CN105439643A - Method for preparing copper/ceramic composite substrate on basis of low-melting-point glass powder - Google Patents
Method for preparing copper/ceramic composite substrate on basis of low-melting-point glass powder Download PDFInfo
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- CN105439643A CN105439643A CN201510785785.2A CN201510785785A CN105439643A CN 105439643 A CN105439643 A CN 105439643A CN 201510785785 A CN201510785785 A CN 201510785785A CN 105439643 A CN105439643 A CN 105439643A
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- 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
- C04B41/5127—Cu, e.g. Cu-CuO eutectic
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
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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
- 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
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- 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
Abstract
The invention provides a method for preparing a copper/ceramic composite substrate on the basis of low-melting-point glass powder. The method comprises the following steps: (1) preparing low-melting-point glass powder; (2) preparing an organic carrier; (3) preparing copper electronic paste; and (4) preparing a copper/ceramic composite substrate. According to the method, the BZBS glass powder which is prepared by employing a sol-gel method is used as a glass binder, and the copper powder is used as a functional phase, so that a copper thick film with good properties is obtained. The glass binder is good in wettability and relatively low in beginning wetting temperature, so that the thick film is sintered to be compacted, and good properties can be obtained. Meanwhile, the sintering temperature is kept for a period of time to melt the glass powder and to sufficiently wet the functional phase and the substrate, so that the increment of copper powder particles is facilitated, and the sintering is promoted.
Description
Technical field
The invention belongs to electronics industry, particularly, relate to a kind of method preparing copper/ceramic composite substrate based on glass powder with low melting point.
Background technology
Ceramic substrate refers to that Copper Foil is at high temperature bonded directly to aluminum oxide (Al
2o
3) or aluminium nitride (AlN) ceramic substrate surface (single or double) on special process plate.Made ultra-thin composite base plate has good electrical insulation performance, high thermal conduction characteristic, excellent solderability and high adhesion strength, and can etch various figure as pcb board, has very large current capacity.Therefore, ceramic substrate has become the base mateiral of high-power electric and electronic circuit structure technology and interconnection technique.
Prepare the common methods of copper/ceramic composite substrate for deposit one deck copper thick-film electronic slurry on ceramic substrate.Thick-film electronic slurry is set electron, chemical industry, metallurgical in the high-tech product of one, is one of electronic industry primary base material.It is also the base mateiral making electronic devices and components, can be used for parts encapsulation, electrode and interconnected, there is applied widely, the feature such as good product quality, high financial profit and advanced technology, occupy an important position in information, electronics, be also widely used in the numerous areas such as sensor, medical equipment, signal equipment, automotive industry, measurement and control system, High temperature IC, aerospace, robot calculator, consumer electronic product.Electric slurry is through silk screen printing and is printed on ceramic substrate, on silicon chip and glass substrate, then through levelling, dry and sinter and form conducting film, hybrid integrated circuit can be made, hot stamping brush termination, thick film pressure transducer, ceramic condenser, mica capacitor, tantalum capacitor, well heater, voltage dependent resistor, PTC thermistor, liquid crystal display (LED), plasma panel (PDP), laminated ceramic capacitor (MLCC), printed circuit board (PCB) (PCB), thin film switch, solar cell, radiator element, windshield heater wire, vibrator, product in the every field such as piezoelectric ceramic vibrator.The development scale of electronic information material related industries and state of the art, the important symbol of a national economic development, scientific-technical progress and military capability of the country, occupy a position of strategic importance in national economy, along with the fast development of information industry, electric slurry, as electronic information material, more and more will be subject to people and pay attention to.At present, the cost of electric slurry occupies 50% of electronic devices and components cost, the fast development of electronic devices and components industry facilitates the development of electric slurry, people are impelled constantly to carry out exploratory development, preparation quality is better, precision is higher, the electric slurry of better reliability to be to satisfy the demands, equally, the researchdevelopment of electric slurry is also conducive to electronic devices and components development, adapts to the development in epoch.
Electric slurry can be divided into again organic materials substrate electric slurry, ceramic substrate electric slurry, electronic paste for soda lime glass substrates and composite base plate electric slurry according to the substrate type used.Wherein, the most frequently used substrate of thick film is ceramic substrate, and conventional ceramic substrate comprises SiC, Si at present
3n
4, BeO, AlN and Al
2o
3deng ceramic substrate.
Although SiC monocrystal has higher thermal conductivity, polycrystalline Si C ceramic substrate thermal conductivity is less than 70W/ (mK), and SiC insulation degree is low, specific inductivity is large, high frequency characteristics is poor, and in circuit substrate, research application is few.Si
3n
4ceramic substrate has excellent mechanical property, and thermal expansivity is almost minimum, but its thermal conductivity is low, and dielectric properties are poor, and production cost is high, limits its application on Electronic Packaging pottery.BeO has high thermal conductivity, but thermal conductivity is unstable, thermal conductivity and Al 800 DEG C time
2o
3ceramic phase is worked as.And BeO pottery also has very strong toxicity, production cost is higher, and this all limits its propagation and employment.AlN ceramic has excellent thermal characteristics, electrical property and mechanical property.It has good thermal conductivity, low thermal expansivity, is a kind of substrate material comparing rationality, is subject to domestic and international favor.But AlN ceramic cost is high, high temperature is oxidizable and not easily metallize.Al
2o
3although pottery thermal conductivity and thermal expansivity are not as AlN ceramic, but it has abundant raw material source, cheap, good mechanical property, the chemical stability excellent over-all properties such as high, thick-film metalliz is studied comparatively ripe, as aspects such as silver thick film, copper thick film, aluminium thick films.Maximum ceramic substrates applied by current thick film circuit is 96%Al
2o
3ceramic substrate.
For being coated on the thick film copper electric slurry of ceramic base plate surface, comprise glass powder, copper powder and organic carrier, at present, the electric slurry of high temperature sintering is easy to reach non-harmful requirement, but in most cases, some parts of element internal or material can not bear high temperature, especially unicircuit, chip, various kinds of sensors part and semiconducter device, very responsive to technological temperature, require that encapsulating temperature is more low better.And the performance of glass powder determines the binding ability such as function phase and metal, glass or ceramic substrate in thick film.
So the application development of performance characteristics to electric slurry of research electric slurry glass system has certain promoter action, also can meet the development need of electric slurry high-performance, low cost, sintering temperature and low.
The research of electric slurry glass must immediately following the development in epoch, and research can meet slurry application requiring, can reduce costs again, improving SNR, broaden application face.Can study from the following aspects:
(1) due to the environmental problem of lead glass, the cost of bismuth glass and application problem, need research few bismuth low-melting-point glass, zinc glass and alkaline earth glass system scheduling theory, the multicomponent glass systems such as quaternary are studied on this glass basis, make up the deficiency of lead-free low-melting-point glass eutectic performance, in conjunction with the further modification electric slurry of composite additive.
(2) because single glass can not meet the problem such as eutectic, thermal expansion matching completely, adopt the mutual supplement with each other's advantages of multiple glass to carry out the deficiency of alternative single glass, can greatly improve research range of application like this.
(3) non-traditional preparation means is adopted, as adopted spray heating decomposition and studying the superior micron of hotter sol-gel method processability even nano-glass powder in recent years, traditional and the non-traditional combination preparing glass powder, make up the deficiency of conventional melt method to a certain extent, increase electric slurry research space further.
(4) inorganic additives of some specific functions is added in glass as ZrO
2etc. preparing devitrified glass or improve sintering process preparation containing special construction glass as isostructural in column, thus reach and obtain zero defect and the good electric slurry of adhesive power.
And in glass system preparation process, sol-gel method (sol-gel method) a kind ofly brand-new prepares material wet chemical method, by organometallics, metal inorganic compound and both mixtures thereof through hydrolytie polycondensation process, gelation gradually, and carry out corresponding aftertreatment, to obtain the novel process of oxide compound and other compounds.Prepare full dimension material wet chemical from zero dimension to three-dimensional material for reaction method as a kind of, there is a lot of advantages and a series of shortcoming.The features such as it has that technique is simple, equipment is cheap, chemical composition is even, preparation process is controlled, stoichiometry is accurate, purity is high, pollute less and preparation temperature is low.But it also has, and self shortcoming is as higher in raw materials cost, the process time long, the easy problem such as shrinkage strain and residual carbon.
Summary of the invention
For solving above-mentioned Problems existing, the object of the present invention is to provide a kind of method preparing copper/ceramic composite substrate based on glass powder with low melting point, described method adopts sol-gel method to prepare BZBS glass powder as glass binder, and copper powder is function phase, obtains copper thick film of good performance.Wherein, glass binder wettability is good and beginning wetting temperature is lower, makes thick film firing densification, obtains good performance.Meanwhile, be incubated for some time in sintering temperature, melt to allow glass powder and abundant wetting function phase and substrate, being conducive to copper powder particle and growing up, acceleration of sintering.
For achieving the above object, technical scheme of the present invention is:
Prepare a method for copper/ceramic composite substrate based on glass powder with low melting point, comprise the steps:
1) glass powder with low melting point is prepared
A. prepare tetraethoxy pre-hydrolyzed solution: get acetic acid, ethanol, tetraethoxy and water, stir lower mixing 30 ~ 40min, obtain the tetraethoxy pre-hydrolyzed solution of clarification;
B. colloidal sol is prepared: get zinc acetate, barium acetate, boric acid is placed in beaker respectively, distilled water is added respectively in zinc acetate, barium acetate place beaker, be stirred to zinc acetate respectively and barium acetate is dissolved completely, the acetic acid zinc solution that must clarify and barium acetate solution, water or alcohol formation boric acid solution is added in the beaker of boric acid place, then boric acid solution, acetic acid zinc solution, barium acetate solution and step a gained tetraethoxy pre-hydrolyzed solution are mixed, adjust ph, stir at 60 ~ 90 DEG C, obtain colloidal sol;
C. xerogel is prepared: dissolved thoroughly to colloidal sol by the colloidal sol sealing 1 ~ 2h obtained, then ageing 3 ~ 5h, obtains wet gel, wet gel is dried 20 ~ 25h at 90 ~ 110 DEG C, obtains xerogel;
D. prepare glass powder with low melting point: grinding gained xerogel, cross 120 ~ 150 order mesh screens, obtain dry gel powder, then dry gel powder is heat-treated in retort furnace just described glass powder with low melting point;
2) organic carrier is prepared
Described organic carrier comprises the chemical composition of following mass percent: ethyl cellulose: 5 ~ 10wt%, Terpineol 350: 80 ~ 90wt%, dibutyl phthalate: 1 ~ 5wt%, polyoxyethylene glycol: 1 ~ 5wt%, Viscotrol C: 1 ~ 5wt%; By ethyl cellulose, Terpineol 350, dibutyl phthalate, polyoxyethylene glycol and Viscotrol C by described mass percent mixing, constantly stir until ethyl cellulose is dissolved completely under 80 ~ 100 DEG C of water bath with thermostatic control conditions, insulation 2 ~ 3h, obtains described organic carrier;
3) copper electric slurry is prepared
By copper powder, step 1) gained glass powder with low melting point mixing rear grinding grinding 20 ~ 40min, then step 2 is added) gained organic carrier, mix and blend, pour in ball grinder, after on ball mill, carry out ball milling with the rotating speed of 250 ~ 350r/min, ball milling 2 ~ 4h, obtains described copper electric slurry;
4) copper/ceramic composite substrate is prepared
By step 3) gained copper electric slurry deposits on ceramic substrate by method for printing screen, through levelling, oven dry, sintering, obtains described copper/ceramic composite substrate.
Further, described quaternary borates with low melting points salt glass comprises the chemical composition of following molar percentage: BaO:10 ~ 40mol%, ZnO:30 ~ 40mol%, B
2o
3: 10 ~ 40mol%, SiO
2: the mol ratio of 10 ~ 40mol%, described ZnO and BaO is 4 ~ 1/4, and the mol ratio of described B2O3 and SiO2 is 4 ~ 1/4.
Separately, step 1) described in be 0.05 ~ 0.1 according to the mol ratio of acetic acid and tetraethoxy, the mol ratio of ethanol and tetraethoxy is 5 ~ 10, and the mol ratio of water and tetraethoxy is 5 ~ 10.
Separately have, step 1) to prepare in sol-process, the solvent temperature of described barium acetate is 40 ~ 60 DEG C, and the mass ratio of barium acetate and water is 79 ~ 80:100, g/g; The solvent temperature of described zinc acetate is room temperature, and the mass ratio of zinc acetate and water is 30 ~ 33:100, g/g; The solvent temperature of described boric acid is 70 ~ 80 DEG C, and the mass ratio of boric acid and water is 20 ~ 30:100, g/g, and pH value is 5 ~ 6, churning time 5 ~ 15h.
Again, step 1) described dry gel powder thermal treatment comprises following four-stage: the first stage: be warming up to 400 DEG C, heat-up rate is 5 DEG C/min, completes dehydration condensation further, to be got rid of by the organism such as residual water-content, ethanol and zinc acetate, barium acetate are thoroughly decomposed; Subordinate phase: be incubated 0.5 ~ 1.5h at 400 DEG C, organism Thorough combustion is decomposed; Phase III: be warming up to 500 DEG C, heat-up rate 10 DEG C/min; Fourth stage: at 500 DEG C, insulation 1 ~ 3h, then cools to room temperature with the furnace.
Further, step 3) described in copper powder median size be 4 ~ 5 μm, in copper electric slurry, content is 60 ~ 80wt%; Glass powder with low melting point median size is less than 3 μm, and in copper electric slurry, content is at 0 ~ 20wt%; Organic carrier in copper electric slurry content at 10 ~ 30wt%.
And, step 4) in described screen printing process, silk screen adopts Stainless Steel Cloth, printing adopts the printing of disengaging-contact process, between silk screen and described ceramic substrate, spacing is 0.5 ~ 2mm, and described copper electric slurry viscosity is 102 ~ 103Pas, and copper electric slurry solid-to-liquid ratio is 8:2.
Separately, described ceramic substrate is 96%Al
2o
3ceramic substrate, is of a size of 24mm × 24mm.
Again, also comprise the pre-treatment of described ceramic substrate, described pre-treatment comprises the steps: described 96%Al with laser
2o
3ceramic substrate cutting becomes the little square of 24mm × 24mm, to put it in alcohol ultrasonic cleaning 10 ~ 20 minutes, then clean with distilled water flushing, and dry in an oven, place it in 1000 DEG C of thermal treatment 0.5 ~ 1.5h in High Temperature Furnaces Heating Apparatus again, the organism on removing surface, last furnace cooling, takes out stand-by.
Further, step 4) in, dry 8 ~ 12min in 100 ~ 150 DEG C, in 500 DEG C of insulation 30 ~ 50min under nitrogen protection condition, be warming up to 900 DEG C with 10 DEG C/min and sinter.
Beneficial effect of the present invention is:
Design a kind of glass powder with low melting point (i.e. BaO-ZnO-B of uniqueness
2o
3-SiO
2quaternary glass powder), raw material is respectively barium acetate, zinc acetate, boric acid, tetraethoxy, can regard the extension expansion of TERNARY GLASS system as, but more stable than ternary system.
Sol-gel method is adopted to prepare BZBS glass powder, the main and SiO of its gelation mechanism
2the sol-gel mechanism of glass is similar, and known except the formation that Siliciumatom participates in gel network by infrared analysis, part of boron atom also take part in the formation of gel network, and organism noresidue after Overheating Treatment.
Wherein, barium acetate is mainly used for introducing barium oxide, can not only reduce the softening temperature of glass further, better soaks ceramic substrate and metallographic phase at a sintering temperature, can also improve adhesivity and the electroconductibility of thick film.Adopt nitrate of baryta as barium source, in water, solubleness very low causing introduces a large amount of water, and gel time extends greatly.If adopt nitrate of baryta to be difficult to ensure that dissolution homogeneity is stablized as barium source, according to barium acetate, solvent adopts dehydrated alcohol, then be also difficult to form stable and uniform solution, and a large amount of alcohol not only raises the cost but also volatile, wayward experiment.The present invention adopts water as the solvent of barium acetate, is so more conducive to evenly solution-stabilized, prepares barium acetate solution, be so more conducive to barium acetate solution and not easily separate out when Hybrid Heating under adopting normal temperature; Adopt zinc acetate to introduce as the zinc source of glass, the water-soluble and ethanol of zinc acetate, but zinc acetate solubleness in ethanolic soln is lower, easily separates out in the colloidal sol ageing stage.Consider that ethanol mainly dissolves the organism that tetraethoxy etc. is slightly soluble in water, adding of a large amount of ethanol easily causes barium acetate to separate out, and is unfavorable for the stable of solution, so adopt water as the solvent of zinc acetate; Boric acid is as B
2o
3source, boric acid belongs to mineral acid, aobvious slightly acidic in water, and in water soluble, ethanol, through inspection, boric acid is difficult to be dissolved in ethanol, and the solubleness in water is not high yet, and the present invention adopts the hydrothermal solution of boric acid, effectively accelerates dissolution rate, raising efficiency; Tetraethoxy (TEOS) is slightly soluble in water, is hydrolyzed very slow in water, can be hydrolyzed very soon under the katalysis of acid or alkali.Because TEOS belongs to organism, according to similar compatibility principle, TEOS is soluble in ethanolic soln.Catalyzer generally has nitric acid, acetic acid, hydrochloric acid, ammoniacal liquor etc.Nitric acid belongs to restriction medicine at present, and easily decomposes volatilization contaminate environment; Hydrochloric acid easily introduces Cl
-impurity, cannot ensure high-purity characteristic of sol-gel; Acetic acid is acid catalyst, effectively can regulate the pH value of dissolving as weak acid, keeps the stable of solution, ammoniacal liquor effect and acetic acid similar, mainly as alkaline catalysts.
Design specific dry gel powder thermal treatment process, effectively promote glass quality.First stage completes dehydration condensation further, got rid of by the organism such as residual water-content, ethanol and zinc acetate, barium acetate are thoroughly decomposed; Subordinate phase can better allow organism Thorough combustion decompose; Fourth stage is so that the material exhaustive oxidations such as residual carbon decompose.
Accompanying drawing explanation
What Fig. 1 provided for the embodiment of the present invention 1 a kind ofly to prepare in the method for copper/ceramic composite substrate XRD figure spectrum before and after dry gel powder thermal treatment based on glass powder with low melting point.
What Fig. 2 provided for the embodiment of the present invention 1 a kind ofly to prepare in the method for copper/ceramic composite substrate IR collection of illustrative plates before and after dry gel powder thermal treatment based on glass powder with low melting point.
What Fig. 3 provided for the embodiment of the present invention 1 ~ 4 a kind ofly to prepare in the method for copper/ceramic composite substrate different B in glass powder with low melting point based on glass powder with low melting point
2o
3/ SiO
2the infared spectrum of mol ratio glass powder.
What Fig. 4 provided for the embodiment of the present invention 1 ~ 4 a kind ofly to prepare in the method for copper/ceramic composite substrate different B in glass powder with low melting point based on glass powder with low melting point
2o
3/ SiO
2the XRD figure spectrum of mol ratio glass powder.
A kind of infared spectrum preparing different ZnO/BaO mol ratio glass powder in glass powder with low melting point in the method for copper/ceramic composite substrate based on glass powder with low melting point that Fig. 5 provides for the embodiment of the present invention 5 ~ 8.
A kind of XRD figure spectrum preparing different ZnO/BaO mol ratio glass powder in glass powder with low melting point in the method for copper/ceramic composite substrate based on glass powder with low melting point that Fig. 6 provides for the embodiment of the present invention 5 ~ 8.
A kind of different glass powder content of preparing based on glass powder with low melting point in the method for copper/ceramic composite substrate that Fig. 7 provides for the embodiment of the present invention 9 ~ 13 is on the impact of sticking power.
A kind of different glass powder content of preparing based on glass powder with low melting point in the method for copper/ceramic composite substrate that Fig. 8 provides for the embodiment of the present invention 9 ~ 13 is on the impact of sheet resistance.
A kind of different glass powder content of preparing based on glass powder with low melting point in the method for copper/ceramic composite substrate that Fig. 9 provides for the embodiment of the present invention 9 ~ 13 is on the impact of copper thick film surface pattern.
Embodiment
With reference to Fig. 1, a kind of method preparing copper/ceramic composite substrate based on glass powder with low melting point of the present invention, comprises the steps:
1) glass powder with low melting point is prepared
A. prepare tetraethoxy pre-hydrolyzed solution: get acetic acid, ethanol, tetraethoxy and water, stir lower mixing 30 ~ 40min, obtain the tetraethoxy pre-hydrolyzed solution of clarification;
B. colloidal sol is prepared: get zinc acetate, barium acetate, boric acid is placed in beaker respectively, distilled water is added respectively in zinc acetate, barium acetate place beaker, be stirred to zinc acetate respectively and barium acetate is dissolved completely, the acetic acid zinc solution that must clarify and barium acetate solution, water or alcohol formation boric acid solution is added in the beaker of boric acid place, then boric acid solution, acetic acid zinc solution, barium acetate solution and step a gained tetraethoxy pre-hydrolyzed solution are mixed, adjust ph, stir at 60 ~ 90 DEG C, obtain colloidal sol;
C. xerogel is prepared: dissolved thoroughly to colloidal sol by the colloidal sol sealing 1 ~ 2h obtained, then ageing 3 ~ 5h, obtains wet gel, wet gel is dried 20 ~ 25h at 90 ~ 110 DEG C, obtains xerogel;
D. prepare glass powder with low melting point: grinding gained xerogel, cross 120 ~ 150 order mesh screens, obtain dry gel powder, then dry gel powder is heat-treated in retort furnace just described glass powder with low melting point;
2) organic carrier is prepared
Described organic carrier comprises the chemical composition of following mass percent: ethyl cellulose: 5 ~ 10wt%, Terpineol 350: 80 ~ 90wt%, dibutyl phthalate: 1 ~ 5wt%, polyoxyethylene glycol: 1 ~ 5wt%, Viscotrol C: 1 ~ 5wt%; By ethyl cellulose, Terpineol 350, dibutyl phthalate, polyoxyethylene glycol and Viscotrol C by described mass percent mixing, constantly stir until ethyl cellulose is dissolved completely under 80 ~ 100 DEG C of water bath with thermostatic control conditions, insulation 2 ~ 3h, obtains described organic carrier;
3) copper electric slurry is prepared
By copper powder, step 1) gained glass powder with low melting point mixing rear grinding grinding 20 ~ 40min, then step 2 is added) gained organic carrier, mix and blend, pour in ball grinder, after on ball mill, carry out ball milling with the rotating speed of 250 ~ 350r/min, ball milling 2 ~ 4h, obtains described copper electric slurry;
4) copper/ceramic composite substrate is prepared
By step 3) gained copper electric slurry deposits on ceramic substrate by method for printing screen, through levelling, oven dry, sintering, obtains described copper/ceramic composite substrate.
Further, described quaternary borates with low melting points salt glass comprises the chemical composition of following molar percentage: BaO:10 ~ 40mol%, ZnO:30 ~ 40mol%, B
2o
3: 10 ~ 40mol%, SiO
2: the mol ratio of 10 ~ 40mol%, described ZnO and BaO is 4 ~ 1/4, and the mol ratio of described B2O3 and SiO2 is 4 ~ 1/4.
Separately, step 1) described in be 0.05 ~ 0.1 according to the mol ratio of acetic acid and tetraethoxy, the mol ratio of ethanol and tetraethoxy is 5 ~ 10, and the mol ratio of water and tetraethoxy is 5 ~ 10.
Separately have, step 1) to prepare in sol-process, the solvent temperature of described barium acetate is 40 ~ 60 DEG C, and the mass ratio of barium acetate and water is 79 ~ 80:100, g/g; The solvent temperature of described zinc acetate is room temperature, and the mass ratio of zinc acetate and water is 30 ~ 33:100, g/g; The solvent temperature of described boric acid is 70 ~ 80 DEG C, and the mass ratio of boric acid and water is 20 ~ 30:100, g/g, and pH value is 5 ~ 6, churning time 5 ~ 15h.
Again, step 1) described dry gel powder thermal treatment comprises following four-stage: the first stage: be warming up to 400 DEG C, heat-up rate is 5 DEG C/min, completes dehydration condensation further, to be got rid of by the organism such as residual water-content, ethanol and zinc acetate, barium acetate are thoroughly decomposed; Subordinate phase: be incubated 0.5 ~ 1.5h at 400 DEG C, organism Thorough combustion is decomposed; Phase III: be warming up to 500 DEG C, heat-up rate 10 DEG C/min; Fourth stage: at 500 DEG C, insulation 1 ~ 3h, then cools to room temperature with the furnace.
Further, step 3) described in copper powder median size be 4 ~ 5 μm, in copper electric slurry, content is 60 ~ 80wt%; Glass powder with low melting point median size is less than 3 μm, and in copper electric slurry, content is at 0 ~ 20wt%; Organic carrier in copper electric slurry content at 10 ~ 30wt%.
And, step 4) in described screen printing process, silk screen adopts Stainless Steel Cloth, printing adopts the printing of disengaging-contact process, between silk screen and described ceramic substrate, spacing is 0.5 ~ 2mm, and described copper electric slurry viscosity is 102 ~ 103Pas, and copper electric slurry solid-to-liquid ratio is 8:2.
Separately, described ceramic substrate is 96%Al
2o
3ceramic substrate, is of a size of 24mm × 24mm.
Again, also comprise the pre-treatment of described ceramic substrate, described pre-treatment comprises the steps: described 96%Al with laser
2o
3ceramic substrate cutting becomes the little square of 24mm × 24mm, to put it in alcohol ultrasonic cleaning 10 ~ 20 minutes, then clean with distilled water flushing, and dry in an oven, place it in 1000 DEG C of thermal treatment 0.5 ~ 1.5h in High Temperature Furnaces Heating Apparatus again, the organism on removing surface, last furnace cooling, takes out stand-by.
Further, step 4) in, dry 8 ~ 12min in 100 ~ 150 DEG C, in 500 DEG C of insulation 30 ~ 50min under nitrogen protection condition, be warming up to 900 DEG C with 10 DEG C/min and sinter.
Wherein, what table 1 provided by each embodiment of the present invention a kind ofly prepares (the i.e. quaternary BZBS glass powder) composition of glass powder with low melting point in the method for copper/ceramic composite substrate and B based on glass powder with low melting point
2o
3/ SiO
2mol ratio change list.Table 2 by each embodiment of the present invention provide a kind of prepare based on glass powder with low melting point (the i.e. quaternary BZBS glass powder) composition of glass powder with low melting point in the method for copper/ceramic composite substrate and ZnO/BaO mol ratio change list.
Table 1
Table 2
Table 3 is a kind ofly prepared pH value and gel time in the method for copper/ceramic composite substrate for provided by the present invention and is affected list to gelation process based on glass powder with low melting point.
Table 3
As shown in Table 2, when pH value is less than 6, gel process increases with pH value and accelerates gradually, and when pH=5 ~ 6, gel is obvious, and when pH<5, gel is slow.But, when pH>6 time, because gelation process is too fast, form a large amount of flocks very soon, upper lower leaf, hinder overall gel on the contrary, and a large amount of crackle appears in xerogel, destroy gel structure, unfavorable to preparing superfine powder.So, the sol-gel mechanism of BZBS glass powder and SiO
2the sol-gel mechanism of glass is basically identical, and belongs to-OH nucleophilic substitution mechanism, is conducive to preparing powder, meanwhile, has again confirmed the judgement started at this chapter, i.e. main the and SiO of the gelation mechanism of experimental glass system
2the gel mechanism of glass is similar.
As shown in Figure 1, before thermal treatment, do not find that crystal exists, can see that xerogel is amorphous state, belong to non-crystalline state.Xerogel is after 500 DEG C of thermal treatment, and be still non-crystalline state substantially, have two steamed bun peaks near 28 ° and 43 ° respectively, this is the feature of BZBS glass
[84].Because barium oxide is network outer body, do not participate in the formation of glass network, easily weaken glass network and cause crystallization, after thermal treatment can be seen, in xerogel, have a small amount of Ba (CO
3)
0.9(SiO
4)
0.1separate out.A small amount of crystallite in glass powder can regulate thermal expansivity and the softening temperature of glass, can make to realize the coefficient of expansion in glass powder and the matrix whole temperature range in process of cooling and be close, reach bonds well, and can avoid reheating.
As shown in Figure 2, after heat treatment, O-H key chattering intensity obviously weakens, and illustrates that the water of chemisorption is tending towards disappearing, and at 1626cm
-1for the water of sample surfaces physical adsorption, this belongs to glass powder common phenomenon.Before heat treatment, Si-O-Si flexural vibration peak, Si-O-Si stretching vibration peak exist, and NE [SiO is described
4] tetrahedron exists.And [BO
3] flexural vibration the peak, [BO of B-O-B in triangle body
4] tetrahedral appearance, illustrate that in xerogel, part B atom has entered in gel network structure.But do not find the characteristic peak of Zn and Ba structure, can think that Zn, Ba do not participate in converging network in gelation process, but be fixed in gel network, only have Si and part B to participate in converging network, to start saying consistent with this chapter.After Overheating Treatment, in network structure, B-O-B, Si-O-Si vibration absorption peak strengthens and moves toward high wave number, illustrates in the xerogel after calcining and has occurred Si-O-Si and O-B-O network.Occurred Si-O-Zn antisymmetric stretching vibration absorption peak after thermal treatment, illustrated that Zn enters glass network as network intermediate, this meets ZnO forms intermediate character as network.
From Fig. 3 and Fig. 4:
Along with B
2o
3/ SiO
2the reduction of ratio, the network structure of glass powder is from [BO
3] triangle body is transformed into gradually with [SiO
4] tetrahedron is main, glass powder structure then first weakens rear enhancing, and ZnO also discharges from network structure simultaneously, and part is separated out with crystal;
Along with B
2o
3/ SiO
2the reduction of ratio, the crystallization strength increases of glass powder is strong, and the kind of crystalline of precipitation also gets more and more.
Along with B
2o
3/ SiO
2the reduction of ratio, time more than 800 DEG C, the wetting angle of glass powder first diminishes and becomes large afterwards, and wettability first improves and is deteriorated afterwards.Along with the raising of temperature, the wetting effect of each component glass powder improves gradually, and glass powder is also clarified gradually.But, B
2o
3/ SiO
2ratio is too high or too low all causes glass clarifying weak effect, and glass powder devitrification, wettability is bad.So only when appropriate ratio (3/2), glass powder softening temperature is low, wetting effect and glass powder clarification all fine, glass powder zero defect.And, SiO
2when content is higher, glass properties performance is the poorest, so content is not easily many.
From Fig. 5 and Fig. 6:
Along with the reduction of ZnO/BaO ratio, glass powder network structure weakened rear enhancing before this, this and ZnO, BaO content and role have much relations: when ZnO content is larger, ZnO forms intermediate as network and adds glass network, reinforcing glass network structure, now BaO content is less, as network outer body, destroys glass network structure; When BaO content is larger, BaO has stronger polarity, works to glass network the effect of gathering, reinforcing glass powder network.
Along with the reduction of ZnO/BaO ratio, the crystallization intensity of glass powder strengthens gradually, and based on barium salt.This and BaO are as network outer body, and do not participate in glass powder network and formed relevant, too much BaO can only separate out with barium salt.
Along with the reduction of ZnO/BaO ratio, glass powder first improves to the wettability of ceramic substrate and is deteriorated afterwards.And all glass powder systems all improve along with the rising wettability of temperature, and glass is clarified gradually.But along with ZnO/BaO ratio is too high or too low all unfavorable to glass properties, too high then ZnO content is high, glass network Stability Analysis of Structures, intensity is comparatively strong, and softening temperature is high, and not easily wetting thawing at a lower temperature, is difficult to clarification; Too low then BaO content is high, and glass network gathers enhancing because of the stronger polarity of BaO on the contrary, and devitrification of glass is too much simultaneously, cause glass powder not only softening temperature high, be difficult to soak, also cause glass powder to be difficult to clarification to such an extent as to produce the defects such as larger crackle.Only have suitable ZnO/BaO ratio (3/2), could obtain wettability better, clarify flawless glass powder.
Therefore, no matter be B
2o
3/ SiO
2or ZnO/BaO, are all the reductions along with ratio, the network structure of glass powder first weakens rear enhancing, and the crystallization intensity of glass powder is all continuous enhancings, and softening temperature is also first reduce rear increase, and wetting angle first reduces rear increase, and wettability is also first improve to be deteriorated afterwards.Too high or too low B
2o
3/ SiO
2ratio all causes defect to glass properties, and this and this two oxides are that glass powder Network former is relevant, both too high levels, and glass powder network tends towards stability, and can increase glass powder softening temperature, reduces wetting effect.Meanwhile, too much SiO
2more be difficult to form glass, be also more difficult to soak, and also cause a large amount of crystallization, cause glass devitrification.Too high or too low ZnO/BaO ratio causes defect to glass powder performance equally, this with this in two oxide compound role differ relevant, ZnO is as network intermediate, network structure can be modified and can also participate in network structure, too high ZnO certainly will cause ZnO to add glass powder network, reinforcing glass powder stability and network structure, cause softening temperature to raise, and glass is difficult to melt.Different from ZnO, BaO as network outer body, but has again very strong polarity simultaneously, destroy glass network effect so have on the one hand, reduce glass powder softening temperature, improve wettability, improve glass powder performance, but can work to network structure the effect of gathering on the other hand, strengthen network, improve softening temperature, be difficult to soak, meanwhile, as network outer body, all the time all can not participation network structure, so cause crystallization intensity enhancing, finally cause glass devitrification, occur the defects such as crackle.In conjunction with electric slurry sintering temperature and the requirement to glass, finally determine to work as B
2o
3/ SiO
23322 system glass powder performances the bests that ratio is 3/2, ZnO/BaO ratio is 3/2, are suitable as glass binder.
In addition, organic carrier is primarily of organic solvent and thickening material composition, and single organic carrier can not meet layering volatilization, so be generally polycomponent organism composition, usual organic solvent is Terpineol 350, and thickening material is ethyl cellulose.Organic solvent is one of main component of organic carrier, can control the drying rate of slurry and the solubleness of thickening material, solvent should have higher boiling point, not volatile under normal temperature, content generally accounts for more than 80% of organic carrier, and conventional organic solvent is Terpineol 350.Conventional thickening material is ethyl cellulose, has excellent thermostability and thermoplasticity, good from different organic solvent intermiscibilities.Except organic solvent and thickening material, sometimes also need to add some additives to improve the character of organic carrier.In order to improve the film forming ability of slurry, the toughness of reinforcing membrane and intensity, need to add softening agent.Experiment adopts dibutyl phthalate as softening agent, carbonyl in its carbonyl ester group and the alcoholic extract hydroxyl group in ethyl cellulose form hydrogen bond, to such an extent as to forming a three-dimensional space net structure, solid particulate distributions, effectively can prevent sedimentation and the condensation of solid particulate therebetween.The quality of electric slurry is mainly reflected in the dispersion effect of slurry to metallographic phase, without sedimentation, reunion.Viscotrol C has less molecular weight, and containing more carbon-carbon double bond and carbon carbon triple bond, electron density high near valence link makes its space steric effect strong, can hinder sedimentation and the reunion of solid particulate, is a kind of well dispersion agent.Meanwhile, in order to prevent occurring foam in slurry, in organic carrier, also with the addition of polyoxyethylene glycol as defoamer.
When solid-to-liquid ratio is 9:1, solid load is too high, and liquid content is very few, and organic carrier well can not soak solid phase surface, and viscosity is excessive, causes forming the electric slurry with certain viscosity, cannot silk screen printing; When solid-to-liquid ratio is 8:2, organic carrier can be good at wetting solid phase surface, modest viscosity, and form the copper electric slurry of certain viscosity, after silk screen printing, figure is clear, pattern edge is neat; When solid-to-liquid ratio is 7:3, solid load is less, organic carrier too high levels, and viscosity is too small, and cause slurry to scatter, cannot form figure clearly, pattern edge is fuzzy.The copper electric slurry of this experiment preparation adopts solid-to-liquid ratio to be that 8:2 prepares, and final viscosity, at 100 ~ 200Pa.s, meets viscosity and the print request of electric slurry.
Electric slurry only has just can have certain adhesivity and electroconductibility through oversintering, and the final most high sintering temperature of this experiment is 900 DEG C, insulation 1h.Cross high sintering temperature (>900 DEG C) easily cause copper particle growth excessive and form closed pore, form the defects such as cavity and crackle, densification cannot be reached; Too low, glass can not soften, melting, occurs raw burn.And the long devitrification of glass that easily causes of soaking time is grown up generation defect, too shortly the abundant melting of glass not only cannot be allowed to soak metal powder and ceramic substrate but also cause copper powder to sinter grow up, good adhesion can not be formed.500 DEG C of insulation for some time, the complete decomposition combustion of organic carrier can be allowed.In order to prevent copper powder high temperature oxidation, whole experimentation all sinters in high pure nitrogen atmosphere.
What table 4 provided by each embodiment of the present invention a kind ofly prepares different low melting glass powder content copper electric slurry formula table in the method for copper/ceramic composite substrate based on glass powder with low melting point.
Table 4. (unit: wt%)
As shown in Figure 7, along with the increase of glass powder content, the sticking power of copper thick film constantly increases, and when glass powder content is increased to 8%, sticking power reaches maximum value, and when continuation increases glass powder, sticking power declines on the contrary fast.When not adding glass powder, copper thick film does not have sticking power substantially; Along with glass powder increases, sticking power increasing degree is obviously accelerated, and when glass powder content reaches 8%, sticking power reaches maximum value 90N; Continue to increase glass powder, sticking power declines fast, and when glass powder content is 16%, sticking power is only 40N.
From Fig. 7 ~ Fig. 9, when glass powder content is 8wt%, sheet resistance is less, and sticking power is maximum, and performance is best, and glass powder content meets the requirement (<10%) of electric slurry.This chapter scans the surface of the copper thick film of different glass powder content and cross section finally by electron microscope, and carry out XRD analysis, show that glass content has a great impact the sticking power of copper electric slurry and electroconductibility, too much very few glass powder all causes copper thick film properties to be deteriorated, the sticking power of copper thick film not only has certain relation with copper thick film surface pattern, also has very large relation with the chemical reaction of cross section intermediate layer thickness and glass and ceramic substrate.Finally, the best over-all properties of the copper electric slurry of gained is sticking power is 90N, and sheet resistance is 1.23m Ω/.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not depart from the scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
Claims (10)
1. prepare a method for copper/ceramic composite substrate based on glass powder with low melting point, it is characterized in that, comprise the steps:
Prepare glass powder with low melting point
Prepare tetraethoxy pre-hydrolyzed solution: get acetic acid, ethanol, tetraethoxy and water, stir lower mixing 30 ~ 40min, obtain the tetraethoxy pre-hydrolyzed solution of clarification;
Prepare colloidal sol: get zinc acetate, barium acetate, boric acid is placed in beaker respectively, distilled water is added respectively in zinc acetate, barium acetate place beaker, be stirred to zinc acetate respectively and barium acetate is dissolved completely, the acetic acid zinc solution that must clarify and barium acetate solution, water or alcohol formation boric acid solution is added in the beaker of boric acid place, then boric acid solution, acetic acid zinc solution, barium acetate solution and step a gained tetraethoxy pre-hydrolyzed solution are mixed, adjust ph, stir at 60 ~ 90 DEG C, obtain colloidal sol;
Prepare xerogel: dissolved thoroughly to colloidal sol by the colloidal sol sealing 1 ~ 2h obtained, then ageing 3 ~ 5h, obtains wet gel, wet gel is dried 20 ~ 25h at 90 ~ 110 DEG C, obtains xerogel;
Prepare glass powder with low melting point: grinding gained xerogel, cross 120 ~ 150 order mesh screens, obtain dry gel powder, then dry gel powder is heat-treated in retort furnace just described glass powder with low melting point;
Prepare organic carrier
Described organic carrier comprises the chemical composition of following mass percent: ethyl cellulose: 5 ~ 10wt%, Terpineol 350: 80 ~ 90wt%, dibutyl phthalate: 1 ~ 5wt%, polyoxyethylene glycol: 1 ~ 5wt%, Viscotrol C: 1 ~ 5wt%; By ethyl cellulose, Terpineol 350, dibutyl phthalate, polyoxyethylene glycol and Viscotrol C by described mass percent mixing, constantly stir until ethyl cellulose is dissolved completely under 80 ~ 100 DEG C of water bath with thermostatic control conditions, insulation 2 ~ 3h, obtains described organic carrier;
Prepare copper electric slurry
By copper powder, step 1) gained glass powder with low melting point mixing rear grinding grinding 20 ~ 40min, then add step 2) and gained organic carrier, mix and blend, pour in ball grinder, after on ball mill, carry out ball milling with the rotating speed of 250 ~ 350r/min, ball milling 2 ~ 4h, obtain described copper electric slurry;
Prepare copper/ceramic composite substrate
By step 3) gained copper electric slurry deposits on ceramic substrate by method for printing screen, through levelling, oven dry, sintering, obtains described copper/ceramic composite substrate.
2. a kind of method preparing copper/ceramic composite substrate based on glass powder with low melting point according to claim 1, it is characterized in that, described quaternary borates with low melting points salt glass comprises the chemical composition of following molar percentage: BaO:10 ~ 40mol%, ZnO:30 ~ 40mol%, B
2o
3: 10 ~ 40mol%, SiO
2: the mol ratio of 10 ~ 40mol%, described ZnO and BaO is 4 ~ 1/4, and the mol ratio of described B2O3 and SiO2 is 4 ~ 1/4.
3. a kind of method preparing copper/ceramic composite substrate based on glass powder with low melting point according to claim 1, it is characterized in that, step 1) described in be 0.05 ~ 0.1 according to the mol ratio of acetic acid and tetraethoxy, the mol ratio of ethanol and tetraethoxy is 5 ~ 10, and the mol ratio of water and tetraethoxy is 5 ~ 10.
4. a kind of method preparing copper/ceramic composite substrate based on glass powder with low melting point according to claim 1, it is characterized in that, step 1) to prepare in sol-process, the solvent temperature of described barium acetate is 40 ~ 60 DEG C, the mass ratio of barium acetate and water is 79 ~ 80:100, g/g; The solvent temperature of described zinc acetate is room temperature, and the mass ratio of zinc acetate and water is 30 ~ 33:100, g/g; The solvent temperature of described boric acid is 70 ~ 80 DEG C, and the mass ratio of boric acid and water is 20 ~ 30:100, g/g, and pH value is 5 ~ 6, churning time 5 ~ 15h.
5. a kind of method preparing copper/ceramic composite substrate based on glass powder with low melting point according to claim 1, it is characterized in that, step 1) described dry gel powder thermal treatment comprises following four-stage: the first stage: be warming up to 400 DEG C, heat-up rate is 5 DEG C/min, completes dehydration condensation further, to be got rid of by the organism such as residual water-content, ethanol and zinc acetate, barium acetate are thoroughly decomposed; Subordinate phase: be incubated 0.5 ~ 1.5h at 400 DEG C, organism Thorough combustion is decomposed; Phase III: be warming up to 500 DEG C, heat-up rate 10 DEG C/min; Fourth stage: at 500 DEG C, insulation 1 ~ 3h, then cools to room temperature with the furnace.
6. a kind of method preparing copper/ceramic composite substrate based on glass powder with low melting point according to claim 1, is characterized in that, step 3) described in copper powder median size be 4 ~ 5 μm, in copper electric slurry, content is 60 ~ 80wt%; Glass powder with low melting point median size is less than 3 μm, and in copper electric slurry, content is at 0 ~ 20wt%; Organic carrier in copper electric slurry content at 10 ~ 30wt%.
7. a kind of method preparing copper/ceramic composite substrate based on glass powder with low melting point according to claim 1, it is characterized in that, step 4) in described screen printing process, silk screen adopts Stainless Steel Cloth, printing adopts the printing of disengaging-contact process, between silk screen and described ceramic substrate, spacing is 0.5 ~ 2mm, and described copper electric slurry viscosity is 102 ~ 103Pas, and copper electric slurry solid-to-liquid ratio is 8:2.
8. a kind of method preparing copper/ceramic composite substrate based on glass powder with low melting point according to claim 1 or 7, is characterized in that, described ceramic substrate is 96%Al
2o
3ceramic substrate, is of a size of 24mm × 24mm.
9. a kind of method preparing copper/ceramic composite substrate based on glass powder with low melting point according to claim 8, is characterized in that, also comprise the pre-treatment of described ceramic substrate, and described pre-treatment comprises the steps: described 96%Al with laser
2o
3ceramic substrate cutting becomes the little square of 24mm × 24mm, to put it in alcohol ultrasonic cleaning 10 ~ 20 minutes, then clean with distilled water flushing, and dry in an oven, place it in 1000 DEG C of thermal treatment 0.5 ~ 1.5h in High Temperature Furnaces Heating Apparatus again, the organism on removing surface, last furnace cooling, takes out stand-by.
10. a kind of method preparing copper/ceramic composite substrate based on glass powder with low melting point according to claim 1; it is characterized in that; step 4) in; 8 ~ 12min is dried in 100 ~ 150 DEG C; in 500 DEG C of insulation 30 ~ 50min under nitrogen protection condition, be warming up to 900 DEG C with 10 DEG C/min and sinter.
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