Ω/) |
| S2 | 82% | 5% | 3% | 10% | Polysilicon (90 Ω/) |
| S3 | 77% | 10% | 3% | 10% | Polysilicon (90 Ω/) |
The formula composition table of table 2 comparative example
| Silver slurry numbering | Silver powder | Aluminium powder | Glass dust | Organic phase | Silicon substrate |
| A1 | 87% | 0 | 3% | 10% | Monocrystalline silicon (80 Ω/) |
| A2 | 82% | 5% | 3% | 10% | Monocrystalline silicon (80 Ω/) |
| A3 | 77% | 10% | 3% | 10% | Monocrystalline silicon (80 Ω/) |
| A1 | 87% | 0 | 3% | 10% | Polysilicon (90 Ω/) |
| A2 | 82% | 5% | 3% | 10% | Polysilicon (90 Ω/) |
| A3 | 77% | 10% | 3% | 10% | Polysilicon (90 Ω/) |
The electrical performance data of the different silver-colored aluminium paste screen-printed metallization n-type crystalline silicon solar cell of table 3 compares (monocrystalline 80 Ω/)
The electrical performance data of the different silver-colored aluminium paste screen-printed metallization n-type crystalline silicon solar cell of table 4 compares (polycrystalline 90 Ω/)
Claims (6)
1. the silver-colored aluminium paste of high-performance N-type front electrode of solar battery, it is characterized in that this silver-colored aluminium paste is by conductive silver powder, additive-aluminium silicon alloy powder, glass dust and organic carrier phase composition, wherein, the content of conductive silver powder is 75-95wt%, the content of additive-aluminium silicon alloy powder is 1-10wt%, the content of glass dust is 1-10wt%, organic carrier phase 3-10wt%.
2. the silver-colored aluminium paste of N-shaped front electrode of solar battery according to claim 1, it is characterized in that described conductive silver powder be one in Ag, Ag-Cu alloy, Ag-Ni alloy, Ag-Pd alloy, Ag-Mg alloy and more than.
3. the silver-colored aluminium paste of N-shaped front electrode of solar battery according to claim 1 and 2, is characterized in that the mean particle size of described conductive silver powder is 0.2-10 μm.
4. the silver-colored aluminium paste of N-shaped front electrode of solar battery according to claim 1, is characterized in that the content of silicon in described additive-aluminium silicon alloy powder is 1-20wt%.
5. the silver-colored aluminium paste of N-shaped front electrode of solar battery according to claim 1 and 4, is characterized in that the mean particle size of described alusil alloy powder is 0.5-10 μm.
6. the silver-colored aluminium paste of N-shaped front electrode of solar battery according to claim 1, is characterized in that the mean particle size of described glass dust is 1-10 μm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110040968A (en) * | 2019-04-29 | 2019-07-23 | 南通天盛新能源股份有限公司 | A kind of glass powder and the silver-colored aluminium paste in N-type double-sided solar battery front including the glass powder |
| CN112489851A (en) * | 2020-11-09 | 2021-03-12 | 广州市儒兴科技开发有限公司 | N-type efficient battery front silver-aluminum paste |
| CN113257457A (en) * | 2021-05-12 | 2021-08-13 | 浙江奕成科技有限公司 | Silver-aluminum paste for high-performance N-type solar cell front surface fine grid and preparation method thereof |
| CN113409986A (en) * | 2021-07-14 | 2021-09-17 | 周静璐 | Silver-aluminum paste for solar cell P + electrode and solar cell |
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| CN102496404A (en) * | 2011-12-27 | 2012-06-13 | 华东理工大学 | Electrode silver paste used by high efficiency crystal silicon solar cell |
| CN103762249A (en) * | 2013-10-16 | 2014-04-30 | 杭州正银电子材料有限公司 | Back-field passivated-aluminum conductive slurry for crystalline-silicon solar cell and preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110040968A (en) * | 2019-04-29 | 2019-07-23 | 南通天盛新能源股份有限公司 | A kind of glass powder and the silver-colored aluminium paste in N-type double-sided solar battery front including the glass powder |
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| CN113257457A (en) * | 2021-05-12 | 2021-08-13 | 浙江奕成科技有限公司 | Silver-aluminum paste for high-performance N-type solar cell front surface fine grid and preparation method thereof |
| CN113409986A (en) * | 2021-07-14 | 2021-09-17 | 周静璐 | Silver-aluminum paste for solar cell P + electrode and solar cell |
| CN113409986B (en) * | 2021-07-14 | 2022-11-15 | 晶澜光电科技(江苏)有限公司 | Silver-aluminum paste for solar cell P + electrode and solar cell |
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Application publication date: 20150729 |