HTCC packaging tube shell glass pigment, preparation method and application
阅读说明：本技术 一种htcc封装管壳玻璃色料、制备方法及应用 (HTCC packaging tube shell glass pigment, preparation method and application ) 是由 李生 邵训达 于 2021-03-01 设计创作，主要内容包括：本发明公开了一种HTCC封装管壳玻璃色料,所述玻璃色料的无机粉体原料包括以下重量份的原料：氧化铝20～32份,高岭土15～22份,滑石粉16～20份,三氧化钼8～13份,氧化铬6～12份,碳酸钙5～14份、互联剂1～6份。本发明较常规配料制备HTCC封装管壳具有以下优势：玻璃色料预制的方法能明显降低制浆粘度,降低制浆难度,方便大规模生产；玻璃色料成瓷色泽更深,对成瓷密度、成瓷抗弯曲强度的提升也非常明显。(The invention discloses an HTCC (high temperature resistant ceramic) packaging tube shell glass pigment, which comprises the following inorganic powder raw materials in parts by weight: 20-32 parts of aluminum oxide, 15-22 parts of kaolin, 16-20 parts of talcum powder, 8-13 parts of molybdenum trioxide, 6-12 parts of chromium oxide, 5-14 parts of calcium carbonate and 1-6 parts of an interconnecting agent. Compared with the conventional method for preparing the HTCC packaging tube shell by using the ingredients, the method has the following advantages that: the method for prefabricating the glass pigment can obviously reduce the pulping viscosity and the pulping difficulty, and is convenient for large-scale production; the color of the porcelain formed by the glass pigment is darker, and the improvement on the density and the bending strength of the porcelain formed is also very obvious.)
1. The HTCC packaging tube shell glass pigment is characterized in that inorganic powder raw materials of the glass pigment comprise the following raw materials in parts by weight:
20-32 parts of aluminum oxide, 15-22 parts of kaolin, 16-20 parts of talcum powder, 8-13 parts of molybdenum trioxide, 6-12 parts of chromium oxide, 5-14 parts of calcium carbonate and 1-6 parts of an interconnecting agent;
the inorganic powder raw material is subjected to a gelation reaction, and the gelation raw material comprises: 2.0-2.5 parts of acrylamide organic monomer, 0.1-0.12 part of N, N' -methylene bisacryloyl cross-linking agent, 0.5-1.0 part of Rohm and Haas OROTAN 1124 dispersant, 0.2-0.4 part of ammonium persulfate initiator, 0.05-0.1 part of tetramethyl ethylene diamine, 10-15 ml of 28% ammonia water solution and 40-50 parts of deionized water;
the preparation method of the interconnecting agent comprises the following steps:
s1: sending cyclodextrin into 10-30% of fatty alcohol-polyoxyethylene ether sodium sulfate solution by mass fraction for low-speed stirring for 20-30min, wherein the stirring speed is 100-200r/min, after stirring, taking out, washing, sending into a proton irradiation box for irradiation treatment, the irradiation power is 300-500W, the irradiation time is 10-20min, after irradiation, obtaining active cyclodextrin, then sending into a silane coupling agent for ultrasonic reaction for 1-2h, the ultrasonic power is 200-300W, the reaction temperature is 100-120 ℃, and after reaction, obtaining amphoteric cyclodextrin;
s2: sending the graphene into an acetone solvent to be stirred for 10-20min, wherein the stirring speed is 100-150r/min, then adding modified bentonite to perform ultrasonic dispersion for 20-30min, wherein the ultrasonic power is 300-500W, and finishing the ultrasonic dispersion to obtain a graphene liquid;
s3: and (3) feeding the amphoteric cyclodextrin into the graphene liquid for reaction treatment, wherein the reaction temperature is 85-95 ℃, the reaction time is 20-30min, and the interconnection agent is obtained after the reaction is finished.
2. The HTCC encapsulation tube glass colorant as claimed in claim 1, wherein the modified bentonite is obtained by carrying out a hot-pressing reaction on bentonite at 800-.
3. The HTCC encapsulation tube glass colorant as claimed in claim 1, wherein the gelation reaction comprises mixing inorganic powder raw materials and gel raw materials, fully ball milling, controlling the particle size of all the powder materials to be D50-3-5 μm, stabilizing and homogenizing the formed gel slurry suspension, controlling the gel reaction speed to form a wet blank, and drying the wet blank to form a gel block.
4. The HTCC encapsulation tube glass pigment as recited in claim 3, wherein the gel block is calcined at a temperature of 1200-1400 ℃, the calcining atmosphere is a weak oxygen atmosphere, and the temperature is kept for 2-4 hours, so that the oxide elements are fully reacted.
5. The HTCC encapsulation tube shell glass pigment as claimed in claim 4, wherein the calcined gel block is jaw-crushed to a particle size of 1-3 mm, wet-ground by a sand mill to a particle D50 of 0.5-0.8 μm, dried by an oven at 100 ℃ and 150 ℃, and screened by a stainless steel screen of 100 meshes to prepare the Al-containing powder2O3-MgO-CaO-SiO2-MoO3-Cr2O3A composite spinel.
6. The HTCC encapsulating envelope glass colorant of claims 1-5, wherein the manufacturing process comprises the steps of:
(1) preparing and ball-milling inorganic powder gel slurry to make the particle size of inorganic powder particles reach D50 ═ 3-5 μm;
(2) initiating a gel reaction to enable the inorganic powder to form a gel block, and calcining the block in a weak oxygen atmosphere to synthesize complex-phase spinel;
(3) and carrying out jaw crushing, wet sanding, drying and sieving on the sintered complex phase spinel to obtain the glass pigment with the particle size of 0.5-0.8 mu m.
7. The glass pigment in claim 6 is prepared by using 65-68% of alumina, 8-10% of glass pigment and 20-25% of casting auxiliary agent according to the following steps of pulping, casting, punching, printing, laminating, cutting, sintering, brazing and electroplating, and is prepared into a black alumina HTCC integrated circuit ceramic packaging shell, a crystal oscillator, an MEMS sensor packaging substrate, an image sensor packaging shell and a black alumina substrate, wherein the co-firing temperature is 1540-1580 ℃.
Technical Field
The invention relates to the technical field of ceramics for packaging microelectronic components, in particular to a glass pigment for an HTCC packaging tube shell, a preparation method and application thereof.
Background
The black alumina ceramic packaging tube shell has a series of excellent performances such as shading property, good air tightness, strong radiation resistance, high strength, high hardness, abrasion resistance, high temperature resistance, good insulativity, acid and alkali resistance and the like, and is widely applied to integrated circuit packaging. With the development of high density and high integration in the microelectronic and semiconductor industries, the requirements on the strength, the air tightness and the circuit design density of the ceramic package tube shell are higher. The traditional method for preparing the tube shell is an HTCC process, namely a high-temperature co-fired ceramic technology, the related process is that casting slurry is prepared from 65-68% of alumina, 8-10% of fluxing agent auxiliary materials, colorant auxiliary materials and 20-25% of casting auxiliary materials, and the cast membrane is subjected to the working procedures of cutting, printing, laminating, hot pressing, co-firing, electroplating and the like. In the batching mode, too many auxiliary materials and too large specific surface area fluctuation are adopted, so that the preparation of the slurry with high solid content is difficult when the casting slurry is prepared, and great inconvenience is brought to factory production; and the densities of the front surface and the back surface of the prepared membrane are not uniform, and pigments are easy to segregate on the surface, so that the design of a product printing circuit is interfered.
Under the condition that the alumina content of a ceramic body of an HTCC packaging tube shell is not more than 92 percent, the whole performance of the ceramic tube shell can be ensured only by realizing fine tillage and fine operation of a ceramic preparation technology, for example, by adopting alumina powder and auxiliary materials with finer particles, adopting a more scientific ceramic formula, carrying out particle grading on powder, carrying out pretreatment on auxiliary materials of a cosolvent in advance to prepare microcrystalline glass and the like, but the problems of uneven surface density of the upper surface and the lower surface of a casting film, pigment segregation, high difficulty in large-scale production and pulping, overhigh co-firing temperature and the like are not essentially solved by the method; based on the above, the invention provides a glass pigment for an HTCC (high temperature capacitor packaging) tube shell.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a HTCC encapsulation tube shell glass pigment, a preparation method and application thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides an HTCC (high temperature resistant ceramic) packaging tube shell glass pigment, which comprises the following inorganic powder raw materials in parts by weight:
20-32 parts of aluminum oxide, 15-22 parts of kaolin, 16-20 parts of talcum powder, 8-13 parts of molybdenum trioxide, 6-12 parts of chromium oxide, 5-14 parts of calcium carbonate and 1-6 parts of an interconnecting agent;
the inorganic powder raw material is subjected to a gelation reaction, and the gelation raw material comprises: 2.0-2.5 parts of acrylamide organic monomer, 0.1-0.12 part of N, N' -methylene bisacryloyl cross-linking agent, 0.5-1.0 part of Rohm and Haas OROTAN 1124 dispersant, 0.2-0.4 part of ammonium persulfate initiator, 0.05-0.1 part of tetramethyl ethylene diamine, 10-15 ml of 28% ammonia water solution and 40-50 parts of deionized water;
the preparation method of the interconnecting agent comprises the following steps:
s1: sending cyclodextrin into 10-30% of fatty alcohol-polyoxyethylene ether sodium sulfate solution by mass fraction for low-speed stirring for 20-30min, wherein the stirring speed is 100-200r/min, after stirring, taking out, washing, sending into a proton irradiation box for irradiation treatment, the irradiation power is 300-500W, the irradiation time is 10-20min, after irradiation, obtaining active cyclodextrin, then sending into a silane coupling agent for ultrasonic reaction for 1-2h, the ultrasonic power is 200-300W, the reaction temperature is 100-120 ℃, and after reaction, obtaining amphoteric cyclodextrin;
s2: sending the graphene into an acetone solvent to be stirred for 10-20min, wherein the stirring speed is 100-150r/min, then adding modified bentonite to perform ultrasonic dispersion for 20-30min, wherein the ultrasonic power is 300-500W, and finishing the ultrasonic dispersion to obtain a graphene liquid;
s3: and (3) feeding the amphoteric cyclodextrin into the graphene liquid for reaction treatment, wherein the reaction temperature is 85-95 ℃, the reaction time is 20-30min, and the interconnection agent is obtained after the reaction is finished.
Preferably, the modified bentonite is obtained by carrying out hot-pressing reaction on the bentonite at 800-1200 ℃ for 20-30min under the hot-pressing pressure of 10-20 MPa.
Preferably, the gelation reaction is performed by mixing inorganic powder raw materials and gel raw materials, sufficiently ball-milling the mixture, controlling the particle size of all the powder materials to be D50-5 μm, stabilizing and homogenizing the formed gel slurry suspension, controlling the speed of the gelation reaction to form a wet blank, and drying the wet blank to form a gel block.
Preferably, the gel block is calcined at the temperature of 1200-1400 ℃, the calcining atmosphere is a weak oxygen atmosphere, and the heat preservation time is 2-4 hours, so that the oxide elements are fully reacted.
Preferably, the calcined gel block is jaw-crushed to a particle size of 1-3 mm, wet-ground by a sand mill to a particle D50 of 0.5-0.8 μm, dried in an oven at 100 ℃ and 150 ℃, and screened by a stainless steel screen of 100 meshes to prepare Al2O3-MgO-CaO-SiO2-MoO3-Cr2O3A composite spinel.
The invention provides an HTCC encapsulation tube shell glass pigment, which comprises the following steps:
(1) preparing and ball-milling inorganic powder gel slurry to make the particle size of inorganic powder particles reach D50 ═ 3-5 μm;
(2) initiating a gel reaction to enable the inorganic powder to form a gel block, and calcining the block in a weak oxygen atmosphere to synthesize complex-phase spinel;
(3) and carrying out jaw crushing, wet sanding, drying and sieving on the sintered complex phase spinel to obtain the glass pigment with the particle size of 0.5-0.8 mu m.
The invention also provides a glass pigment application, wherein the glass pigment application comprises the steps of preparing a black alumina HTCC integrated circuit ceramic packaging shell, a crystal oscillator, an MEMS sensor packaging substrate, an image sensor packaging shell and a black alumina substrate by using 65-68% of alumina, 8-10% of glass pigment and 20-25% of casting auxiliary agent according to the steps of pulping, casting, punching, printing, laminating, cutting, sintering, brazing and electroplating, wherein the co-firing temperature is 1540-plus-material 1580 ℃.
Compared with the prior art, the invention has the following beneficial effects:
compared with the conventional method for preparing the HTCC packaging tube shell by using ingredients, the method for prefabricating the glass pigment can obviously reduce the pulping viscosity and the pulping difficulty, and is convenient for large-scale production; the color of the porcelain formed by the glass pigment is darker, and the improvement on the density and the bending strength of the porcelain formed is also obvious; meanwhile, the method for preparing the glass pigment is simpler in material preparation, the sintering temperature is lower than that of the preparation process of the common HTCC packaging tube shell, and the energy-saving and emission-reducing effects are better;
the introduced interconnecting agent is modified by cyclodextrin, the cyclodextrin has the double properties of organophilic property and inorganophilic property, the cyclodextrin is subjected to inorganic activation firstly, then is subjected to coupling organic treatment to enhance the amphiprotic property of the cyclodextrin, and then is subjected to co-coupling treatment with graphene, hot-pressing calcined bentonite is added in the retreatment of the graphene, the lamellar structure of the graphene is shrunk, so that the shrinkage of the graphene is improved, and then inorganic powder is introduced after the graphene reacts with the interconnecting agent, so that gel raw materials are interconnected, the reaction degree among the raw materials is enhanced, the gelation reaction is improved, and the performance of a glass pigment is improved.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the HTCC encapsulating tube glass colorant of this embodiment, the inorganic powder raw materials of the glass colorant include the following raw materials in parts by weight:
20-32 parts of aluminum oxide, 15-22 parts of kaolin, 16-20 parts of talcum powder, 8-13 parts of molybdenum trioxide, 6-12 parts of chromium oxide, 5-14 parts of calcium carbonate and 1-6 parts of an interconnecting agent;
the inorganic powder raw material is subjected to a gelation reaction, and the gelation raw material comprises: 2.0-2.5 parts of acrylamide organic monomer, 0.1-0.12 part of N, N' -methylene bisacryloyl cross-linking agent, 0.5-1.0 part of Rohm and Haas OROTAN 1124 dispersant, 0.2-0.4 part of ammonium persulfate initiator, 0.05-0.1 part of tetramethyl ethylene diamine, 10-15 ml of 28% ammonia water solution and 40-50 parts of deionized water;
the preparation method of the interconnecting agent comprises the following steps:
s1: sending cyclodextrin into 10-30% of fatty alcohol-polyoxyethylene ether sodium sulfate solution by mass fraction for low-speed stirring for 20-30min, wherein the stirring speed is 100-200r/min, after stirring, taking out, washing, sending into a proton irradiation box for irradiation treatment, the irradiation power is 300-500W, the irradiation time is 10-20min, after irradiation, obtaining active cyclodextrin, then sending into a silane coupling agent for ultrasonic reaction for 1-2h, the ultrasonic power is 200-300W, the reaction temperature is 100-120 ℃, and after reaction, obtaining amphoteric cyclodextrin;
s2: sending the graphene into an acetone solvent to be stirred for 10-20min, wherein the stirring speed is 100-150r/min, then adding modified bentonite to perform ultrasonic dispersion for 20-30min, wherein the ultrasonic power is 300-500W, and finishing the ultrasonic dispersion to obtain a graphene liquid;
s3: and (3) feeding the amphoteric cyclodextrin into the graphene liquid for reaction treatment, wherein the reaction temperature is 85-95 ℃, the reaction time is 20-30min, and the interconnection agent is obtained after the reaction is finished.
The modified bentonite of the embodiment is prepared by carrying out hot-pressing reaction on the bentonite at 800-1200 ℃ for 20-30min under the hot-pressing pressure of 10-20 MPa.
In the gelation reaction of this example, the inorganic powder raw material and the gel raw material are mixed and sufficiently ball-milled, the particle size of all powders is controlled to be D50 ═ 3 to 5 μm, so that the formed gel slurry suspension is stable and uniform, the rate of the gelation reaction is controlled to form a wet blank, and the wet blank is dried to form a gel block.
The gel block is calcined at the temperature of 1200-1400 ℃, the calcining atmosphere is a weak oxygen atmosphere, and the heat preservation time is 2-4 hours, so that the oxide elements are fully reacted.
The calcined gel block of this embodiment is jaw-crushed to a particle size of 1-3 mm, wet-ground with a sand mill to a particle D50 of 0.5-0.8 μm, oven-dried at 100-2O3-MgO-CaO-SiO2-MoO3-Cr2O3A composite spinel.
The preparation process of the HTCC encapsulating tube glass colorant of this embodiment includes the following steps:
(1) preparing and ball-milling inorganic powder gel slurry to make the particle size of inorganic powder particles reach D50 ═ 3-5 μm;
(2) initiating a gel reaction to enable the inorganic powder to form a gel block, and calcining the block in a weak oxygen atmosphere to synthesize complex-phase spinel;
(3) and carrying out jaw crushing, wet sanding, drying and sieving on the sintered complex phase spinel to obtain the glass pigment with the particle size of 0.5-0.8 mu m.
The glass pigment of the embodiment is prepared by using 65-68% of alumina, 8-10% of glass pigment and 20-25% of casting auxiliary agent according to the following steps of pulping, casting, punching, printing, laminating, cutting, sintering, brazing and electroplating, and is prepared into a black alumina HTCC integrated circuit ceramic packaging shell, a crystal oscillator, an MEMS sensor packaging substrate, an image sensor packaging shell and a black alumina substrate, wherein the co-firing temperature is 1540-doped 1580 ℃.
Example 1
In an embodiment of the invention, a preparation process of a glass colorant for an HTCC encapsulating tube shell includes the following steps: (1) preparing and ball-milling inorganic powder gel slurry to make the particle size of inorganic powder particles reach D50 ═ 4 μm; (2) initiating a gel reaction to enable inorganic powder to form a gel block, and calcining the block in a weak oxygen atmosphere to synthesize complex-phase spinel; (3) and carrying out jaw crushing, wet sanding, drying and sieving on the sintered complex phase spinel to obtain the glass pigment with the particle size of 0.6 mu m.
The inorganic powder raw materials comprise: 28 parts of aluminum oxide, 18 parts of kaolin, 18 parts of talcum powder, 10 parts of molybdenum trioxide, 12 parts of chromium oxide, 8 parts of calcium carbonate and 1 part of an interconnection agent.
The preparation method of the interconnecting agent of the embodiment comprises the following steps:
s1: sending cyclodextrin into a fatty alcohol-polyoxyethylene ether sodium sulfate solution with the mass fraction of 10% for low-speed stirring for 20min, wherein the stirring speed is 100r/min, after stirring, taking out, washing, sending into a proton irradiation box for irradiation treatment, wherein the irradiation power is 300W, the irradiation time is 10min, after irradiation, obtaining active cyclodextrin, then sending into a silane coupling agent for ultrasonic reaction for 1h, the ultrasonic power is 200W, the reaction temperature is 100 ℃, and after reaction, obtaining amphoteric cyclodextrin;
s2: feeding graphene into an acetone solvent, stirring for 10min at the stirring speed of 100r/min, then adding modified bentonite, performing ultrasonic dispersion for 20min at the ultrasonic power of 300W, and finishing the ultrasonic treatment to obtain a graphene solution;
s3: and (3) feeding the amphoteric cyclodextrin into the graphene liquid for reaction treatment, wherein the reaction temperature is 85 ℃, the reaction time is 20min, and the interconnection agent is obtained after the reaction is finished.
The modified bentonite of the example was prepared by reacting bentonite at 800 ℃ for 20min under 10 MPa.
The gel raw materials comprise: 2.2 parts of organic monomer (acrylamide), 0.1 part of cross-linking agent (N, N' -methylene bisacrylamide), 0.8 part of dispersing agent (Rohm and Haas OROTAN 1124), 0.2 part of initiator (ammonium persulfate), 0.07 part of catalyst (tetramethyl ethylene diamine), 12ml of pH regulator (28% ammonia water solution) and 43 parts of deionized water.
The gelation process is that inorganic powder is weighed and then mixed with gel raw materials for ball milling, the speed of gel reaction is controlled to form a wet blank, and the wet blank is dried to prepare a gel block.
And calcining the gel block at 1250 ℃, wherein the calcining atmosphere is weak oxygen atmosphere, and the heat preservation time is 2 hours, so that the oxide elements are fully reacted.
Crushing the calcined material block in a jaw crusher to particle size of 1mm, wet grinding the particles in a sand mill to obtain slurry with particle D50 of 0.6 μm, pouring out the slurry, drying in an oven at 100-150 deg.C, and sieving with a 100-mesh stainless steel sieve to obtain Al2O3-MgO-CaO-SiO2-MoO3-Cr2O3The composite spinel is marked as glass pigment.
The method for preparing the ceramic packaging tube shell material by using the glass pigment comprises the following steps: 67.69% of alumina, 9.23% of glass pigment (I) and 23.08% of casting auxiliary agent are prepared into casting slurry powder, and then the casting slurry powder is uniformly mixed and cast for molding.