CN116514402A - Glass powder applied to negative thick film photoresist paste and preparation method thereof - Google Patents

Glass powder applied to negative thick film photoresist paste and preparation method thereof Download PDF

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Publication number
CN116514402A
CN116514402A CN202310498969.5A CN202310498969A CN116514402A CN 116514402 A CN116514402 A CN 116514402A CN 202310498969 A CN202310498969 A CN 202310498969A CN 116514402 A CN116514402 A CN 116514402A
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thick film
glass powder
film photoresist
oxide
negative
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伍佩铭
许迪
董鹏程
高辉
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Qianyu Micro Nano Technology Shenzhen Co ltd
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Qianyu Micro Nano Technology Shenzhen Co ltd
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Priority to CN202310498969.5A priority Critical patent/CN116514402A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses glass powder applied to negative thick film photoetching slurry and a preparation method thereof, belonging to the technical field of electronic materials, wherein the glass powder applied to the negative thick film photoetching slurry comprises the following components in percentage by mass: 30-40% of silicon dioxide, 25-35% of bismuth oxide, 15-25% of boric acid, 5-10% of titanium dioxide and 2-10% of additive. The glass powder applied to the negative thick film photoresist paste does not contain alkaline oxide, has good binding force with a matrix, does not react with acid groups in the thick film photoresist paste, has good acid resistance, can stably exist in the thick film photoresist paste, and does not influence the development performance.

Description

Glass powder applied to negative thick film photoresist paste and preparation method thereof
Technical Field
The invention relates to the technical field of electronic materials, in particular to glass powder applied to negative thick film photoetching paste and a preparation method thereof.
Background
The photoetching thick film Technology PI-TF (Photoimageable Thick-film Technology) is a novel photoetching Technology combining photoetching technologies such as exposure and development with a traditional thick film printing Technology, is a technological process for forming a thick film circuit by a photosensitive development mode, can realize ultra-high precision and ultra-fine wire layout, realizes miniaturization and high density of advanced electronic components and semiconductor packaging, and has great application value and market prospect.
Because of the special nature of the application process, glass powder also needs to be specially customized, a photoetching thick film paste system contains acid group resin capable of reacting with sodium carbonate, while the traditional glass powder contains alkaline oxides such as copper oxide, zinc oxide and the like in the raw materials for manufacturing, and free alkaline oxides are also generated after the preparation or alkaline oxides are generated in the process of preparing glass, and the alkaline oxides can react with the acid groups of the paste system, so that the reduction of the acid groups affects the development performance on one hand and the stability of the paste on the other hand; in addition, a large amount of conventional glass powder also contains alkaline earth metal compounds, which also affect the stability of the negative thick film photoresist paste.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide glass powder applied to negative thick film photoetching slurry and a preparation method thereof, wherein the glass powder has good binding force with a matrix, can not react with acid groups in the thick film photoetching slurry, has good acid resistance, can stably exist in the thick film photoetching slurry, and can not influence the development performance.
In order to achieve the above object, in a first aspect of the present invention, there is provided a glass frit for a negative thick film photoresist paste, comprising the following components in mass percent: 30-40% of silicon dioxide, 25-35% of bismuth oxide, 15-25% of boric acid, 5-10% of titanium dioxide and 2-10% of additive.
As a preferred embodiment of the invention, the composition comprises the following components in percentage by mass: 32-38% of silicon dioxide, 25-32% of bismuth oxide, 18-25% of boric acid, 6-10% of titanium dioxide and 4-10% of additive.
As a preferred embodiment of the invention, the composition comprises the following components in percentage by mass: 35% of silicon dioxide, 30% of bismuth oxide, 20% of boric acid, 8% of titanium dioxide and 7% of additives.
As a preferred embodiment of the present invention, the additive includes at least one of antimony oxide, zirconium oxide, and tungsten trioxide.
As a preferred embodiment of the present invention, the additive includes antimony oxide, zirconium oxide and tungsten trioxide;
the mass ratio of the antimony oxide, the zirconium oxide and the tungsten trioxide is (2-5): (1-3): (0.5-2).
As a preferred embodiment of the present invention, the mass ratio of the antimony oxide, the zirconium oxide and the tungsten trioxide is 4:2:1.
in a second aspect of the invention, the invention provides a method for preparing glass frit for use in a negative-working thick film photoresist paste, comprising the steps of:
uniformly mixing silicon dioxide, bismuth oxide, boric acid, titanium dioxide and additives to obtain a mixture;
and smelting, annealing, cooling and crushing the mixture to obtain glass powder.
As a preferred embodiment of the invention, the smelting temperature is 1500-1600 ℃ and the smelting time is 30-60 min.
As a preferred embodiment of the present invention, the annealing temperature is 350 to 500 ℃ and the annealing time is 1 to 4 hours.
As a preferred embodiment of the present invention, the annealing temperature is 400℃and the annealing time is 2 hours.
The invention has the beneficial effects that: (1) The glass powder applied to the negative thick film photoresist paste does not contain alkaline oxide and alkaline earth metal, has good binding power with a matrix, does not react with acid groups in the thick film photoresist paste, has good acid resistance, can stably exist in the thick film photoresist paste, and does not influence the development performance.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (a), b, or c)", or "at least one (a, b, and c)", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.
In the present invention, the specific dispersing and stirring treatment method is not particularly limited.
The reagents or apparatus used in the present invention are conventional products commercially available without the manufacturer's knowledge.
The embodiment of the invention provides glass powder applied to negative thick film photoetching slurry, which comprises the following components in percentage by mass: 30-40% of silicon dioxide, 25-35% of bismuth oxide, 15-25% of boric acid, 5-10% of titanium dioxide and 2-10% of additive.
The glass powder applied to the negative thick film photoresist paste does not contain alkaline oxide, has good binding power with the substrate, can not react with acid groups in the thick film photoresist paste, has good acid resistance, can stably exist in the thick film photoresist paste, and can not influence the development performance.
The inventors of the present invention studied the effect of the amount of raw materials on the adhesion and stability in thick film photoresist paste systems and found that within the above ranges, both stability and adhesion are good, but if the components deviate from the above ranges, the stability and/or adhesion are reduced,
and the acid-resistant polymer can not react with acid groups in thick film photoresist paste, has good acid resistance, can exist in the thick film photoresist paste stably, and can not influence the development performance.
Illustratively, the silica may be present in a mass percent of 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, but is not limited to the recited values, as other non-recited values within the range are equally applicable.
Illustratively, the bismuth oxide may be 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35% by mass, but is not limited to the recited values, as other non-recited values within the range are equally applicable.
Illustratively, the boric acid may be 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25% by mass, but is not limited to the recited values, as other non-recited values within the range are equally applicable.
The mass percent of titanium dioxide may be, for example, 5%, 6%, 7%, 8%, 9%, 10%, but is not limited to the recited values, as other non-recited values within the range are equally applicable.
The mass percentages of the additives may be, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, but are not limited to the recited values, as other non-recited values within the range are equally applicable.
In one embodiment, the composition comprises the following components in percentage by mass: 32-38% of silicon dioxide, 25-32% of bismuth oxide, 18-25% of boric acid, 6-10% of titanium dioxide and 4-10% of additive.
In one embodiment, the composition comprises the following components in percentage by mass: 35% of silicon dioxide, 30% of bismuth oxide, 20% of boric acid, 8% of titanium dioxide and 7% of additives.
In one embodiment, the additive comprises at least one of antimony oxide, zirconium oxide, tungsten trioxide.
In one embodiment, the additives include antimony oxide, zirconium oxide, and tungsten trioxide;
the mass ratio of the antimony oxide, the zirconium oxide and the tungsten trioxide is (2-5): (1-3): (0.5-2).
The inventor of the invention discovers that antimony oxide, zirconium oxide and tungsten trioxide are added at the same time, and under the combined action of the three, the stability and the cohesive force of the system are further improved; if antimony oxide, zirconium oxide and tungsten trioxide are used singly, the effect cannot be achieved.
In one embodiment, the mass ratio of the antimony oxide, the zirconium oxide and the tungsten trioxide is 4:2:1.
research shows that the chemical stability of glass powder depends on structural integrity and dissolution capacity of components, and the more complete the network structure is, the more tightly the structural units are linked, and the better the chemical stability is; the smaller the ion radius is, the lower the ion electricity price is, and the more easily the ions migrate out; the larger the network void, the easier the ions migrate.
SiO 2 (silica) as a network former to form a basic skeleton, which can make the network structure denser and improve the mechanical strength and chemical stability of the glass frit, it is necessary to control the content thereof to 30% or more in order to obtain a glass having good acid resistance, and SiO 2 If the content of (C) is more than 40%, the system viscosity and softening point are too high, and the fluidity is poor, and therefore, siO is used in thick film resist 2 The content is controlled between 30% and 40%, which is favorable for compacter network structure, improves the mechanical strength and chemical stability of the glass powder, improves the acid resistance and further improves the development performance.
Bi 2 O 3 The (bismuth oxide) is mainly composed of [ BiO 4 ]Form participates in the structural construction of the network, and [ SiO 4 ]Together form a network skeleton, when Bi 2 0 3 At a content of 20 to 30%, the network structure is enhanced, but when Bi is contained 2 0 3 When the content is too high, the excessive Bi 3+ The free oxygen in the network structure competes for free oxygen, weakens the network structure, increases network voids, and further reduces chemical stability, so that the content of bismuth oxide needs to be strictly controlled to be 20-30%.
ZrO 2 The (zirconia) is mainly cubic [ ZrO 8 ]The coordination form exists, belongs to a network exosome in the structure, has smaller solubility in glass, and can further improve the stability of the glass and improve the acid and alkali resistance and the glass hardness.
TiO 2 The addition of (3) can further improve the chemical stability of the system, thereby improving the development performance.
Sb 2 O 3 (antimony oxide, the bismuth oxide of the present invention means antimony trioxide) can reduce the melting temperature of the glass frit, and as a network forming agent, it can improve network compactness, and when the content is too low, network compactness is poor, and when the content is too high, the phase separation tendency is increased and the boron volatilization amount is increased, homogenization is difficult to achieve, stability is not improved, and acid resistance is further reduced.
WO 3 The (tungsten oxide) contributes to an increase in softening point of the glass frit and an increase in adhesion.
An embodiment of the present invention provides a method for preparing glass frit for negative thick film photoresist paste, comprising the steps of:
uniformly mixing silicon dioxide, bismuth oxide, boric acid, titanium dioxide and additives to obtain a mixture;
and smelting, annealing, cooling and crushing the mixture to obtain glass powder.
In one embodiment, the smelting temperature is 1500-1600 ℃ and the smelting time is 30-60 min.
The smelting temperature may be 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃, 1000 ℃, by way of example, but is not limited to the values recited, and other values not recited in the range are equally applicable.
By way of example, the smelting time may be 30min, 40min, 50min, 60min, but is not limited to the recited values, as other non-recited values within the range are equally applicable.
In one embodiment, the annealing temperature is 350-500 ℃ and the annealing time is 1-4 h.
The annealing temperature may be, for example, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, and not limited to the recited values, but other non-recited values within the range of values are equally applicable.
The annealing time may be, for example, 1h, 2h, 3h, 4h, and is not limited to the recited values, but other non-recited values within the range are equally applicable.
In one embodiment, the annealing temperature is 400 ℃ and the annealing time is 2h.
The following examples are provided to facilitate an understanding of the present invention. These examples are not provided to limit the scope of the claims.
Example 1
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 35% silica, 30% bismuth oxide, 20% boric acid, 8% titanium dioxide, 4% antimony oxide, 2% zirconium oxide, 1% tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide, antimony oxide, zirconium oxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1550 ℃ for 50min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Example 2
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 30% silicon dioxide, 35% bismuth oxide, 18% boric acid, 8% titanium dioxide, 5% antimony oxide, 3% zirconium oxide, 1% tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide, antimony oxide, zirconium oxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1600 ℃ for 30min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Example 3
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 40% silica, 26% bismuth oxide, 20% boric acid, 7% titanium dioxide, 3% antimony oxide, 2% zirconium oxide, 2% tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide, antimony oxide, zirconium oxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1530 ℃ for 60min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Example 4
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 32% silicon dioxide, 30% bismuth oxide, 22% boric acid, 8% titanium dioxide, 4% antimony oxide, 3% zirconium oxide, 1% tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide, antimony oxide, zirconium oxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1580 ℃ for 45min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Example 5
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 36% silica, 29% bismuth oxide, 21% boric acid, 9% titanium dioxide, 2.5% antimony oxide, 2% zirconium oxide, 0.5% tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide, antimony oxide, zirconium oxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1580 ℃ for 45min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Example 6
A glass powder applied to negative thick film photoetching slurry comprises the following components in percentage by mass of 37% of silicon dioxide, 27% of bismuth oxide, 23% of boric acid, 7% of titanium dioxide, 4% of antimony oxide, 1% of zirconium oxide and 1% of tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide, antimony oxide, zirconium oxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting, wherein the smelting temperature is 1560 ℃, the smelting time is 48min, obtaining glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing, the annealing temperature is 400 ℃, the annealing time is 2h, cooling to room temperature along with the furnace, and crushing into powder, thus obtaining glass powder.
Example 7
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 35.5% silica, 32.5% bismuth oxide, 17% boric acid, 8.5% titanium dioxide, 3% antimony oxide, 2% zirconium oxide, 1.5% tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide, antimony oxide, zirconium oxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1580 ℃ for 50min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Example 8
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 36.5% silica, 33% bismuth oxide, 16% boric acid, 7.5% titanium dioxide, 3% antimony oxide, 3% zirconium oxide, 1% tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide, antimony oxide, zirconium oxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1530 ℃ for 60min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Example 9
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 39.6% silica, 32.6% bismuth oxide, 20.9% boric acid, 2.9% titanium dioxide, 1.5% antimony oxide, 1.5% zirconium oxide, 1% tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide, antimony oxide, zirconium oxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting, wherein the smelting temperature is 1560 ℃, the smelting time is 50min, obtaining glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing, the annealing temperature is 400 ℃, the annealing time is 2h, cooling to room temperature along with the furnace, and crushing into powder, thus obtaining glass powder.
Example 10
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 38.1% silica, 32.9% bismuth oxide, 21.3% boric acid, 3.2% titanium dioxide, 3% antimony oxide, 1% zirconium oxide, 0.5% tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide, antimony oxide, zirconium oxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1550 ℃ for 60min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Comparative example 1
Comparative example 1 differs from examples 1 to 10 in that the raw material ratio of comparative example 1 is not within the scope of the present invention.
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 42% silica, 18% bismuth oxide, 26% boric acid, 12% titanium dioxide, 0.5% antimony oxide, 0.5% zirconium oxide, 1% tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide, antimony oxide, zirconium oxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1550 ℃ for 50min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Comparative example 2
Comparative example 2 is different from examples 1 to 10 in that the raw material ratio of comparative example 2 is not within the scope of the present invention.
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 28% silicon dioxide, 38% bismuth oxide, 14% boric acid, 12% titanium dioxide, 5% antimony oxide, 0.5% zirconium oxide, 2.5% tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide, antimony oxide, zirconium oxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1550 ℃ for 50min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Comparative example 3
Comparative example 3 differs from example 1 in that the additive of comparative example 3 is a single antimony oxide, all of which are identical.
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 35% silicon dioxide, 30% bismuth oxide, 20% boric acid, 8% titanium dioxide and 7% antimony oxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide and antimony oxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1550 ℃ for 50min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Comparative example 4
Comparative example 4 differs from example 1 in that the additive of comparative example 4 is a single zirconia, all of which are identical.
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 35% silica, 30% bismuth oxide, 20% boric acid, 8% titanium dioxide, 7% zirconium oxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide and zirconium oxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1550 ℃ for 50min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Comparative example 5
Comparative example 5 differs from example 1 in that the additive of comparative example 5 is a single tungsten trioxide, all of which are identical.
The glass powder applied to the negative thick film photoresist paste comprises the following components in percentage by mass: 35% silicon dioxide, 30% bismuth oxide, 20% boric acid, 8% titanium dioxide, 7% tungsten trioxide.
The preparation method of the glass powder applied to the negative thick film photoresist paste comprises the following steps:
placing silicon dioxide, bismuth oxide, boric acid, titanium dioxide and tungsten trioxide into an agate mortar, uniformly mixing, placing into a corundum crucible, then placing into a high-temperature furnace for smelting at 1550 ℃ for 50min to obtain glass liquid, cooling and molding the glass liquid in a stainless steel mold, placing into a muffle furnace for annealing at 400 ℃ for 2h, cooling to room temperature along with the furnace, and crushing into powder to obtain glass powder.
Test case
The glass powders of examples 1 to 10 and comparative examples 1 to 5 according to the present invention were prepared into yellow silver paste according to the method of example 1 of CN111929989 (the glass powders of examples 1 to 10 and comparative examples 1 to 5 were used instead of the glass powders thereof, and other conditions were kept unchanged) for testing.
1. Adhesion (GB/T17473.4-2008 adhesion measurement for noble metal paste test methods for microelectronics, PET/glass substrates), test results are shown in Table 1.
2. Yellow silver paste was coated on 96% alumina substrate by screen printing, dried, sintered to obtain a substrate, and the substrate was put in 20% hydrochloric acid aqueous solution, kept for 48 hours, and the substrate was subject to falling off, cracking or bubbling, and the test results are shown in table 1.
TABLE 1
adhesion/N Soaking in 20% hydrochloric acid for 48 hr
Example 1 39.5 No change
Example 2 34.1 No change
Example 3 34.6 No change
Example 4 35.1 No change
Example 5 35.3 No change
Example 6 35.5 No change
Example 7 36.0 No change
Example 8 35.8 No change
Example 9 35.7 No change
Example 10 34.9 No change
Comparative example 1 29.5 Crack occurrence
Comparative example 2 26.7 Slight falling off occurs
Comparative example 3 30.7 Crack occurrence
Comparative example 4 31.9 Bubble occurrence
Comparative example 5 31.2 Crack occurrence
As can be seen from Table 1, the glass powder of the present invention has good adhesion to the substrate, does not react with acidic groups in the thick film photoresist paste, has good acid resistance, and can be stably present in the thick film photoresist paste.
As can be seen from comparative examples 1 to 10, example 1 is the best mode for carrying out the present invention, and has the best adhesive force and acid resistance.
As can be seen from comparative examples 1 and 2, the different raw material ratios can affect the performance of the glass frit, and by controlling the ratios within the scope of the present invention, the adhesion and acid resistance are effectively improved, while if the raw material ratios deviate slightly from the scope of the present invention, the adhesion and acid resistance are significantly reduced.
As can be seen from comparative examples 1 and 3 to 5, the present invention requires the simultaneous addition of antimony oxide, zirconium oxide and tungsten trioxide, and under the combined action thereof, the adhesion and acid resistance of the glass frit are improved, and the three have a certain synergistic effect.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

1. The glass powder applied to the negative thick film photoresist paste is characterized by comprising the following components in percentage by mass: 30-40% of silicon dioxide, 25-35% of bismuth oxide, 15-25% of boric acid, 5-10% of titanium dioxide and 2-10% of additive.
2. The glass powder applied to the negative-type thick film photoresist paste according to claim 1, wherein the glass powder comprises the following components in percentage by mass: 32-38% of silicon dioxide, 25-32% of bismuth oxide, 18-25% of boric acid, 6-10% of titanium dioxide and 4-10% of additive.
3. The glass powder applied to the negative-type thick film photoresist paste according to claim 1, wherein the glass powder comprises the following components in percentage by mass: 35% of silicon dioxide, 30% of bismuth oxide, 20% of boric acid, 8% of titanium dioxide and 7% of additives.
4. The glass frit for use in a negative-type thick film photoresist paste according to claim 1, wherein said additive comprises at least one of antimony oxide, zirconium oxide, tungsten trioxide.
5. The glass frit for use in a negative-type thick film photoresist paste according to claim 4, wherein said additives comprise antimony oxide, zirconium oxide and tungsten trioxide;
the mass ratio of the antimony oxide, the zirconium oxide and the tungsten trioxide is (2-5): (1-3): (0.5-2).
6. The glass frit for a negative thick film photoresist paste according to claim 5, wherein the mass ratio of antimony oxide, zirconium oxide, tungsten trioxide is 4:2:1.
7. the method for preparing glass frit for negative-type thick film photoresist paste according to any one of claims 1 to 6, comprising the steps of:
uniformly mixing silicon dioxide, bismuth oxide, boric acid, titanium dioxide and additives to obtain a mixture;
and smelting, annealing, cooling and crushing the mixture to obtain glass powder.
8. The method for preparing glass powder for negative thick film photoresist paste according to claim 7, wherein the melting temperature is 1500-1600 ℃ and the melting time is 30-60 min.
9. The method of claim 7, wherein the annealing temperature is 350-500 ℃ and the annealing time is 1-4 hours.
10. The method of claim 7, wherein the annealing temperature is 400 ℃ and the annealing time is 2 hours.
CN202310498969.5A 2023-05-06 2023-05-06 Glass powder applied to negative thick film photoresist paste and preparation method thereof Pending CN116514402A (en)

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