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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- conductive silver
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052709 silver Inorganic materials 0.000 claims abstract description 81
- 239000004332 silver Substances 0.000 claims abstract description 81
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 42
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- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 10
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
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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 invention relates to conductive silver paste and a preparation method of the conductive silver paste. In particular to a conductive silver paste for a printed electrode of a high-conductivity electrical appliance, in particular to a conductive silver paste for a printed electrode of a high-efficiency solar cell and a preparation method thereof.
Background
Semiconductor-based devices have become more and more popular for use in everyday life in recent years. For these devices, high-performance miniaturization is sought. The fabrication of such high performance micro devices typically requires conductive silver electrodes formed by printing. The better the conductivity of the silver electrode is, the smaller the resistance loss is, the thinner the wire can be made; accordingly, the less silver (conductive silver paste) is required for preparing the silver electrode. Silver is a noble metal, and the high-performance conductive silver paste not only improves the performance of devices, but also can reduce the comprehensive cost. For example, the prior literature shows that the photoelectric conversion efficiency is improved by increasing the conductivity of silver by using a silver wire as a front conductive electrode in the preparation process of a solar cell. Therefore, the preparation of the high-efficiency conductive silver paste is the aim of continuous efforts of modern industries. Recent research results show that silver paste prepared with silver powder of micron size (1-2 μm) can improve conductivity. This is because the finer the silver powder is, the higher the tap density (tap density) is, and the particle-to-particle contact surface increases. However, if the silver powder reaches the nano-scale (particle diameter 5-500 nm), the conductive performance is rather degraded because the specific surface area of the nanoparticle is increased, and thus the ratio of the surface contact conductivity to the bulk conductivity in the particle is increased. The effect is rather poor since surface-to-surface contact conduction is not always as good as bulk conduction. In addition, more additives are needed to disperse nano silver particles to prepare stable silver paste. Accordingly, the increase in impurities also reduces the conductivity of the final silver wire. Furthermore, the silver surface always has a very thin surface oxide layer. The surface area of the nano silver is increased compared with the volume area, more oxygen is introduced, and the conductivity is reduced.
CN101304050A of prankauso et al discloses a paste for forming electrodes of solar cells. Wherein, a part of nano silver powder is participated in the micron silver particles. Because the nano silver powder is positioned in the gaps of the micro silver particles, the gaps between the micro silver particles can be compensated, and the conductivity between the micro silver particles is increased. High performance silver powders made from such mixed silver powders have begun to exhibit the advantage of increased conversion efficiency in solar cell fabrication.
However, the preparation of the nano silver powder is difficult, so that the manufacturing cost of the new silver paste increases. Nano-silver is usually prepared by dissolving a reducing agent (such as N) in a silver salt solution2H4) And (4) generating. The purification process of the nano silver is complicated due to the existence of other negative ions and positive ions. Typically, the price of nanosilver on the market is at least 10 times the price of microsilver. Another method for preparing nano silver is gas phase condensation, which collects silver nanoparticles in a gas phase using a solid filter. The recovery rate of the collection method is very low (1-10%), so that the cost of the silver powder is very high. Therefore, the industrial application value of this method is not great.
A process for preparing ultrafine gold and silver particles by gas phase evaporation and solvent collection is disclosed by Sato et al in the Production of ultra fine gold and solvent particles by means of medium of gas evolution and solvent trap technology, Inorganic Chemical Acta, 148(1988), 21-24. Specifically, it prepares ultrafine particles of gold or silver having a particle size distribution of about 5 to 20nm by heating and evaporating pure metal under a certain vacuum degree and then collecting the volatilized particles with a solvent. However, this design is only suitable for laboratory use and does not allow continuous production.
There is still a need for a method of preparing conductive silver paste, in which nano silver can be industrially mass-produced, thereby efficiently utilizing silver raw materials and realizing low-cost production with high performance and low cost for silver paste for solar industry and other industries.
Disclosure of Invention
The invention aims to reduce the production cost of the silver paste, but still maintain excellent conductive performance, so that the silver paste can be used for producing solar cells and other high-performance electric appliances.
Therefore, the invention provides a preparation method of conductive silver paste, which comprises the following steps: gasifying the silver raw material at high temperature in a vacuum environment; introducing inert gas which does not react with the silver to condense the silver vapor into nano particles; collecting silver nanoparticles in a solvent to form a mother liquor containing silver nanoparticles; and adding micron silver particles and glass frit (glass frit) into the mother solution containing the silver nanoparticles to form the conductive silver paste.
The invention also relates to the conductive silver paste obtained by the method.
Drawings
Advantages and other features of the present invention will become more apparent from the following detailed description, which proceeds with reference to the accompanying drawings. Wherein,
fig. 1 is a schematic view of an apparatus for preparing a mother liquor containing silver nanoparticles according to the present invention.
Detailed description of the invention
FIG. 1 shows an apparatus for preparing a mother liquor containing silver nanoparticles according to the present invention. The device includes a silver nanoparticle generation section and a silver nanoparticle collection section (8). The silver nanoparticle generation section includes: the silver nanoparticle collecting device comprises a vacuum container (2), a heating device (1) arranged in the vacuum container (2), a gas guide pipe (3) with an opening arranged above the heating device (1), and a carrier gas inlet pipe (6) arranged between the heating device (1) and the gas guide pipe (3), wherein the gas guide pipe (3) is connected with a silver nanoparticle collecting part (8) through a pumping device (4). The silver nanoparticle collection portion (8) includes: the silver nanoparticle collecting device comprises a spraying device (9) positioned at the upper part of the silver nanoparticle collecting part (8) and a liquid circulating pump (11) positioned at the lower part of the silver nanoparticle collecting part (8), wherein the liquid circulating pump (11) is connected with the spraying device (9) through a pipeline. The silver nanoparticle collection portion (8) includes a vent (10) for exhaust gases.
The vacuum container (2) can be made of stainless steel, aluminum and the like. In one embodiment, a cooling system is added to the external surface of the vacuum vessel (2) to ensure that the surface temperature of the vacuum vessel (2) is not too hot.
The heating device (1) is preferably a crucible. The crucible can be made of high temperature materials such as graphite, platinum, tungsten and the like. An electric furnace wire (13) is arranged outside the heating device (1) and is used for directly heating and gasifying the silver raw material (12) at high temperature. The silver raw material (12) can also be gasified at high temperature by adopting a high-frequency power supply indirect induction method. It is also possible to produce a powder by the arc process, as disclosed in US0065170a1, and then to heat up and gasify the silver feedstock (12) in a plasma.
The silver source (12) may be in any shape such as a rod, block, powder, etc. Preferably, the silver source material (12) has a purity of greater than 98%.
In order to avoid the problem of stopping replenishment after the silver raw material is completely gasified, a device for continuously adding the silver raw material can be further included in the silver nanoparticle generation part. Such a design will be apparent to one skilled in the art familiar with this technology.
The temperature of the silver raw material (12) can be measured by infrared remote control or by a high-temperature thermocoupleAnd (6) measuring. The temperature of the silver raw material (12) can be controlled to be 1200-2000-oC. The specific temperature may be determined according to the particle size of the silver nanoparticles. Generally, the higher the temperature, the larger the particle size of the silver nanoparticles formed.
The opening of the gas guide tube (3) is positioned above the crucible, and the distance from the opening of the gas guide tube to the crucible can be adjusted at will, so that silver steam can effectively enter the gas guide tube. The gas-guide tube can be added with temperature control measures such as condensation or heating, etc. to keep the gas-guide tube at a constant temperature. The temperature will determine the particle size and particle size distribution of the silver nanoparticles. The preferable temperature is 5 to 400 DEGoC. High temperatures reduce the condensation of silver on the tube wall, but the particles formed become smaller.
The pumping means (4) is a vacuum pump, preferably a mechanical vacuum pump. Such mechanical vacuum pumps are commercially available. The degree of vacuum is preferably 0.1 to 10 Torr.
The carrier gas (7) is introduced through a carrier gas inlet tube (6). Preferably, a carrier gas inlet tube (6) is located between the crucible and the gas-guide tube (3). The carrier gas (7) may be supplied from a conventional steel cylinder. A flow meter (not shown) is installed on the gas supply line to control the flow rate of the carrier gas. The carrier gas flow is directly related to the area of the crucible and also affects particle formation and particle size. Preferably, the flow rate of the carrier gas is 0.5 to 10 slm. The carrier gas (7) may be heated or cooled before entering the container. The carrier gas temperature affects the particle size of the particles. The preferred carrier gas temperature is-100 to +400 deg.CoC. The carrier gas (7) is preferably a gas which does not react with silver, such as He, Ne, Ar, N2、H2And mixtures thereof.
A gas release valve (5) is also arranged between the pumping device (4) and the silver nano particle collecting part (8) and is used for adjusting the pressure of the gas flow entering the silver nano particle collecting part (8).
The silver nanoparticle collecting portion (8) may be arbitrarily designed as long as the silver nanoparticles can be efficiently washed out from the gas phase. The invention uses a spraying method: a solvent (14), preferably a pressurized solvent, is sprayed from the top down by a spray device (9) while a carrier gas carrying silver nanoparticles is moved from the bottom up. The carrier gas carrying the silver nanoparticles and the solvent are sent to be mixed in a reverse direction, thereby washing the silver nanoparticles into the solvent. In order to sufficiently wash out the silver nanoparticles, the height of the shower device (9) may be increased to increase the washing out. High-pressure air or nitrogen can also be injected into the spraying device (9) at the same time to atomize the solvent, thereby being more beneficial to washing out the silver nano particles. It is also possible to use a stack of several showers (9) to achieve more complete washing. The tail gas is exhausted through a tail gas exhaust port (10). The release of silver nanoparticles into the air can affect the environment. If the silver nanoparticles can be effectively collected, the yield is improved, the cost is reduced, and the environment is protected. Therefore, it can be considered that the off-gas is introduced into another silver nano-particle collecting section (8) to wash out the silver nano-particles deeply.
The solvent (14) is recycled by means of a liquid circulation pump (11). The liquid circulation pump (11) also pressurizes the solvent. When the silver nano particles reach a certain concentration in the solvent, the silver nano particles can be taken out to be used as mother liquor containing the silver nano particles. In practice, continuous operation can be achieved by adding fresh solvent and removing the mother liquor containing silver nanoparticles at the same rate. The faster the withdrawal rate, the lower the silver nanoparticle concentration. It is preferable that the mother liquor containing silver nanoparticles has a silver nanoparticle concentration of 10 to 60% by weight, preferably 20 to 50% by weight.
Preferably, solvent (7) is selected from butyl carbitol acetate, propylene glycol methyl ether acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether acetate, petroleum ether, turpentine, terpineol, and mixtures thereof, preferably butyl carbitol acetate. The choice of solvent is dependent on the printing process and the properties of the paste.
In one embodiment, a dispersant and a stabilizer may be added to the solvent to form a stable suspension of the silver particles in the solvent. Preferred dispersants are selected from the group consisting of polyvinylpyrrolidone (PVP), polyols, oleic acid, aromatic alcohol esters, oleic acid, linoleic acid, linolenic acid, and mixtures thereof. The dispersing agent can be quantitatively and chemically adsorbed on the surfaces of the silver nano particles to form a monomolecular layer, so that oxygen is isolated, and the silver nano particles are prevented from being oxidized and agglomerated. The silver particles produced by the method have fresh surfaces and strong chemical activity, and can be easily combined with a dispersing agent. The preferable amount of the dispersant is 0.2-0.5 wt% of the weight of the silver nanoparticles plus the weight of the dispersant.
And adding micron silver particles and glass powder into the mother solution containing the silver nanoparticles to form the conductive silver paste. Preferably, the conductive silver paste contains 10-40 wt% of mother liquor containing silver nanoparticles, 30-85 wt% of micron silver particles and 0.5-4 wt% of glass powder. The conductive silver paste further contains a functional additive, such as a functional additive selected from a dispersant, a stabilizer, a surface tension improver or a fluidity improver, according to the requirements of a specific application on the conductive silver paste. If the functional additive is used, it is used in an amount of 5 to 20 wt% of the conductive silver paste. In another embodiment, the conductive silver paste further contains a conductivity enhancing agent, such as a conductivity enhancing agent selected from a phosphorus-containing compound, a silver-containing compound, or a transition metal compound. If the conductivity enhancer is used, the amount of the conductivity enhancer is 1-5 wt% of the conductive silver paste.
The particle size of the micron silver particles is 1-2 μm. The micro silver particles are preferably spherical, platelet, needle-shaped or mixtures thereof.
The glass powder can also contain PbO and B2O3、Bi2O3、Al2O3、SiO2、SnO2、TiO2And mixtures thereof. This enables the conductive silver paste to penetrate the anti-reflection film of the solar cell in the high-temperature sintering step of the solar cell manufacturing process.
The conductive silver paste for the front side printing electrode of the crystalline silicon solar cell requires the following properties:
high electrical conductivity;
the anti-reflection film of the solar cell is penetrated in the high-temperature sintering process, and good ohmic contact is formed between the anti-reflection film and the inner layer silicon; and
high aspect ratios can be maintained during printing.
Research shows that the conductive silver paste of the present invention can meet these requirements. In addition, the conductive silver paste can also contain aluminum powder, so that the conductive silver paste can be used for preparing a crystalline silicon solar back electrode. The conductive silver paste produced by the invention has the following advantages: the nano silver generated by the method is embodied as mother liquor (different from the mother liquor, the dried nano silver powder purchased from the market is generally directly used), and the nano silver can be directly used for preparing silver paste. The mother liquor containing silver nano particles is used for directly preparing the high-performance silver paste, and the oxidation of the nano silver is avoided due to full utilization, so that the cost is low, and the performance is good. Therefore, the invention solves a core problem of preparing the high-performance silver paste.
Examples
EXAMPLE 1 preparation of mother liquor containing silver nanoparticles
Placing the silver block in a graphite crucible, and heating to 1500 deg.C with electric furnace wireoC, the carrier gas was 3 slm of nitrogen, and the vacuum of the vacuum vessel was controlled at 2 Torr. The formed silver nanoparticles and carrier gas were pumped by a mechanical vacuum pump to the silver nanoparticle collection portion. The solvent used was butyl carbitol acetate to which was added 5% by weight of polyvinylpyrrolidone (PVP) dispersant. The solution carrying the silver nanoparticles was circulated until the final silver nanoparticle concentration was 30 wt%. The mother liquor containing silver nanoparticles was taken out. The particle size of the silver nanoparticles in the mother liquor was measured by a Zetasizer laser particle sizer (manufactured by Malvern) to be 50 to 300 nm.
Example 2 conductive silver paste for front side printing electrode of crystalline silicon solar cell
Taking 30 g of the mother liquor of the embodiment 1, adding 60 g of flaky micron silver particles (0.5-2 μm), 2 g of bismuth-based glass powder, 7 g of ethyl cellulose and 1 g of surfactant, uniformly dispersing the mixture by a three-roll machine after mixing and stirring, and filtering to obtain the conductive silver paste for the front printed electrode of the crystalline silicon solar cell. The conductive silver paste had a viscosity of 320Pa.s measured at room temperature at 25 ℃ and at 10RPM using a Brookfield company HBDV-IIpro + type viscometer in the United states and a rotor # SC 4-14.
Example 3 conductive aluminum silver paste for Back printing electrode of crystalline silicon solar cell
Taking 20 g of the mother liquor of the embodiment 1, adding 10 g of flaky micron silver particles (0.5-2 μm), 60 g of spherical aluminum powder (particle size of 1-5 μm), 8 g of ethyl cellulose and 1 g of surfactant, uniformly dispersing the mixture by a three-roll machine after mixing and stirring, and filtering to obtain the conductive aluminum silver paste for the back printing electrode of the crystalline silicon solar cell. The conductive aluminum silver paste was measured to have a viscosity of 120Pa.s using a Brookfield company HBDV-IIpro + type viscometer using a SC4-14# rotor at 25 ℃ at 10RPM at room temperature.
The above examples are merely references and do not limit the scope of the invention. And that those skilled in the art will be able to make all changes and modifications thereto without departing from the spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (11)
1. A preparation method of conductive silver paste comprises the following steps: gasifying the silver raw material at high temperature in a vacuum environment; introducing inert gas which does not react with the silver to condense the silver vapor into nano particles; collecting silver nanoparticles in a solvent to form a mother liquor containing silver nanoparticles; and adding micron silver particles and glass powder into the mother solution containing the silver nanoparticles to form the conductive silver paste.
2. The process as claimed in claim 1, wherein the mother liquor containing silver nanoparticles has a silver nanoparticle concentration of 10 to 60 wt.%, preferably 20 to 50 wt.%.
3. The method of claim 1, wherein the micron silver particles have a particle size of 1-2 μm.
4. The method of claim 1, wherein the conductive silver paste comprises 10-40 wt% of a mother liquor comprising silver nanoparticles, 30-85 wt% of micro silver particles, and 0.5-4 wt% of glass frit.
5. The method of claim 1, wherein the glass frit further comprises PbO, B2O3, Bi2O3, Al2O3, SiO2, SnO2, TiO2And mixtures thereof.
6. The method of claim 1, wherein the conductive silver paste further comprises a functional additive selected from the group consisting of a dispersant, a stabilizer, a surface tension improver, and a fluidity improver.
7. The method of claim 6, wherein the conductive silver paste contains 5-20 wt% of the functional additive.
8. The method of claim 1, wherein said conductive silver paste further comprises a conductivity enhancing agent selected from the group consisting of phosphorus-containing compounds, silver-containing compounds, and transition metal compounds.
9. The method of claim 8 wherein said conductive silver paste contains 1-5 wt% conductivity enhancer.
10. The method of claim 1, wherein the conductive silver paste further comprises aluminum powder.
11. Conductive silver paste prepared according to the method of any one of claims 1 to 10.
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| 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 |
| CN111495298A (en) * | 2020-05-15 | 2020-08-07 | 广东先导稀材股份有限公司 | Plasma arc magnetic force rotary gasification powder making furnace |
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| 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 |
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| 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 |
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| 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 |
| CN111495298A (en) * | 2020-05-15 | 2020-08-07 | 广东先导稀材股份有限公司 | Plasma arc magnetic force rotary gasification powder making furnace |
| 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 |