A particle-free glass component ink for conductive paste / ink, preparation and application thereof

Abstract

The application belongs to the technical field of conductive paste, and discloses a non-particle type glass component ink applied to conductive paste / ink, and a preparation and application thereof. 20-50% of bismuth precursor components, 1-20% of glass components containing silicon and boron, 10-20% of amine complexing agents, and 0.001-10% of organic additives, and the rest is solvent. The non-particle type glass component ink is used as a sintering aid to replace part of the glass powder in the conductive paste, and decomposes to form a glass phase at a lower temperature, fills the gaps between metal particles, and densifies the metal film. The glass phase penetrates into the surface of the substrate during sintering, improves the bonding force between the metal and the substrate, forms a good ohmic contact between the metal and the substrate, improves the difference in the thermal expansion coefficient between the metal and the substrate after the decomposition of the conductive paste, and reduces the stress unevenness and cracks caused by the thermal expansion mismatch during the sintering process.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of conductive paste, in particular to a particle-free glass component ink applied to conductive paste / ink, preparation and application thereof. BACKGROUND

[0002] Conductive pastes are a commonly used functional material, widely used in photovoltaics, microelectronic packaging, sensors, displays, RFID and printed antennas, integrated circuit printing, etc. In the production of crystalline silicon solar cells, silver-based conductive pastes are used as front and back electrodes (backside paste for BSF or PERC structures) to ensure efficient photocurrent collection and low contact resistance. Conductive pastes also play a key role in semiconductor packaging, especially in high-density interconnection technology and flip-chip technology, for screen printing to form reliable circuit connections and heat dissipation paths. Silver / palladium paste is commonly used for the manufacture of internal electrodes of multilayer ceramic capacitors (MLCCs). In the manufacture of liquid crystal displays (LCDs) and organic light-emitting diodes (OLEDs), conductive pastes are used to make transparent conductive electrodes, which can replace traditional indium tin oxide (ITO) electrodes, improve the stretchability of the electrodes while reducing costs. With the rapid innovation and development of electronic, information and microelectronic technologies, electronic devices are developing towards environmental protection, integration and miniaturization, which puts higher and higher requirements on the performance of conductive pastes. The development of new environmentally friendly electronic pastes with high performance and low cost has become a research hotspot.

[0003] Conductive pastes are composed of conductive particles (such as noble metal powders, carbon-based nanomaterials, composite conductive particles, etc.), glass powder and organic carrier, wherein the glass powder is usually composed of low-melting inorganic oxides. During the subsequent sintering process of the conductive paste, the glass powder is heated to a molten state to wet the surface of the substrate, promoting the densification and arrangement of the metal. The molten glass powder forms a glass phase between the metal particles after cooling, forming a dense metal film that improves the mechanical strength and electrical properties of the metal circuit or electrode. During the sintering process, the molten glass powder penetrates and adheres to the surface of the substrate, and after cooling, it bonds the metal and the substrate, while reducing the difference in thermal expansion coefficient between the metal and the substrate, forming a firm connection between the metal and the substrate.

[0004] Traditional conductive paste mostly uses lead-containing glass powder as binder, while lead is harmful to health and environment, and its use and emission should be limited, which makes the preparation of silver conductive paste with lead-free glass powder as binder a research direction. Common lead-free glass powder is calcium oxide system, bismuth oxide system and aluminum oxide system. The glass transition temperature of calcium oxide system and aluminum oxide system glass powder is relatively high, and the higher the temperature, the higher the cost, and the too high sintering temperature affects the integrity of the metal circuit after sintering. The bismuth oxide system glass powder usually has a relatively low melting point, and the glass transition can be completed at about 800℃, and can form a firm connection with various substrates. However, for some substrates that cannot withstand high temperatures, such as PVA, PET, PI and other polymers, irreversible damage will occur at this sintering temperature, which greatly limits the application range of conductive paste.

[0005] In addition, the particle size of glass powder has a great influence on the performance of conductive paste. The oxide particles in common glass powder are mechanically crushed by ball milling and other methods, and are uniform particles with an average particle size of several microns. The average size of the glass melt contained in the conductive paste is large, which is filled between the metals and the substrate during sintering, so that the metal is not easy to form a continuous conductive path due to poor contact and metallization. In "Jeon S J, Koo SM, Am Hwang S. Optimization of lead-and cadmium-free front contact silver paste formulation to achieve high fill factors for industrial screen-printed Si solar cells [J]. Solar Energy Materials and Solar Cells, 2009, 93(6-7): 1103-1109", the effect of average particle size of glass powder on the conductivity of conductive paste is studied. The solar cell made of paste with larger particle glass powder has higher junction shunt and leakage rate, and when using glass melt with smaller average size particles, the amount of glass powder can be reduced, and higher fill factor and conversion efficiency can be obtained.

[0006] The main components of the particle-free glass phase ink proposed in the present application are some low-melting organic solvents, bismuth-containing precursors and boron-silicon-containing components, which can decompose to produce bismuth oxide and other glass phase components at a lower temperature. The glass phase ink is added to the conductive paste, and the glass phase material produced during sintering can bond the metal and the substrate, so as to produce ohmic contact between the metal and the substrate, improve the bonding force between the metal and the substrate, and replace the function of traditional glass powder.

[0007] The glass phase ink provided by the application is a non-particle type and does not contain large-particle oxide components. A certain proportion of the traditional glass powder is replaced to add into the conductive paste to mix uniformly, and in the sintering process, the nanoscale glass phase particles are generated in situ to fill between the metal particles to densify them. The small-particle glass phase can also reduce the influence of the traditional large-particle glass melt on the interface connectivity between the metal particles, so as to produce good ohmic contact and improve the metal conductivity. SUMMARY

[0008] The application provides a non-particle type glass component ink preparation method which is simple in process and green in environment and solves the problems of high glass transition temperature of the traditional glass powder in the existing conductive paste, high sintering temperature of the conductive paste which limits the application scene, and large particle size of the glass powder which affects the ohmic contact between the metal particles. The ink is used as a sintering aid to replace part of the glass powder in the existing conductive paste, can be sintered at a lower temperature to produce a glass phase component to bond the metal and the substrate, and improve the bonding force between the metal and the substrate. At the same time, small-particle glass phase substances are generated in situ to fill between the micron-level metal particles, and the bad influence of the large-particle glass melt in the traditional glass phase on the ohmic contact between the metal is improved.

[0009] In order to achieve the above object, the main technical scheme adopted by the application is as follows: a non-particle type glass component ink applied to conductive paste / ink, wherein the non-particle type glass component ink is formed by using a bismuth precursor component and an amine complexing agent to form a stable complex, adding a glass component containing silicon and boron, dissolving in an organic solvent to filter to form a non-particle type ink, and then adding into the traditional conductive paste as a sintering aid; the non-particle type glass component ink is in-situ decomposed to generate bismuth oxide, boron oxide and silicon oxide in the sintering process, and fill between the metal particles and between the metal and the substrate, and further heated to become a molten state, and after cooling and solidification, a dense ohmic contact is generated.

[0010] An additive is added into the non-particle type glass component ink to adjust the viscosity and leveling property, and adjust the glass phase transition temperature after decomposition of the glass phase component.

[0011] The non-particle type glass powder ink has strong stability and no precipitation is generated after being stored at room temperature for 1 month.

[0012] A preparation method of a non-particle type glass component ink applied to conductive paste / ink, comprising the following steps:

[0013] 1) The non-particulate glass component ink is composed of the following components with mass percentage: 20-50% bismuth precursor component, 1-20% boron and silicon containing glass component, 10-20% amine complexing agent and 0.001-10% organic additive, and the rest is solvent; the amine complexing agent is fully dissolved in the solvent according to the above proportion, then the bismuth precursor is added and stirred until completely dissolved to prepare the basic bismuth-based ink;

[0014] 2) The boron and silicon containing glass component is added to the bismuth-based ink prepared in step 1) and stirred at room temperature until completely dissolved;

[0015] 3) The different additives for reducing the decomposition temperature of the ink, adjusting the viscosity and surface tension of the ink are added to the ink prepared in step 2) in proportion; in various configurations, the additives are one or more of viscosity modifier, surface tension modifier, film forming agent, defoaming agent; the ink is stirred at room temperature for 1-10 h until the particles are dissolved to obtain the glass component ink;

[0016] 4) The glass component ink prepared in step 3) is filtered through a 0.22 μm microporous filter membrane to obtain the non-particulate glass component ink.

[0017] The bismuth precursor is various bismuth-containing organic compounds; the solvent is one or a mixture of more than one of the organic solvents with boiling point below 300°C at normal pressure; the amine complexing agent is one or more than one of ammonia, aliphatic amine, alcohol amine, amide, aromatic amine; the boron and silicon containing glass component is various organic compounds containing boron and silicon.

[0018] The viscosity modifier is gum arabic, pectin, agar, gelatin, algin, carrageenan, universal gelatin or polysaccharide derivatives; the organic polymer viscosity modifier is a homopolymer or copolymer; the defoaming agent is one or more than one of fluorosilicone, mineral oil, vegetable oil, polysiloxane, ester wax, fatty alcohol, glycerol, stearate, silicone, polypropylene-based polyether.

[0019] The viscosity of the ink is affected by different additives, which is 10-40 m Pa·s, and the surface tension is 5-40 mN / m.

[0020] The application of a non-particulate glass component ink applied to conductive paste / ink, which is added to the conductive paste as a sintering aid; the prepared non-particulate glass component ink is added to different conductive pastes in a volume fraction of 1-20%, and stirred for 1 h to obtain a mixed ink with uniform components; the mixed ink is coated or printed on different substrates by drop coating, dip coating, spin coating or printing to form a layer or pattern, which is sintered by a certain method to obtain a metal thin film.

[0021] The substrate material is silicon, silicon carbide, quartz, glass, ceramic; the sintering temperature range is 400-800 DEG C, and the time is 10 min-5 h.

[0022] The conductive paste includes glass-based conductive paste and resin-based conductive paste; according to the classification of conductive functional phase fillers, the conductive paste includes carbon paste and various metal paste.

[0023] The beneficial effects of the present application are that the particle-free glass component ink is used as a sintering aid to replace part of the traditional glass powder in the conductive paste, and the glass component can be decomposed at a lower temperature to connect the metal and the substrate. The particle-free glass component ink generates small particle glass melt in situ during the sintering process of the conductive paste, and the dense glass component is filled between the metal particles after solidification, which reduces the influence of the traditional micron-sized glass powder on the intermetallic ohmic contact and further improves the conductivity of the metal via after sintering. Moreover, the preparation process is simple, green and environmentally friendly. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 SEM image of the film after sintering of the mixed ink of Example 3. DETAILED DESCRIPTION

[0025] The present application provides a particle-free glass component ink, preparation and application. The particle-free glass component ink uses a bismuth precursor component and an amine complexing agent to form a stable complex, then adds a glass component containing silicon and boron, dissolves in an organic solvent to form a particle-free ink, and then adds it to the traditional conductive paste as a sintering aid. The ink decomposes in situ to generate bismuth oxide, boron oxide and silicon oxide to fill between the metal particles and the metal and the substrate during sintering, and further heating to become a molten state, and after cooling and solidification, it produces a dense ohmic contact to improve its electrical performance and mechanical connection strength. Adding various additives to the ink can adjust its viscosity and leveling property, adjust the glass phase component decomposition temperature after the glass phase transformation, and improve its sintering performance. The new ink has strong stability, can be stored at room temperature for 1 month without precipitation, and the preparation method is simple, easy to operate, low in cost, green and environmentally friendly, and easy to realize industrialized production.

[0026] The preparation method of the particle-free glass component ink includes the following steps:

[0027] 1) The particle-free glass component ink according to the present application is composed of the following mass percentage components: 20-50% bismuth precursor component, 1-20% glass component containing boron and silicon, 10-20% amine complexing agent and 0.001-10% organic additive, and the rest is solvent. First, the amine complexing agent is fully dissolved in the solvent according to the above proportion, then the bismuth precursor is added to the mixed solution and stirred until completely dissolved to prepare the basic bismuth-based ink.

[0028] 2) To the bismuth-based ink prepared in step 1), glass components containing boron and silicon are added, and stirred at room temperature until completely dissolved.

[0029] 3) To the ink prepared in step 2), different additives are added in proportion for lowering the decomposition temperature of the ink, adjusting the viscosity and surface tension of the ink. In various configurations, one or more of a viscosity modifier, a surface tension modifier, a film former, an antifoaming agent, or any mixture thereof can be included in the ink. The ink is stirred at room temperature for 1 to 10 hours until no particles are present, and a glass component ink is obtained.

[0030] 4) The glass component ink prepared in step 3) is filtered through a 0.22 μm microporous filter to obtain a particle-free glass component ink.

[0031] The process of adding the particle-free glass component ink to the conductive paste as a sintering aid includes the following steps:

[0032] The particle-free glass component ink prepared is added to different conductive pastes in a volume fraction of 1 to 20%, and the mixed ink is stirred for 1 hour to obtain a uniform mixture. The mixed ink is coated or printed on different substrates using drop coating, dip coating, spin coating, or printing, to form a layer or pattern, which is sintered by a certain method to obtain a metal thin film.

[0033] Further, the bismuth precursor in step 1) can be various bismuth-containing organic compounds. The optimal proportion of the bismuth precursor is 20 to 50 wt%, and by increasing the amount of the bismuth precursor, the complexing efficiency of the metal precursor can be improved.

[0034] Further, the solvent in step 1) can be one or more of an alcohol, an ether, an ester, or a mixture thereof; and to prevent affecting the decomposition temperature of the ink, the solvent is preferably a solvent having a boiling point below 300°C at normal pressure (1 atm). The organic solvent can be an aromatic solvent, a non-aromatic solvent, or a mixture of an aromatic and a non-aromatic solvent. Examples of the solvent include methanol, ethanol, ethylene glycol, n-propanol, isopropanol, 1,2-butanediol, glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, dimethyl adipate, diethyl adipate, dimethyl succinate, dimethyl glutarate, DBE, and the like. The amount of the solvent is in the range of about 10 to 70 wt%.

[0035] Further, the amine complexing agent in step 1) is one or a mixture of several of ammonia, aliphatic amines, alcohol amines, amides, aromatic amines. As ligands, 1,2- propylenediamine, ethylenediamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, n-hexylamine, ethanolamine, isopropanolamine, diethylethylenediamine, dihydroxyethylenediamine, and trihydroxyethylenediamine, etc. can be listed. The amine complexing agent is preferably added in a range of 10 to 20 wt%.

[0036] Further, the glass component containing boron and silicon in step 2) is various organic compounds containing boron and silicon. For example, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, sodium perborate, silane, polysiloxane, polysilane, ethyl orthosilicate, butyl orthosilicate, tetraphenyl orthosilicate, isoamyl orthosilicate, tetrabenzyl orthosilicate, and mixtures thereof. The amount is in a range of about 1 to 20 wt%.

[0037] Further, the viscosity modifier in step 3) functions mainly to adjust the viscosity of the ink, so that the ink is suitable for different conductive pastes. The viscosity of the ink is preferably adjusted to 1 to 60 mPa-s at room temperature 25°C by adding an additive such as gum arabic, pectin, agar, gelatin, algin, carrageenan, universal gelatin, polysaccharide derivatives, etc. The preferred viscosity modifier also includes cellulose polymers, polyacrylates, polystyrene, polyolefins, polyvinylpyrrolidone, polypyrrolidone, polyvinyl acetal, polyesters, polyimides, polyetherimides, polyols, silicones, polyurethanes, epoxy resins, phenolic resins, phenol formaldehyde resins, polyalkylene carbonates, and mixtures thereof. The preferred organic polymer viscosity modifier can be a homopolymer or a copolymer. The amount is in a range of about 0.001 to 5 wt%.

[0038] Further, the ink in step 3) is affected by different additives, and the viscosity is preferably 10 to 40 mPa-s, and the surface tension is preferably 5 to 40 mN / m.

[0039] Further, the defoaming agent in step 3) can prevent the formation of foam, reduce or eliminate the existing foam. The preferred defoaming agent can be fluorosilicone, mineral oil, vegetable oil, polysiloxane, ester wax, fatty alcohol, glycerol, stearate, silicone, polypropylene polyether, and mixtures thereof. The amount is in a range of about 0.001 to 5 wt%.

[0040] Further, the printed substrate material in step 5) is silicon, silicon carbide, quartz, glass, ceramic, and various suitable substrates. For example, polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), polystyrene, acrylonitrile, butadiene, styrene, polycarbonate, polyimide (e.g., Kapton™), polyetherimide (e.g., Ultem™), thermoplastic polyurethane (TPU), silicone rubber film, printed wiring board substrate (e.g., FR4), glass, metal, dielectric coating, etc.

[0041] Further, the various film forming methods in step 5) include drop coating, coating, spraying, lamination, suspension coating; the printing methods include screen printing, inkjet printing, roll-to-roll printing, silk screen printing, offset printing, flexographic printing, lithographic printing, intaglio printing, stencil printing, pad printing or any other method.

[0042] Further, in step 5), the conductive paste coating is dried or sintered by heat treatment or laser sintering to form a metal film. The conductive ink can be sintered and cured in an inert atmosphere (such as nitrogen and / or argon), a reducing atmosphere (such as hydrogen), air, or vacuum. The sintering temperature is preferably in the range of 400-800°C, and the time is 10 min-5 h.

[0043] Further, the conductive paste in step 6) is a conductive paste configured with various functional phases. It includes glass-based conductive paste and resin-based conductive paste. According to the classification of conductive functional phase fillers, the conductive paste includes carbon paste (graphite conductor) and various metal paste such as gold powder paste, silver powder paste, copper powder paste, silver-plated copper powder paste, nickel powder paste and various modified metal paste. The volume fraction of the non-particulate glass component ink added to the conductive paste is 1-20%.

[0044] The application will be described in more detail by the following examples, but the scope of the application is not limited to these examples. The bismuth octoate, silver oxalate, silver powder, complexing agent, organic additive and solvent used in the examples of the application are all commercially available products.

[0045]

Example 1

[0046] The high-stability non-particulate glass component ink is composed of 32% bismuth isopropyl alcohol, 14% 1,2-propylenediamine, 4% tetraethyl orthosilicate, 4% tributyl borate, 1% epoxy resin and 45% acetone in terms of mass percentage. The preparation method is as follows:

[0047] According to the above proportions, first mix 1,2-propylenediamine with the solvent, then add bismuth isopropyl alcohol to the mixed solution, stir at room temperature for 3 h until fully dissolved, then add tetraethyl orthosilicate, tributyl borate and epoxy resin and stir until dissolved, filter through a 0.22 μm microporous filter membrane to obtain the non-particulate glass component ink of the application. The viscosity is 24.63 mPa·s and the surface tension is 26.2 mN / m; take 200 μL of the ink and spin coat it on a 2.2 cm glass substrate, set the spin coating parameters as follows during the spin coating process: uniform coating speed 500 r / min, uniform coating time 10 s, spin coating speed 1000 r / min, spin coating time 15 s. Increase the temperature to 500°C at a rate of 40°C / min, and sinter for 90 min to obtain a glass powder film.

[0048]

Comparative Example 1

[0049] High stability particle-free glass component ink, according to the mass percentage of 32% bismuth isopropyl alcohol, 14% 1,2-propylenediamine, 15% tetraethyl orthosilicate, 10% tributyl borate, 1% epoxy resin and 28% acetone. The preparation method is:

[0050] According to the above proportion, first mix 1,2-propylenediamine with solvent, after mixing evenly, add bismuth isopropyl alcohol into the mixed solution, stir at room temperature for 3h to fully dissolve, then add tetraethyl orthosilicate and epoxy resin, stir and dissolve, add tributyl borate, white turbidity is generated during stirring, white precipitate is deposited at the bottom after standing, and particle-free ink is not formed.

[0051]

Example 2

[0052] High stability particle-free glass component ink, according to the mass percentage of 45% bismuth neodecanoate, 15% ethylamine, 10% tetraphenyl silicate, 5% trimethyl borate, 1% epoxy resin and 24% diethylene glycol ethyl ether.

[0053] The preparation method is:

[0054] According to the above proportion, first mix ethylamine with solvent, after mixing evenly, add bismuth neodecanoate into the mixed solution, stir at room temperature for 3h to fully dissolve, then add tetraphenyl silicate, trimethyl borate and epoxy resin, stir to dissolve, filter through a microporous filter membrane with a pore size of 0.22μm to obtain the particle-free glass component ink of the present application. The viscosity is 28.72mPa·s, and the surface tension is 31.6mN / m; take 200μL of the ink and spin it on a 2·2cm silicon carbide substrate, set the spin coating parameters during spin coating as spin coating speed 500r / min, spin coating time 10s, spin coating speed 1000r / min, spin coating time 15s. Heat to 500℃ at a heating rate of 40℃ / min, sinter for 90min to obtain a glass powder film.

[0055]

Example 3

[0056] High stability particle-free glass component ink as sintering aid, according to the mass percentage of 40% bismuth isooctanoate, 15% 1,2-propylenediamine, 3% n-butyl orthosilicate, 5% trimethyl borate, 1% epoxy resin and 36% diethylene glycol ethyl ether.

[0057] Silver ink according to the mass percentage of 40% silver oxalate, 21% 1,2-propylenediamine and 39% ethanol, the volume fraction of the glass component ink added is 9vol%. The preparation method is:

[0058] The 1,2-propanediamine is mixed with the solvent first, and then the bismuth isooctoate is added into the mixed solution. After stirring at room temperature for 3 hours until it is fully dissolved, the tetraethyl orthosilicate, trimethyl borate and epoxy resin are added and stirred until dissolved. The solution is filtered through a 0.22 μm microporous filter to obtain the particle-free glass component ink of the present application. 9 vol% of the ink is added into the silver ink and stirred for 1 hour, and then filtered to obtain the mixed ink. 200 μL of the ink is spin-coated on a 2.2 cm silicon carbide substrate. The spin-coating parameters are set as follows: 500 r / min for the uniform coating speed, 10 s for the uniform coating time, 1000 r / min for the spin-coating speed, and 15 s for the spin-coating time. The temperature is raised to 500 °C at a rate of 40 °C / min, and sintered for 90 min to obtain the metal thin film. The bonding strength between the silver film and the substrate is tested by the 3M tape test, and the result shows that the bonding strength is 5B grade, and the highest bonding strength is 26 MPa.

[0059]

Comparative Example 3

[0060] The silver ink is composed of 40% silver oxalate, 21% 1,2-propanediamine and 39% ethanol by mass percentage, and the particle-free glass component ink of the present application is not added. The preparation method of the silver ink is as follows:

[0061] The 1,2-propanediamine is mixed with the solvent first, and then the silver oxalate precursor is added into the mixed solution. After stirring at room temperature for 3 hours until it is fully dissolved, the solution is filtered through a 0.22 μm microporous filter to obtain the particle-free glass component ink of the present application. 200 μL of the ink is spin-coated on a 2.2 cm silicon carbide substrate. The spin-coating parameters are set as follows: 500 r / min for the uniform coating speed, 10 s for the uniform coating time, 1000 r / min for the spin-coating speed, and 15 s for the spin-coating time. The temperature is raised to 500 °C at a rate of 40 °C / min, and sintered for 90 min to obtain the metal thin film. The bonding strength between the silver film and the substrate is tested by the 3M tape test, and the result shows that the bonding strength is only 3B grade.

[0062]

Example 4

[0063] The particle-free glass component ink with high stability as the sintering aid is composed of 40% bismuth isooctoate, 15% 1,2-propanediamine, 5% tetraethyl orthosilicate, 5% trimethyl borate, 1% epoxy resin and 34% diethylene glycol ether by mass percentage. The conductive silver paste is prepared by mixing 65% commercial silver powder, 14% isopropyl alcohol, 7% ethylene glycol and 14% terpineol by mass percentage. The volume fraction of the glass component ink added is 6 vol%, 9 vol% and 12 vol%, and the glass component inks are numbered as S1, S2 and S3, respectively. The preparation method is as follows:

[0064] According to the above ratio, first mix 1,2-propylenediamine with solvent, after mixing evenly, add bismuth isooctoate into the mixed solution, stir at room temperature for 3h to fully dissolve, then add tetraethyl orthosilicate, trimethyl borate and epoxy resin and stir until dissolved, filter through a 0.22μm microporous filter to obtain the particle-free ink of the present application. Then take the ink and add it into the conductive silver paste to stir and mix to obtain a mixed ink. Take 200μL of the ink and spin coat it on a 2·2cm silicon carbide substrate, and set the spin coating parameters during the spin coating process as follows: uniform coating speed 500r / min, uniform coating time 10s, spin coating speed 1000r / min, spin coating time 15s. Heat to 500℃ at a heating rate of 40℃ / min, and sinter for 90min to obtain a metal thin film. Through testing, the shear strength of the ink with a glass component ink addition amount of 12vol% is increased from 23MPa to 43.6MPa.

Claims

1. A method for producing a non-particulate type glass component ink for conductive paste / ink, characterized by, The particle-free glass component ink is prepared by forming a stable complex with a bismuth precursor component and an amine complexing agent, adding a glass component containing silicon and boron, dissolving in an organic solvent, filtering to form a particle-free ink, and then adding to a traditional conductive paste as a sintering aid; the particle-free glass component ink decomposes in situ during sintering to produce bismuth oxide, boron oxide and silicon oxide, which fill between metal particles and between the metal and the substrate, and then become molten at a higher temperature, and after cooling and solidification, a dense ohmic contact is formed; The preparation method comprises the following steps: 1) The particle-free glass component ink is prepared by dissolving the amine complexing agent in the solvent according to the above proportions, then adding the bismuth precursor and stirring until completely dissolved to prepare the basic bismuth-based ink; 2) The glass component containing boron and silicon is added to the bismuth-based ink prepared in step 1) and stirred at room temperature until completely dissolved; 3) The different additives are added to the ink prepared in step 2) in proportion to reduce the decomposition temperature of the ink, adjust the viscosity and surface tension of the ink; in various configurations, the additives are one or more of a viscosity modifier, a surface tension modifier, a film former, and a defoaming agent; the ink is stirred at room temperature for 1-10 hours until it is particle-free, and a glass component ink is obtained; 4) The glass component ink prepared in step 3) is filtered through a 0.22 μm microporous filter membrane to obtain a particle-free glass component ink.

2. The production method according to claim 1, characterized by, The particle-free glass component ink is added with additives to adjust its viscosity and leveling properties, and to adjust the glass phase component decomposition temperature.

3. The preparation method according to claim 1, characterized in that, The bismuth precursor is various bismuth-containing organic compounds; the solvent is one or a mixture of more than one of various organic solvents with a boiling point below 300°C at normal pressure; the amine complexing agent is one or more of ammonia, aliphatic amine, alcohol amine, amide, and aromatic amine; the glass component containing boron and silicon is various organic compounds containing boron and silicon.

4. The method of claim 1, wherein, The viscosity modifier is gum arabic, pectin, agar, gelatin, algin, carrageenan, universal gelatin, or polysaccharide derivatives; the viscosity modifier is a homopolymer or a copolymer; the defoaming agent is one or more of fluorosilicone, mineral oil, vegetable oil, polysiloxane, ester wax, fatty alcohol, glycerol, stearate, silicone, and polypropylene-based polyether.

5. The production method according to any one of claims 1 to 4, characterized by, The ink is affected by different additives, with a viscosity of 10-40 m Pa·s and a surface tension of 5-40 m N / m.

6. Use of a particle-free glass component ink for conductive paste / ink prepared by the method according to any one of claims 1 to 5, characterized in that, The particle-free glass component ink is added to the conductive paste as a sintering aid; The particle-free glass component ink is prepared by dissolving the amine complexing agent in the solvent according to the above proportions, then adding the bismuth precursor and stirring until completely dissolved to prepare the basic bismuth-based ink; 7. Use of a particle-free glass component ink according to claim 6, characterized in that The substrate material is silicon, silicon carbide, quartz, glass, ceramic; the sintering temperature ranges from 400 to 800 DEG C, and the time ranges from 10 min to 5 h.

8. Use of a particle-free glass component ink according to claim 6 or 7, characterized in that The conductive paste includes glass-based conductive paste and resin-based conductive paste; according to the classification of conductive functional phase fillers, the conductive paste includes carbon paste and various metal paste.

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