CN102262942A - Method for preparing conductive silver paste - Google Patents
Method for preparing conductive silver paste Download PDFInfo
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- CN102262942A CN102262942A CN2011102065929A CN201110206592A CN102262942A CN 102262942 A CN102262942 A CN 102262942A CN 2011102065929 A CN2011102065929 A CN 2011102065929A CN 201110206592 A CN201110206592 A CN 201110206592A CN 102262942 A CN102262942 A CN 102262942A
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Abstract
The invention provides a method for preparing a conductive silver paste, which comprises the following steps of: gasifying silver raw materials at high temperature in a vacuum environment; introducing inert gases which do not react with silver, so that silver steam is condensed into nanoparticles; collecting the silver nanoparticles in a solvent to obtain a mother solution containing the silver nanoparticles; and adding micron silver particles and glass powder into the mother solution containing the silver nanoparticles to obtain the conductive silver paste. The prepared conductive silver paste has the advantages of high electrical conductivity, low sintering temperature and low cost.
Description
Technical field
The present invention relates to the preparation method of conductive silver paste and this conductive silver paste.Specifically, the present invention relates to the conductive silver paste of usefulness and preparation method thereof that prints electrode of printing electrode of high conduction performance electrical equipment, particularly high performance solar batteries.
Background technology
More and more widely in recent years, based on the device application in daily life of semiconductor.For these devices, high-performance microization is pursued by people.Usually need be and prepare this high-performance micro device by printing the conductive silver electrode that forms.The electric conductivity of described silver electrode is good more, and resistance loss is more little, and electric wire just can be done carefully more; Correspondingly, it is just few more to be used to prepare the required silver of described silver electrode (conductive silver paste).Silver is precious metal, and high performance conductive silver paste not only improves device performance, and can reduce integrated cost.Show such as existing document, in the solar cell preparation process with silver-colored line as positive conductive electrode, the conductance that increases silver has increased photoelectric conversion efficiency.So preparing this high-effective conductive silver slurry is the target that modern industry is constantly made great efforts.Nearest result of study shows, starches with the silver of the silver powder preparation of micron order (1-2 μ m) and can improve conductance.This is that (tap density) is high more for tap density because silver powder is thin more, and the contact-making surface between particle and the particle increases.But if silver powder reaches nanoscale (particle diameter 5-500nm), electric conductivity descends on the contrary, and this is because the specific surface of nano particle increases, thereby face contact conductive phase is for the ratio increase of particle endosome conduction.Because face contacts conduction always not as the body conduction, so effect is bad on the contrary with face.In addition, the dispersing nanometer silver granuel is made stable silver slurry also needs more additive.Accordingly, the impurity increase has also reduced the conductivity of last silver-colored line.What is more, and silver surface always has the very thin surface oxide layer of one deck.The surface area of Nano Silver increases than bulk area, has also just introduced more polyoxy, and conductivity is reduced.
The CN101304050A of Piao Zanshuo etc. discloses a kind of slurry that is used to form electrode of solar battery.Wherein, in the micron silver granuel, joined a part of nano-silver powder.Because nano-silver powder is in the slit of micron silver granuel, can remedies the space between micron silver like this, thereby increase the conductivity between the micron silver.The high performance silver powder that this mixing silver powder is made has begun to demonstrate the advantage that increases conversion efficiency in the solar cell manufacturing.
But nano-silver powder preparation difficulty increases the manufacturing cost of this new silver paste.Nano Silver normally uses reducing agent (as N in the solution of silver salt
2H
4) generate.Owing to the existence of other anion and cation, make the purification process complexity of Nano Silver.Generally, the price of Nano Silver is at least 10 times of price of micron silver on the market.The another kind of method for preparing Nano Silver is the gas phase cohesion, and its solid filter commonly used is collected the Nano silver grain of gas phase.The rate of recovery of this collection mode very low (1～10%) makes that the silver powder cost will be very high.So the industrial application value of this method is little.
W. Sato etc. is at Production of ultrafine gold and silver particles by means of gas evaporation and solvent trap technique, Inorganic Chemical Acta, 148 (1988), 21-24 discloses the method for preparing ultra-fine gold and silver particles by gas evaporation and solvent collection.Specifically, its by under certain vacuum degree with the simple metal heating evaporation, with solvent the particle of volatilization is collected then, prepared the golden or silver-colored ultrafine particle of particle size distribution for about 5-20nm.But this design is only applicable to the laboratory to be used, and can not produce continuously.
So still need a kind of method for preparing conductive silver paste, wherein can produce Nano Silver, thereby high efficiency is utilized silver material with large-scale industrialization, again can low-cost production, make solar industry and other industrial silver paste realize high-performance, low cost.
Summary of the invention
The object of the invention is to reduce the production cost of silver paste, but still keeps excellent electric conductivity, thereby can be used for the production of solar cell and other high-performance electrical equipment.
For this reason, the invention provides a kind of preparation method of conductive silver paste, it comprises step: in vacuum environment the silver material high-temperature gasification; Import not the inert gas with the silver reaction, make silver-colored devaporation become nano particle; Nano silver grain is collected in the solvent, forms the mother liquor of silver nanoparticle-containing; With adding micron silver particles and glass dust (glass frit) in the mother liquor of silver nanoparticle-containing, form described conductive silver paste.
The invention still further relates to the conductive silver paste that obtains by said method.
Description of drawings
By the detailed description of carrying out below with reference to accompanying drawing, advantage of the present invention and further feature will be more apparent.Wherein,
Fig. 1 is the schematic representation of apparatus that the mother liquor of silver nanoparticle-containing produced according to the present invention is used.
Specific implementation method
Fig. 1 has provided the device that mother liquor that the present invention prepares silver nanoparticle-containing is used.Described device comprises Nano silver grain generating portion and Nano silver grain collection part (8).Described Nano silver grain generating portion comprises: vacuum tank (2), be arranged in the heater (1) of vacuum tank (2), opening is positioned at the wireway (3) of heater (1) top, be positioned at the carrier gas inlet pipe (6) between heater (1) and the wireway (3), wherein wireway (3) connects Nano silver grain collection part (8) by pump picking device (4).Described Nano silver grain is collected part (8) and being comprised: be positioned at Nano silver grain and collect the spray equipment (9) on part (8) top and be positioned at the liquid circulation pump (11) that Nano silver grain is collected part (8) bottom, described liquid circulation pump (11) links to each other with described spray equipment (9) by pipeline.Described Nano silver grain is collected part (8) and is comprised and exhaust port (10).
Described vacuum tank (2) can be used made such as stainless steel, aluminium.In one embodiment, additional cooling system is unlikely too warm with the surface temperature that guarantees described vacuum tank (2) on described vacuum tank (2) outer surface.
Described heater (1) is preferably crucible.Described crucible can be by graphite, platinum, and high-temperature materials such as tungsten are made.Heater (1) is outer to be equipped with electric furnace heating wire (13), is used to directly heat, and makes silver material (12) high-temperature gasification.Also can adopt high frequency electric source indirect induction method to make silver material (12) high-temperature gasification.Can also be disclosed as U.S. Pat 0065170A1, generate powder by arc process, in plasma, heat up again and gasification silver material (12).
Silver material (12) can be Any shape such as rod, piece, powder.Preferred silver material (12) has the purity more than 98%.
For avoiding silver material all will shut down additional problem after the gasification, can also comprise a device that adds silver material continuously in the Nano silver grain generating portion.This design is clearly for those skilled in the art that are familiar with this technology.
The temperature of silver material (12) can record by infrared remote control, and also available high temperature thermocouple is measured.The temperature of silver material (12) can be controlled at 1200-2000
oC.It is fixed that actual temp can come according to the particle diameter of Nano silver grain.Typical temperature is high more, and formed Nano silver grain particle diameter is big more.
The opening of wireway (3) is positioned at crucible top, and the opening of wireway can regulated at will to the distance of crucible, its objective is to allow silver-colored steam can enter wireway effectively.Wireway also can add temperature control measures such as condensation or heating, makes it keep stationary temperature.This temperature can determine the particle size and the particle size distribution of Nano silver grain.Preferred temperature is 5～400
oC.Temperature is high can to reduce silver condensing on tube wall, but formed particle can diminish.
Pump picking device (4) is vacuum pump, preferably oil-sealed rotary pump.This oil-sealed rotary pump is the commercially available prod.Preferred vacuum degree is 0.1-10 Torr.
Carrier gas (7) is introduced by carrier gas inlet pipe (6).Preferred carrier gas inlet pipe (6) is positioned between crucible and the wireway (3).Carrier gas (7) can provide by steel cylinder commonly used.A flowmeter (not shown) is housed, so that the control carrier gas flux on steam line.Carrier gas flux is directly related with the area of crucible, also influences the formation and the particle diameter of particle simultaneously.Preferred carrier gas flux is 0.5～10slm.Carrier gas (7) can be heated or cool off before entering container.The carrier gas temperature can influence the particle diameter of particle.Preferred carrier gas temperature is-100～+ 400
oC.Preferred carrier gas (7) is and the silver gas of chemically reactive not, as He, Ne, Ar, N
2, H
2With its mixture.
Between pump picking device (4) and Nano silver grain collection part (8), also be provided with vent valve (5), be used for regulating the pressure of the air-flow that enters described Nano silver grain collection part (8).
Nano silver grain is collected part (8) and can arbitrarily be designed, as long as can come out Nano silver grain effectively from gas phase.What the present invention used is spray process: make solvent (14), preferred pressurized solvent is sprayed from the top down by spray equipment (9), carries the carrier gas of Nano silver grain simultaneously and moves from bottom to top.The carrier gas and the solvent that carry Nano silver grain send reverse mixing, thereby Nano silver grain is washed in the solvent.In order fully to wash out Nano silver grain, can increase spray equipment (9) highly increases and washes out.Also can in spray equipment (9), inject pressure-air or nitrogen simultaneously, make the solvent atomizing, thereby more help washing out Nano silver grain.Also available a plurality of spray equipments (9) stacked, make wash out more complete.Tail gas is by exhaust port (10) emptying.Nano silver grain is discharged in the air can influence environment.If can not only improve productive rate by the effective collection Nano silver grain, reduce cost, and the protection environment.Therefore, can consider that tail gas is introduced another Nano silver grain collects part (8), thereby the degree of depth washes out Nano silver grain.
Solvent (14) recycles, and this finishes by liquid circulation pump (11).Liquid circulation pump (11) also pressurizes to solvent simultaneously.When Nano silver grain reached finite concentration in solvent, the mother liquor that just can take out as silver nanoparticle-containing used.In practical operation, can realize continued operation so that the adding fresh solvent is identical with the speed of the mother liquor of removing out silver nanoparticle-containing.Take-off speed is fast more, and Nano silver grain concentration is low more.The Nano silver grain concentration of the mother liquor of preferred silver nanoparticle-containing is 10-60 weight %, preferred 20-50 weight %.
Preferred solvent (7) is selected from acetate of butyl carbitol, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monomethyl ether acetate, benzinum, turpentine oil, terpinol and composition thereof, preferred acetate of butyl carbitol.Choice of Solvent be come according to the typography of slurry and performance fixed.
In one embodiment, in solvent, can add dispersant and stabilizer, make silver particles in solvent, form stable suspension-turbid liquid.Preferred dispersing agent is selected from polyvinylpyrrolidone (PVP), polyalcohol, oleic acid, fragrant alcohol ester, oleic acid, linoleic acid, leukotrienes and composition thereof.Dispersant chemisorbed quantitatively forms one deck monolayer in the nano grain of silver sub-surface, thereby starvation is avoided the oxidized and reunion of Nano silver grain.Fresh with the silver particles surface that the present invention generates, chemism is strong, is easy to and the dispersant combination.The preferred dispersants consumption adds 0.2～0.5 weight % of dispersant weight for Nano silver grain weight.
In the mother liquor of silver nanoparticle-containing, add micron silver particles and glass dust, form described conductive silver paste.Preferred described conductive silver paste contains the mother liquor of the silver nanoparticle-containing of 10-40 weight %, the micron silver particles of 30-85 weight %, 0.5-4 weight % glass dust.According to the requirement of concrete application to conductive silver paste, described conductive silver paste also contains functional additive, as is selected from dispersant, stabilizer, the functional additive of surface tension improver or flow promoter.If function of use additive, its consumption are the 5-20 weight % of conductive silver paste.In another embodiment, described conductive silver paste also contains the electric conductivity reinforcing agent, as is selected from phosphorus-containing compound, the electric conductivity reinforcing agent of Ag-containing compound or transistion metal compound.If electric conductivity reinforcing agent, its consumption are the 1-5 weight % of conductive silver paste.
The particle diameter of described micron silver particles is 1-2 μ m.That described micron silver particles is preferably is spherical, sheet, needle-like or its mixture.
Described glass dust can also contain PbO, B
2O
3, Bi
2O
3, Al
2O
3, SiO
2, SnO
2, TiO
2And composition thereof.This makes the anti-reflective film that can penetrate solar cell at conductive silver paste described in the high temperature sintering step of solar cell preparation process.
Be used for the following performance of conductive silver paste needs that prints electrode in the front of crystal silicon solar batteries:
High conductance;
In high-temperature sintering process, to penetrate the anti-reflective film of solar cell, form good Ohmic contact with internal layer silicon; With
In printing process, can keep high depth-width ratio.
Studies show that conductive silver paste of the present invention just can satisfy these requirements.In addition, described conductive silver paste can also contain aluminium powder, thereby can be used to prepare the crystal silicon solar backplate.Have the following advantages with the conductive silver paste that the present invention produced: the Nano Silver that the inventive method generated embodies (different therewith is directly to use the nano-silver powder by the drying of buying on the market usually) with mother liquor, and it can directly be used for being mixed with the silver slurry.Mother liquor with silver nanoparticle-containing of the present invention directly prepares the high-performance silver slurry, and owing to the oxidation that utilizes fully and avoided Nano Silver, thereby cost is low, and performance is good.So the invention solves a core difficult problem of preparation high-performance silver slurry.
Embodiment
The preparation of the mother liquor of embodiment 1. silver nanoparticle-containing
Silver bullion is placed in the graphite crucible, is heated to 1500 with electric furnace heating wire
oC, carrier gas is 3 slm nitrogen, the vacuum control of vacuum tank is at 2Torr.Nano silver grain that forms and carrier gas are extracted into Nano silver grain by oil-sealed rotary pump and collect part.Solvent for use is an acetate of butyl carbitol, wherein adds polyvinylpyrrolidone (PVP) dispersant of 5% (weight).The solution of Nano silver grain is carried in circulation, and Nano silver grain concentration to the last is 30 weight %.Taking-up is as the mother liquor of silver nanoparticle-containing.Measure the grain of Nano silver grain in the mother liquor through being 50-300nm by Zetasizer laser particle analyzer (making) by Malvern.
Get mother liquor 30 grams of embodiment 1, add flake micron silver particles (0.5-2 μ m) 60 grams, bismuth glass powder 2 grams, ethyl cellulose 7 grams, surfactant 1 gram, after mix stirring again through three Kun machines to its even dispersion, filter, thereby obtain being used for the conductive silver paste that prints electrode in the front of crystal silicon solar batteries.Use the U.S. HBDV-IIpro+ of Brookfield company type viscosimeter, adopt the SC4-14# rotor under the condition of 25 ℃ of rotating speed 10RPM of room temperature, the viscosity that records this conductive silver paste is 320Pa.s.
Get mother liquor 20 grams of embodiment 1, add flake micron silver particles (0.5-2 μ m) 10 grams, add spherical aluminium powder 60 grams (particle diameter 1-5 μ m), ethyl cellulose 8 grams, surfactant 1 gram, after mix stirring again through three Kun machines to its even dispersion, filter, thereby obtain being used for the conductive aluminum silver paste of the back up electrode of crystal silicon solar batteries.Use the U.S. HBDV-IIpro+ of Brookfield company type viscosimeter, adopt the SC4-14# rotor under the condition of 25 ℃ of rotating speed 10RPM of room temperature, the viscosity that records this conductive aluminum silver paste is 120Pa.s.
Above example only is reference, does not limit the scope of the invention.Those skilled in the art carry out fully it can any modification and change, and can not deviate from flesh and blood of the present invention.The scope of the invention is defined by the following claims.
Claims (11)
1. the preparation method of a conductive silver paste, it comprises step: in vacuum environment the silver material high-temperature gasification; Import not the inert gas with the silver reaction, make silver-colored devaporation become nano particle; Nano silver grain is collected in the solvent, forms the mother liquor of silver nanoparticle-containing; With adding micron silver particles and glass dust in the mother liquor of silver nanoparticle-containing, form described conductive silver paste.
2. the method for claim 1, wherein the Nano silver grain concentration of the mother liquor of silver nanoparticle-containing is 10-60 weight %, preferred 20-50 weight %.
3. the method for claim 1, wherein a micron silver particles particle diameter is 1-2 μ m.
4. the method for claim 1, wherein said conductive silver paste contains the mother liquor of the silver nanoparticle-containing of 10-40 weight %, the micron silver particles of 30-85 weight % and 0.5-4 weight % glass dust.
5. the method for claim 1, wherein said glass dust also contains PbO, B
2O
3, Bi
2O
3, Al
2O
3, SiO
2, SnO
2, TiO
2With its mixture.
6. the method for claim 1, wherein said conductive silver paste also contain and are selected from dispersant, stabilizer, the functional additive of surface tension improver and flow promoter.
7. method as claimed in claim 6, wherein said conductive silver paste contains the functional additive of 5-20 weight %.
8. the method for claim 1, wherein said conductive silver paste also contain and are selected from phosphorus-containing compound, the electric conductivity reinforcing agent of Ag-containing compound and transistion metal compound.
9. method as claimed in claim 8, wherein said conductive silver paste contain the electric conductivity reinforcing agent of 1-5 weight %.
10. the method for claim 1, wherein said conductive silver paste also contains aluminium powder.
11. conductive silver paste according to each described method preparation of claim 1-10.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102831953A (en) * | 2012-08-24 | 2012-12-19 | 合肥中南光电有限公司 | Aluminum powder mixed silver paste for crystalline silicon solar cell anode and preparation method of aluminum powder mixed silver paste |
| CN103310870A (en) * | 2012-03-12 | 2013-09-18 | 深圳市圣龙特电子有限公司 | Lead-free copper slurry applied to silicon solar battery electrode and preparation method thereof |
| CN104379247A (en) * | 2012-06-05 | 2015-02-25 | 道康宁公司 | Fluid capture of nanoparticles |
| CN104751935A (en) * | 2013-12-26 | 2015-07-01 | 湖南利德电子浆料有限公司 | High-sheet-resistance efficient solar cell front silver paste and preparation method thereof |
| CN111117368A (en) * | 2019-12-10 | 2020-05-08 | 深圳第三代半导体研究院 | Preparation method of nano-metal in-situ conductive ink |
| CN114242339A (en) * | 2021-12-24 | 2022-03-25 | 西南科技大学 | Nano silver wire preparation device and preparation method of front silver paste for solar cell |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103310870A (en) * | 2012-03-12 | 2013-09-18 | 深圳市圣龙特电子有限公司 | Lead-free copper slurry applied to silicon solar battery electrode and preparation method thereof |
| CN104379247A (en) * | 2012-06-05 | 2015-02-25 | 道康宁公司 | Fluid capture of nanoparticles |
| CN102831953A (en) * | 2012-08-24 | 2012-12-19 | 合肥中南光电有限公司 | Aluminum powder mixed silver paste for crystalline silicon solar cell anode and preparation method of aluminum powder mixed silver paste |
| CN102831953B (en) * | 2012-08-24 | 2014-07-30 | 合肥中南光电有限公司 | Aluminum powder mixed silver paste for crystalline silicon solar cell anode and preparation method of aluminum powder mixed silver paste |
| CN104751935A (en) * | 2013-12-26 | 2015-07-01 | 湖南利德电子浆料有限公司 | High-sheet-resistance efficient solar cell front silver paste and preparation method thereof |
| CN111117368A (en) * | 2019-12-10 | 2020-05-08 | 深圳第三代半导体研究院 | Preparation method of nano-metal in-situ conductive ink |
| CN114242339A (en) * | 2021-12-24 | 2022-03-25 | 西南科技大学 | Nano silver wire preparation device and preparation method of front silver paste for solar cell |
| CN114242339B (en) * | 2021-12-24 | 2023-09-22 | 西南科技大学 | Device and method for preparing nano silver wire of front silver paste for solar cell |
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Application publication date: 20111130 |