CN115536402A - Preparation method of silicon nitride/tungsten high-temperature co-fired ceramic substrate - Google Patents
Preparation method of silicon nitride/tungsten high-temperature co-fired ceramic substrate Download PDFInfo
- Publication number
- CN115536402A CN115536402A CN202211172774.3A CN202211172774A CN115536402A CN 115536402 A CN115536402 A CN 115536402A CN 202211172774 A CN202211172774 A CN 202211172774A CN 115536402 A CN115536402 A CN 115536402A
- Authority
- CN
- China
- Prior art keywords
- silicon nitride
- powder
- raw material
- temperature
- silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
- C04B35/593—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by pressure sintering
- C04B35/5935—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by pressure sintering obtained by gas pressure sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5133—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the refractory metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6025—Tape casting, e.g. with a doctor blade
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/606—Drying
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/612—Machining
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Products (AREA)
Abstract
The invention relates to a preparation method of a silicon nitride/tungsten high-temperature co-fired ceramic substrate, which comprises the following steps: (1) Taking silicon powder/silicon nitride powder as raw material powder, taking rare earth oxide and alkaline earth metal oxide as composite sintering aids, carrying out primary ball milling mixing with a solvent, adding a plasticizer and a binder for secondary ball milling, and finally carrying out vacuum deaeration to obtain mixed slurry; (2) Adopting tape casting equipment to tape-cast the mixed slurry to prepare a raw material tape; (3) Drawing a conductive pattern on the casting film by using metal W slurry as printing conductive slurry through a screen printing machine, and drying to obtain a raw material belt printed with the conductive pattern; (4) And cutting and laminating the raw material belt printed with the conductive pattern to obtain a silicon nitride membrane with required thickness, and then performing vacuum de-bonding and air pressure sintering to obtain the silicon nitride/tungsten high-temperature co-fired ceramic.
Description
Technical Field
The invention relates to a preparation method of a silicon nitride/tungsten high-temperature co-fired ceramic substrate, belonging to the technical field of power device packaging.
Background
With the increasing development of electronic technology, power electronic devices are gradually developed in the directions of high integration, high power, high energy consumption and the like. The power electronic device is used as a digital-to-electric conversion center and a signal propagation path in electronic equipment, and the application fields of the power electronic device cover various fields such as energy, traffic, basic industry and the like. The characteristics of high power, high frequency and integration lead the power to reach GW level. The problem that the heat generation is serious due to high energy density and the working stability and the service life of the device are seriously influenced is increasingly prominent. Therefore, a ceramic substrate with higher heat dissipation performance becomes a reasonable choice. Alumina and aluminum nitride are currently the commonly used ceramic substrate materials. But the thermal conductivity of the alumina is lower, and the increasing heat dissipation requirement cannot be met; the aluminum nitride ceramic has a relatively high thermal conductivity, but has a poor mechanical property, and cannot bear the mechanical property challenge of the substrate caused by application environments such as thermal shock and impact. The silicon nitride ceramic has the advantage of high reliability, and as the research on the high-thermal conductivity silicon nitride ceramic is matured day by day, the problem of thermal conductivity is gradually solved. Silicon nitride ceramics are therefore currently a very advantageous candidate. However, few reports are reported on the research based on metallization of silicon nitride ceramics, which directly limits the application of the silicon nitride ceramics in power electronic devices. Therefore, the invention provides a metallization method of a silicon nitride ceramic substrate, which provides reference for the application of the silicon nitride ceramic substrate in the field of power electronic devices.
Disclosure of Invention
The invention aims to provide a method for metalizing a silicon nitride ceramic substrate so as to solve the problems of heating and working stability of a substrate material caused by a high-power-density electronic device.
In one aspect, the invention provides a preparation method of silicon nitride/tungsten high-temperature co-fired ceramic, which comprises the following steps:
(1) Taking silicon powder/silicon nitride powder as raw material powder, taking rare earth oxide and alkaline earth metal oxide as composite sintering aids, carrying out primary ball milling mixing with a solvent, adding a plasticizer and a binder for secondary ball milling, and finally carrying out vacuum defoaming to obtain mixed slurry;
(2) Adopting tape casting equipment to tape-cast the mixed slurry to prepare the raw material tape;
(3) Drawing a conductive pattern on the casting film by using metal W slurry as printing conductive slurry through a screen printing machine, and drying to obtain a raw material belt printed with the conductive pattern;
(4) And cutting and laminating the obtained raw material belt printed with the conductive pattern to obtain a silicon nitride membrane with required thickness, and then performing vacuum de-bonding and gas pressure sintering to obtain the silicon nitride/tungsten high-temperature co-fired ceramic.
In the course of previous research, the present inventors found through research (as shown in fig. 3) that molybdenum tends to react more thermodynamically with silicon nitride at high temperatures than tungsten and molybdenum. However, the present inventors have found that the bonding strength between the metal layer and the substrate should not be provided by the metal functional phase, and excessive interfacial reaction may adversely affect the conductivity of the metal layer. Thus, the inventors selected metallic tungsten. Further, the invention has the following technical difficulties: (1) The silicon nitride with high thermal conductivity is prepared by using the raw material containing silicon powder, and the thermal conductivity of the silicon nitride is improved mainly by optimizing the proportion of sintering aids and controlling the reaction sintering and post-sintering process technology; (2) And good interface combination between the tungsten metal layer and the silicon nitride substrate is realized, so that sintering matching and metal layer conductivity are realized. Performing pretreatment on powder by ball milling to obtain a finer powder raw material; the porosity of the substrate and the metal layer after debonding is reduced by optimizing the solid content of the slurry; obtaining a proper tungsten metallized film on the ceramic green ceramic chip obtained by the tape casting process by using a screen printing technology; finally, a smaller sintering shrinkage rate is achieved, and the shrinkage rate matching of the two is realized. To achieve sinter matching and metal layer conduction. The invention realizes the conduction of the metal layer and provides test data.
Preferably, the solvent is ethanol, ethyl acetate, 2-butanone or a mixture of ethanol/butanone and ethyl acetate/butanone.
Preferably, the rare earth oxide is at least one of erbium oxide and samarium oxide; the alkaline earth metal oxide is at least one of MgO and CaO; wherein the mass ratio content of the alkaline earth metal oxide to the rare earth oxide is (20-40): (60-80).
Preferably, the raw material is at least one of silicon powder and silicon nitride powder, when the content of the silicon powder is more than 0%, the mass of the silicon powder is calculated as the mass after complete nitridation, and the mass content of the sintering aid is obtained based on the total mass of the powder obtained by the calculation method.
Preferably, when silicon powder and silicon nitride are used as raw materials, the mass content of the sintering aid is 5-13%. Preferably, the content of the silicon powder is more than or equal to 0wt% (more preferably 20-100 wt%), and the total mass of the silicon powder and the silicon nitride powder is recorded as 100wt%.
Preferably, the grain size range of the silicon powder is 0.5-20 μm, and the oxygen content is 0.42wt%; the grain diameter of the silicon nitride powder is 0.3-2 mu m.
Preferably, the binder is one of polyvinyl butyral, polymethyl methacrylate and polypropylene carbonate.
Preferably, the dispersant is one of triolein, castor oil phosphate and terpineol.
Preferably, the plasticizer is at least one of butyl benzyl phthalate, dioctyl phthalate and polyethylene glycol 400, such as butyl benzyl phthalate-polyethylene glycol 400 or dioctyl phthalate-polyethylene glycol 400.
Preferably, the vacuum degree of the vacuum defoaming is 15-400 Pa, and the defoaming time is 15-40 min.
Preferably, the parameters of the tape casting include: the height of the scraper is 100 mu m-1.00 mm; the thickness of each raw material belt is 50 mu m-0.50 mm.
Preferably, the setting parameters of the screen printer include: the rubber scraper is 30-50 degrees, the plate pitch is 1-10mm, the lifting stroke is 100-200mm, and the printing speed and the ink returning speed are 10% and 30% respectively.
Preferably, the size of the cut raw material tape printed with the conductive pattern is 50mm × 50mm;
the number of the laminated layers is at least 10, the pressure is 2-30MPa, and the time is 15-40 min.
Preferably, the temperature for debonding is 400-700 ℃, and the time is 1-6 hours under a vacuum condition; preferably, the heating rate of the vacuum debonding is 1-5 ℃/min.
Preferably, the temperature of the air pressure sintering is 1800-1950 ℃, the nitrogen pressure is 200-900KPa, and the heat preservation time is 2-24 hours; preferably, the temperature rise rate of the air pressure sintering is 1-5 ℃/min.
Preferably, when the raw material contains silicon powder, before the air pressure sintering, the silicon nitride membrane after the debonding is subjected to nitriding treatment; the temperature of the nitriding treatment is 1350-1550 ℃, and the heat preservation time is 2-24 hours; preferably, the temperature increase rate of the nitriding treatment is 1 to 5 ℃/min.
In another aspect, the invention provides a silicon nitride/tungsten high-temperature co-fired ceramic prepared according to the preparation method.
Has the advantages that:
the invention provides a tape casting preparation method of a silicon nitride ceramic substrate, which comprises the following steps: preparing uniformly mixed silicon casting slurry by taking the mixed solvent, the silicon powder, the sintering aid, the binder and the plasticizer as raw materials, and obtaining a crimpable green body with proper strength and plasticity through casting forming;
the invention uses commercial AlN tungsten metallization slurry as ink, and coats a metallization circuit with uniform thickness and clearness on the surface of the green body by a screen printing process. And obtaining the silicon/tungsten multilayer green compact through laser cutting and laminating hot pressing. Then, through the common de-bonding, nitriding and sintering processes, the silicon nitride/tungsten high-temperature co-fired ceramic with a smooth W metal layer, no warpage, stable interface bonding and stable performance of a silicon nitride substrate is obtained;
the invention provides a silicon nitride ceramic substrate with reliable quality, and metallization of the silicon nitride ceramic substrate is successfully realized on the silicon nitride ceramic substrate. The method provides experimental basis for the application of the silicon nitride ceramic substrate in the multilayer co-fired component, and is favorable for expanding the application of the silicon nitride ceramic in the electronic industry.
Drawings
FIG. 1 is a surface view of a W-containing multilayer sintered sample;
FIG. 2 is a side view of a W-containing multilayer sintered sample;
FIG. 3 shows W/Mo and Si 3 N 4 The reaction Gibbs energy of the substrate is changed at 0-1850 ℃;
FIG. 4 is an XRD pattern of a cross section of a sintered body of the silicon nitride multilayer assembly in the example.
Detailed Description
The present invention is further illustrated by the following examples, which are to be construed as merely illustrative, and not a limitation of the present invention.
The invention takes silicon nitride/silicon powder as raw materials, obtains a silicon nitride biscuit by tape casting, and performs nitridation and sintering after debonding to prepare the silicon nitride ceramic substrate. The silicon nitride/silicon powder is adopted as the raw material for reaction sintering, and the silicon powder can avoid the problems of high cost, easy deliquescence restriction and the like of the high-purity silicon nitride raw material, realize the low-cost preparation of the silicon nitride ceramic and promote the mass production of the silicon nitride ceramic. And the silicon powder has the advantage of low oxygen content, and a silicon nitride substrate with higher thermal conductivity is easy to obtain.
The invention uses tape casting technology to prepare silicon nitride biscuit, silicon nitride/silicon powder is used as raw material powder, rare earth oxide Re 2 O 3 And metal oxide MgO/CaO as a composite sintering aid to obtain mixed powder. And mixing the raw materials with the dispersing agent and the solvent through primary ball milling, then adding the binder and the dispersing agent, performing secondary ball milling mixing and defoaming to obtain slurry, and performing tape casting to obtain a biscuit. Then the silicon nitride ceramic substrate is obtained through debonding, nitriding and sintering.
According to the metallization technology of the silicon nitride ceramic substrate, the biscuit obtained by the tape casting technology is used as a substrate, commercial tungsten metallization slurry is used as ink, and screen printing is carried out to prepare the silicon nitride/tungsten co-fired biscuit.
Tape casting: using silicon nitride/silicon powder as raw material, rare earth oxide RE 2 O 3 And alkali metal oxide (MgO/CaO) as a composite sintering aid. Using ethanol, ethyl acetate, 2-butanone or mixture of ethanol/butanone and ethyl acetate/butanone as solvent, and using trioleinOne of castor oil phosphate and terpineol is used as a dispersing agent, one of polyvinyl butyral, polymethyl methacrylate and polypropylene carbonate is used as a binder, one of butyl benzyl phthalate and dioctyl phthalate is used as a plasticizer I, and polyethylene glycol 400 is used as a plasticizer II. Firstly, carrying out primary ball milling on a solvent, a dispersing agent, silicon nitride/silicon powder and a sintering aid, adding a binder and a plasticizer for secondary ball milling after 24-36 hours, obtaining uniformly mixed slurry after 48-72 hours, defoaming, and carrying out tape casting by using a tape casting machine.
Silicon nitride ceramic biscuit and tungsten metallization slurry obtained by tape casting process.
And (3) printing tungsten slurry with uniform thickness on the silicon nitride ceramic biscuit by using a screen printing device. And cutting the biscuit dried at room temperature into square blocks with the same size, and performing multilayer isobaric laminating to obtain a multilayer biscuit with the required thickness. Preferably, a laser cutting method is used to obtain a square block having a size of 50mm × 50mm, and lamination is performed.
As an example of screen printing, there are: and after the parameters of the screen printing machine are set, screen printing is carried out on the biscuit through the screen printing machine. The parameters of the screen printer are set as follows, a rubber scraper is 30-50 degrees, the plate distance is 1-10mm, the lifting stroke is 100-200mm, and the printing speed and the ink returning speed are respectively 10% and 30%. Then, the square sheets with the same size of 50mm multiplied by 50mm are obtained through laser cutting, 10 to 20 sheets are laminated for 15 to 40min under the pressure of 2 to 30MPa each time to obtain square blocks with uniform thickness, and then the square blocks are subjected to de-bonding, nitriding and sintering.
Debinding, nitriding and sintering. Firstly, a debonding process is carried out, the debonding temperature is usually 400-700 ℃, the temperature is kept for 1-6 hours under the vacuum condition, and the heating rate is 1-5 ℃/min. If the book raw material contains silicon powder, nitriding treatment is carried out after the debonding is finished, wherein the nitriding temperature is 1350-1550 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 2-24 hours. Sintering the periphery of the nozzle by adopting a gas pressure sintering process, wherein the atmosphere is a nitrogen atmosphere, the temperature is 1800-1950 ℃, the gas pressure is 200-900KPa, the time is 2-24 hours, and the temperature rise rate of the sintering is 1-5 ℃/min.
In the invention, a tape casting method is used for preparing the silicon nitride ceramic substrate, a silk screen printing process is used for printing tungsten slurry on a silicon nitride ceramic biscuit, and then the silicon nitride ceramic biscuit is subjected to joint debonding, nitriding and sintering after cutting and laminating. On the basis of the performance of the traditional silicon nitride substrate, the preparation method has the advantages of low cost, higher thermal conductivity and high production efficiency, and is a preparation scheme with the advantage of mass production.
The relative density of the silicon nitride ceramic substrate material measured by the Archimedes drainage method is 90-97%. The thermal conductivity of the silicon nitride ceramic substrate material is measured to be 65-70W/m.K by adopting a laser thermal conductivity meter method. The bending strength of the silicon nitride ceramic substrate material is 700-900 MPa measured by a three-point bending method. Through measurement, 100wt% of silicon powder is used as a raw material, and the sintering shrinkage is 8% -12%. 100wt% of silicon nitride is used as a raw material, and the sintering shrinkage rate is 15-20%. When the content of the silicon powder is changed, the sintering shrinkage rate is different from 8% to 20%. After measurement, the thickness of the metallized layer after co-firing is 7-10 μm. The W is obtained by adopting X-ray diffraction analysis on the silicon nitride/W interface after co-firing 5 Si 3 And (5) phase generation. The sheet resistance of the metal layer is 0.8-1.0 omega/sq measured by a square resistance method.
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also merely one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Using silicon powder as raw material (107.67 g), using an azeotropic mixture of 78wt% ethyl acetate and 22wt% 2-butanone as solvent, mgO and Er 2 O 3 As a sintering aid, 3wt% MgO and Er 2 O 3 The content was 9wt%. Triolein is a dispersant. And carrying out ball milling on the solvent, the dispersing agent and the powder for 24 hours.The preparation method comprises the steps of taking the polypropylene carbonate as a binder, taking butyl benzyl phthalate and polyethylene glycol 400 as plasticizers, adding the materials, performing secondary ball milling for 48 hours to obtain uniformly mixed slurry, defoaming the slurry for 25-30 minutes, performing tape casting by using a tape casting machine, wherein the height of a scraper is 0.4mm, and the tape casting speed is 120mm/min. And taking out the reel after the casting film is dried. The tungsten paste is printed by using a screen printer, a rubber scraper is arranged at 45%, the plate distance is 2mm, the lifting stroke is 150mm, and the printing speed and the ink returning speed are respectively 10% and 30%. And printing tungsten slurry on the obtained silicon nitride biscuit, and airing at room temperature. Cutting the casting film into rectangles with the size of 50mm multiplied by 50mm, taking 10 pieces each time, maintaining the pressure for 1min under a manual hydraulic press, putting the rectangles into a 60 ℃ oven, preserving the temperature for 30min, continuously applying the same pressure to the die after taking out the rectangles, and taking out the samples from the die after natural cooling. Preserving the heat for 1h at 600 ℃ in a vacuum debonding furnace. After the debonding, the temperature is kept for 2h at 1450 ℃ under the nitrogen atmosphere. And after nitriding, further heating the product to 1830 ℃, and preserving heat for 2h to finish sintering. And cooling along with the furnace after the completion to prepare the silicon nitride/tungsten high-temperature co-fired ceramic with a smooth and warp-free W metal layer, stable interface bonding and stable silicon nitride substrate performance.
Example 2
In this example 2, the preparation process of the silicon nitride/tungsten high temperature co-fired ceramic is as in example 1, except that: selecting Si powder and Si 3 N 4 The powder was used as a raw material (total 107.67 g), in which the Si powder content was 80%. The prepared silicon nitride/tungsten high-temperature co-fired ceramic has the advantages of smooth and warp-free W metal layer, stable interface bonding and stable silicon nitride substrate performance.
Example 3
In this example 3, the preparation process of the silicon nitride/tungsten high temperature co-fired ceramic is as in example 1, except that: selecting Si powder and Si 3 N 4 The powder was used as a raw material (total 107.67 g), in which the Si powder content was 60%. The prepared silicon nitride/tungsten high-temperature co-fired ceramic has the advantages of smooth and warp-free W metal layer, stable interface bonding and stable silicon nitride substrate performance.
Example 4
In this example 4, the preparation process of the silicon nitride/tungsten high temperature co-fired ceramic is as in example 1, except that: selectingSi powder and Si 3 N 4 Powder as a raw material (total 107.67 g), in which the Si powder content was 40%. The prepared silicon nitride/tungsten high-temperature co-fired ceramic has the advantages of smooth and warp-free W metal layer, stable interface bonding and stable silicon nitride substrate performance.
Example 5
In this example 5, the preparation process of the silicon nitride/tungsten high temperature co-fired ceramic is as in example 1, except that: selecting Si powder and Si 3 N 4 Powder as a raw material (107.67 g in total), wherein the content of Si powder is 0%; to ensure compact sintering, an azeotropic mixture of 78wt% ethyl acetate and 22wt% 2-butanone as a solvent, mgO and Er 2 O 3 As a sintering aid, 3wt% MgO and Er 2 O 3 The content was 9wt%. The prepared W metal layer is smooth and warpage-free, but the pattern shrinkage of the metal layer is inconsistent.
Through experimental exploration, si/Si in powder is changed in the silicon nitride tape casting process 3 N 4 The results of the sheet resistance of the metal layer are as follows. Si powder and Si3N4 powder were selected as raw materials (total 107.67 g), and the sheet resistance of the metal layer was 0.89. Omega./sq, when the Si powder content was 100%. When the content of the Si powder is 80%, the sheet resistance of the metal layer is 1.22 omega/sq. When the content of the Si powder is 60%, the sheet resistance of the metal layer is 1.09 omega/sq. When the content of the Si powder is 40%, the sheet resistance of the metal layer is 1.14 omega/sq. When the content of the Si powder is 20%, the sheet resistance of the metal layer is 1.47 omega/sq. When the content of Si powder is 0%, the sheet resistance of the metal layer is 1.21 omega/sq. In addition, the bonding strength of the metal to ceramic interface lacks an accurate means of testing. Macroscopically, the sintering matching result without defects of warping, delaminating, peeling and the like is shown.
Claims (12)
1. A preparation method of silicon nitride/tungsten high-temperature co-fired ceramic is characterized by comprising the following steps:
(1) Taking silicon powder/silicon nitride powder as raw material powder, taking rare earth oxide and alkaline earth metal oxide as composite sintering aids, carrying out primary ball milling mixing with a solvent, adding a plasticizer and a binder for secondary ball milling, and finally carrying out vacuum defoaming to obtain mixed slurry;
(2) Adopting tape casting equipment to tape-cast the mixed slurry to prepare a raw material tape;
(3) Drawing a conductive pattern on the casting film by using metal W slurry as printing conductive slurry through a screen printing machine, and drying to obtain a raw material tape printed with the conductive pattern;
(4) And cutting and laminating the obtained raw material belt printed with the conductive pattern to obtain a silicon nitride membrane with required thickness, and then performing vacuum de-bonding and gas pressure sintering to obtain the silicon nitride/tungsten high-temperature co-fired ceramic.
2. The method according to claim 1, wherein the solvent is ethanol, ethyl acetate, 2-butanone or a mixture of ethanol/butanone, ethyl acetate/butanone;
the rare earth oxide is at least one of erbium oxide and samarium oxide; the alkaline earth metal oxide is at least one of MgO and CaO; wherein the mass ratio content of the alkaline earth metal oxide to the rare earth oxide is (20-40): (60-80).
3. The preparation method according to claim 1 or 2, characterized in that the raw material is at least one of silicon powder and silicon nitride powder, when the content of the silicon powder is more than 0%, the mass of the silicon powder is calculated as the mass after complete nitridation, and the mass content of the sintering aid is calculated based on the total powder mass obtained after the calculation;
when silicon powder and silicon nitride are used as raw materials, the mass content of the sintering aid is 5-13%; the content of the silicon powder is more than or equal to 0wt%, and the total mass of the silicon powder and the silicon nitride powder is recorded as 100wt%.
4. The method according to any one of claims 1 to 3, wherein the silicon powder has a particle size in the range of 0.5 to 20 μm and an oxygen content of 0.42wt%; the grain diameter of the silicon nitride powder is 0.3-2 mu m.
5. The production method according to any one of claims 1 to 4, characterized in that the binder is one of polyvinyl butyral, polymethyl methacrylate, polypropylene carbonate;
the dispersant is one of triolein, castor oil phosphate and terpineol;
the plasticizer is at least one of butyl benzyl phthalate, dioctyl phthalate and polyethylene glycol 400.
6. The preparation method of any one of claims 1-5, wherein the vacuum degree of the vacuum defoaming is 15-400 mbar, and the defoaming time is 15-40 min.
7. A production method according to any one of claims 1 to 6, wherein the parameters of the tape casting include: the height of the scraper is 100 mu m-1.00 mm; the thickness of each raw material belt is 50 mu m-0.50 mm.
8. The preparation method of any one of claims 1 to 7, wherein the setting parameters of the screen printing machine comprise: the rubber scraper is 30-50 degrees, the plate pitch is 1-10mm, the lifting stroke is 100-200mm, and the printing speed and the ink returning speed are 10% and 30% respectively.
9. The method for preparing a printed material tape according to any one of claims 1 to 8, wherein the cut raw material tape printed with the conductive pattern has a size of 50mm x 50mm;
the number of the laminated layers is at least 10, the pressure is 2-30MPa, and the time is 15-40 min.
10. The method according to any one of claims 1 to 9, wherein the temperature of the de-binding is 400 to 700 ℃, and the time is 1 to 6 hours under vacuum; preferably, the heating rate of the vacuum debonding is 1-5 ℃/min;
the temperature of the air pressure sintering is 1800-1950 ℃, the nitrogen pressure is 200-900KPa, and the heat preservation time is 2-24 hours; preferably, the heating rate of the air pressure sintering is 1-5 ℃/min.
11. The preparation method according to any one of claims 1 to 10, characterized in that when the raw material contains silicon powder, before the air pressure sintering, the silicon nitride membrane after the debonding is subjected to nitriding treatment; the temperature of the nitriding treatment is 1350-1550 ℃, and the heat preservation time is 2-24 hours; preferably, the temperature increase rate of the nitriding treatment is 1 to 5 ℃/min.
12. A silicon nitride/tungsten high temperature co-fired ceramic prepared according to the preparation method described in any one of claims 1 to 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211172774.3A CN115536402A (en) | 2022-09-26 | 2022-09-26 | Preparation method of silicon nitride/tungsten high-temperature co-fired ceramic substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211172774.3A CN115536402A (en) | 2022-09-26 | 2022-09-26 | Preparation method of silicon nitride/tungsten high-temperature co-fired ceramic substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115536402A true CN115536402A (en) | 2022-12-30 |
Family
ID=84728677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211172774.3A Pending CN115536402A (en) | 2022-09-26 | 2022-09-26 | Preparation method of silicon nitride/tungsten high-temperature co-fired ceramic substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115536402A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050013989A1 (en) * | 2002-05-28 | 2005-01-20 | Yoshiyuki Hirose | Aluminum nitride sintered compact having metallized layer and method for preparation thereof |
| CN106376107A (en) * | 2016-11-24 | 2017-02-01 | 常德科锐新材料科技有限公司 | Large-power silicon nitride ceramic heating plate and inner-soft outer-hard manufacturing method thereof |
| CN109363247A (en) * | 2018-11-29 | 2019-02-22 | 深圳顺络电子股份有限公司 | A kind of preparation method of electronic cigarette and its chip heater and chip heater |
| CN109987944A (en) * | 2019-03-06 | 2019-07-09 | 清华大学 | A kind of high thermal conductivity silicon nitride ceramic substrate and preparation method thereof |
| CN114890797A (en) * | 2022-04-25 | 2022-08-12 | 中国科学院上海硅酸盐研究所 | Preparation method of silicon nitride ceramic substrate |
| CN115028461A (en) * | 2022-05-31 | 2022-09-09 | 浙江多面体新材料有限公司 | Method for preparing high-thermal-conductivity silicon nitride ceramic substrate through silicon powder tape casting |
-
2022
- 2022-09-26 CN CN202211172774.3A patent/CN115536402A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050013989A1 (en) * | 2002-05-28 | 2005-01-20 | Yoshiyuki Hirose | Aluminum nitride sintered compact having metallized layer and method for preparation thereof |
| CN106376107A (en) * | 2016-11-24 | 2017-02-01 | 常德科锐新材料科技有限公司 | Large-power silicon nitride ceramic heating plate and inner-soft outer-hard manufacturing method thereof |
| CN109363247A (en) * | 2018-11-29 | 2019-02-22 | 深圳顺络电子股份有限公司 | A kind of preparation method of electronic cigarette and its chip heater and chip heater |
| CN109987944A (en) * | 2019-03-06 | 2019-07-09 | 清华大学 | A kind of high thermal conductivity silicon nitride ceramic substrate and preparation method thereof |
| CN114890797A (en) * | 2022-04-25 | 2022-08-12 | 中国科学院上海硅酸盐研究所 | Preparation method of silicon nitride ceramic substrate |
| CN115028461A (en) * | 2022-05-31 | 2022-09-09 | 浙江多面体新材料有限公司 | Method for preparing high-thermal-conductivity silicon nitride ceramic substrate through silicon powder tape casting |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106145914B (en) | A kind of rapid shaping and sintering method of ultrathin type low-temperature co-fired ceramic substrate | |
| CN106631039A (en) | Preparation method of silicon nitride ceramic substrate | |
| US20050215417A1 (en) | Dense cordierite based sintered body and method of manufacturing the same | |
| CN109053196B (en) | Sintering method of large-size high-temperature co-fired ceramic | |
| CN115028460A (en) | Preparation method of high-thermal-conductivity silicon nitride ceramic substrate | |
| CN113563085B (en) | AlN electronic ceramic material with high dielectric property | |
| CN115536402A (en) | Preparation method of silicon nitride/tungsten high-temperature co-fired ceramic substrate | |
| CN104844250A (en) | High-temperature-resistant porous interlayer wave-transmitting material and preparation method thereof | |
| KR102189481B1 (en) | Dielectric ceramics composition for high frequency device, ceramic substrate thereby and manufacturing method thereof | |
| KR102072287B1 (en) | Fabrication method of Harmful gas Sensing sensor using Low Tepmerature Co-fired Ceramic | |
| JPH05286776A (en) | Metal-ceramics composite structure and production therefor | |
| JP3741556B2 (en) | Low-temperature fired porcelain and electronic component equipped with the same | |
| CN102040375A (en) | Low temperature co-fired ceramic material, low temperature co-fired ceramic body, and multilayer ceramic substrate | |
| CN114195527A (en) | Sintering method of step-structured high-temperature co-fired ceramic | |
| JP4859267B2 (en) | Aluminum nitride sintered body and manufacturing method thereof | |
| JPH0881267A (en) | Aluminum nitride sintered compact, its production, aluminum nitride circuit board and its production | |
| KR100421435B1 (en) | Method of manufact uring and ceramic sheet for heat to high strength and high heat conduction | |
| JP5073135B2 (en) | Aluminum nitride sintered body, production method and use thereof | |
| JP3363227B2 (en) | Manufacturing method of ceramic sintered body | |
| KR100459868B1 (en) | Composition for low temperature sinterable ceramic heater and fabrication method of ceramic heater | |
| JP3053949B2 (en) | Manufacturing method of aluminum nitride multilayer substrate | |
| KR100511109B1 (en) | Method for manufacturing multilayer ceramics with improved interlayer bonding | |
| JP2666744B2 (en) | Alumina multilayer wiring board, method of manufacturing the same, and method of manufacturing alumina sintered body | |
| CN112552055A (en) | Method for high-temperature co-firing of metal and silicon nitride ceramic composite substrate | |
| CN117658599A (en) | Ceramic heating element with high thermal shock property and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |