CN103482985A - Low-temperature co-fired ceramic tape casting material and preparing method and application thereof - Google Patents
Low-temperature co-fired ceramic tape casting material and preparing method and application thereof Download PDFInfo
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Abstract
The invention relates to a low-temperature co-fired ceramic tape casting material and a preparing method and application of the low-temperature co-fired ceramic tape casting material. The low-temperature co-fired ceramic tape casting material comprises, by weight, 35-50% of inorganic-phase components and 50-65% of organic-phase components. The inorganic-phase components include borosilicate glass powder and aluminum oxide ceramic powder, wherein the weight ratio of the borosilicate glass powder to the aluminum oxide ceramic powder is 2:3-3:2, and the borosilicate glass powder includes CuO which accounts for less than 3% of the power in weight. The organic-phase components include a solvent, an adhesion agent, a plasticizing agent and a dispersing agent, wherein the solvent is an alcohol-ester mixed solvent, and alcohol accounts for 20-70% in the mixed solvent in weight.
Description
Technical field
The present invention relates to a kind of LTCC and give birth to carrying material and its preparation method and application, belong to electronic ceramics baseplate material and manufacture field thereof.
Background technology
LTCC (Low temperature co-fired ceramics, LTCC) as the ceramic packaging substrate material, there is low specific inductivity and loss, low thermal expansivity (with being complementary of silicon), high chemical stability, good mechanical property, and can be with the metal of high conductivity (as gold, silver, copper etc.) integrated burning altogether under 900 ℃, thereby realize the many merits such as multilayer wiring of ceramic substrate, the LTCC technology now has been widely used in microelectronics Packaging and device is manufactured field.The ltcc substrate material mainly forms by glass/ceramic is compound.In the ltcc substrate material of marketization application, its body material is generally selected the borosilicate glass of low softening point, and ceramic packing is mainly with Al
2o
3ceramic main, in addition, also may contain a small amount of for improving the additive of sintering characteristic and substrate performance.The preparation process of ltcc substrate is the glass/ceramic powder to be made to smooth, fine and close thick film ceramic by flow casting molding give birth to band, then by laser boring, micropore slip casting, the techniques such as conductor paste printing are made required circuitous pattern, and passive device is imbedded in multilayer ceramic substrate, then overlap together, at 850～900 ℃ of lower sintering, obtain ltcc substrate.
With other ceramic substrates, with encapsulation technology, compare, although LTCC has many unrivaled technological merits, but in the preparation and moulding process of ltcc substrate, still have some gordian techniquies and technique to need further investigation, for example, in preparation LTCC gives birth to the casting slurry of band, composition and the content of the proportion of composing of glassy phase and ceramic phase, the organic additive in casting slurry (solvent, softening agent, dispersion agent, binding agent etc.) are most important, and they will directly have influence on LTCC and give birth to the quality of band and follow-up sintering process.In addition, it is also an emphasis in the LTCC technical study with the matching problem of electrocondution slurry (silver or copper) while burning altogether that LTCC gives birth to band, because the contraction when common burn of metal and pottery is inconsistent and interfacial diffusion can directly have influence on the performance of ceramic substrate, serious will cause internal circuit and device global failure.
China starts late in the preparation of LTCC material and the research of process aspect, and at present, the product of domestic LTCC mainly still depends on from the LTCC of external import and gives birth to band.In existing patent application, main component optimization, sintering characteristic and the performance of take the LTCC material of most of research is main (patent publication No. CN1693286A, patent publication No. CN101148323A, patent publication No. CN101717245A, patent publication No. CN102206076A, patent publication No. 102432280A), the research of giving birth to the key process technology such as the casting slurry allotment of carrying material, living band preparation and metal matching co-firing for LTCC is relatively less, lacks the consideration to the practical application effect of LTCC material.For example, in the LTCC casting slurry, the selection of solvent is main mainly with toxic organic solvent such as toluene, dimethylbenzene (patent publication No. CN101077835A, CN103145336A), very large to human body and environmental hazard, is unfavorable for environmental protection.In addition, the disclosed LTCC slurry of Chinese patent CN103044035A be take methyl alcohol, ethanol and/or propyl alcohol as solvent, but this solvent system is limited to the solubleness of binding agent, is difficult to meet the dispersed of each composition.
Summary of the invention
The object of the invention is to, from the practical application of LTCC material, provide a kind of have low specific inductivity and loss, can realize with argent living carrying material of LTCC that matched well is burnt altogether and its preparation method and application simultaneously.
At this, on the one hand, the invention provides a kind of LTCC and give birth to carrying material, the component that described LTCC is given birth to carrying material comprises that inorganic phase composition and weight percentage that weight percentage is 35～50wt% are 50～65wt% organic phase composition, wherein, described inorganic phase composition comprises borosilicate glass powder and the alumina ceramic powder that weight ratio is 2:3～3:2, described borosilicate glass powder contains CuO, CuO weight percentage in this powder is greater than zero and below 3wt%, described organic phase composition comprises solvent, binding agent, softening agent and dispersion agent, described solvent is pure-ester mixed solvent, the weight percentage of alcohol in mixed solvent is 20～70wt%.
According to the present invention, selected pure-ester mixed solvent in the casting slurry of preparation ceramic green band, cost is relatively low, environmental friendliness, and also good to the solvability of binding agent, be conducive to improve solid load in slurry and also can reduce viscosity, be conducive to flow casting molding; In addition, described borosilicate glass powder contains a small amount of CuO, can regulate and improve the performance of borosilicate glass powder, and efficiently solve the silver-colored diffusion problem in common burning process, has realized that LTCC gives birth to carrying material and silver-colored matching co-firing.And it is smooth that described LTCC is given birth to belt surface, even thickness, can be at 850～900 ℃ of densified sintering products after lamination, and can realize good matching co-firing with silver.In addition, the shrinking percentage of agglomerated material is adjustable, has low specific inductivity and loss, and higher physical strength, meets the application requiring of low-temperature co-fired ceramic substrate, has fabulous application prospect.The present invention, for the over-all properties that promotes low-temperature co-fired ceramic substrate material, promotes the autonomous production of low-temperature co-burning ceramic material and research and development that positive effect is arranged.
Preferably, described borosilicate glass powder also contains 15～25wt%CaO, 5～20wt%Al
2o
3, 5～25wt%B
2o
3, and 30～45wt%SiO
2.
Preferably, the weight percentage that each in described organic phase composition forms is: solvent 30～50wt%, binding agent 4～8wt%, softening agent 3～5wt%, dispersion agent 1～3wt%.Wherein, in described solvent, the shared weight percentage of alcohol can be 20～70wt%, is preferably 40～60wt%.The present invention's solvent used is pure-ester mixed solvent, and wherein the content of alcohol is higher, good to the solvability of binding agent, is conducive to improve in slurry solid load and can reduces viscosity, is conducive to flow casting molding.
Preferably, the alcohol in described mixed solvent is one or more the mixture in ethanol, propyl alcohol, Virahol, ethylene glycol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, phenylethyl alcohol and diacetone alcohol; Ester in described mixed solvent is one or more the mixture in methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butylacetate and isobutyl acetate.In the present invention's mixed solvent used, enrich in alcohol and ester source, cheap and easy to get, has reduced production cost.
Preferably, described binding agent is polyvinyl butyral acetal, the mixture that described softening agent is phthalic ester and polyoxyethylene glycol, and described dispersion agent is triolein, wherein, in described softening agent, the weight ratio of phthalic ester and polyoxyethylene glycol can be 1:1～3:2.
On the other hand, the present invention also provides a kind of described LTCC to give birth to the preparation method of carrying material, and comprising: the formula by described borosilicate glass powder takes raw materials of Ca O, Al
2o
3, B
2o
3, SiO
2, CuO and ground and mixed even; By the raw materials melt after mixing, be that uniform glass metal pour in cold water forms wet ball grinding after the glass cullet particle, drying obtains the borosilicate glass powder; And each matched of giving birth in carrying material by described LTCC takes described borosilicate glass powder, alumina ceramic powder, add described mixed solvent, dispersion agent, binding agent and softening agent to carry out disposable mixing and ball milling 24～48 hours, after vacuum defoamation, flow casting molding, obtain described LTCC and give birth to carrying material.
Preparation method's technical process of the present invention is simple, and controllability is high, reproducible, has Environmental compatibility preferably, is applicable to scale production.
Preferably, the median size of described borosilicate glass powder is 0.3～1 μ m.
Preferably, described melting is to rise to 1300～1500 ℃ and be incubated 1～2 hour from room temperature with 5～10 ℃/min.
Again on the one hand, the present invention also provides described LTCC to give birth to the application of carrying material in preparing low-temperature co-fired ceramic substrate: at first, described LTCC is given birth to the carrying material section, and print required electrode pattern at the living belt surface cut by silk-screen printing technique, then above-mentioned LTCC is given birth to the band lamination, adopt hip moulding to form biscuit; Finally, described biscuit being warming up to 400～500 ℃ of insulations 40～80 minutes with 1～2 ℃/min continues to be warming up to 850～900 ℃ of insulations with 5～10 ℃/min and within 15～30 minutes, carries out sintering and make described low-temperature co-fired ceramic substrate to get rid of after organism.
The present invention has solved the silver-colored diffusion problem in common burning process by the optimization of borosilicate glass formula, can realize that LTCC gives birth to carrying material and silver-colored matching co-firing, the over-all properties of lifting low-temperature co-fired ceramic substrate material.
Preferably, the pressure of described hot isostatic pressing is 40～50MPa, and temperature is 60～80 ℃.
The accompanying drawing explanation
The rolling LTCC that Fig. 1 is one example according to the present invention is given birth to the pictorial diagram of band;
The LTCC that Fig. 2 is one example according to the present invention is given birth to band and is schemed with the section SEM that Ag inner electrode burns altogether;
Fig. 3 gives birth to metallization ltcc substrate photo in kind prepared by band for the LTCC that adopts one example according to the present invention;
The LTCC that Fig. 4 is one example according to the present invention is given birth to and is with photo in kind and the XPS collection of illustrative plates burnt altogether with the silver surface electrode, and the oval frame that in figure, right side is left side goes out the enlarged view of part.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that following embodiment and/or accompanying drawing are only for the present invention is described, and unrestricted the present invention.
One aspect of the present invention provides a kind of LTCC to give birth to carrying material, and the component that described LTCC is given birth to carrying material comprises that inorganic phase composition and weight percentage that weight percentage is 35～50wt% are 50～65wt% organic phase composition.
Wherein, described inorganic phase composition comprises borosilicate glass powder and alumina ceramic powder, and their weight ratio can be 2:3～3:2.
Described borosilicate glass powder can be CaO-Al
2o
3-B
2o
3-SiO
2glass, each component and weight percentage thereof are as follows: 15～25wt%CaO, 5～20wt%Al
2o
3, 5～25wt%B
2o
3, 30～45wt%SiO
2, and be greater than zero and the CuO below 3wt%.Wherein, the interpolation of CuO is mainly used to regulate and improve the performance of borosilicate glass, and can effectively solve the silver-colored diffusion problem in common burning process.Fig. 2 illustrates LTCC and gives birth to the section SEM figure that band and Ag inner electrode burn altogether, and as seen from the figure, the present invention has realized that LTCC gives birth to the good matching co-firing of band and silver.
Described organic phase composition comprises solvent, binding agent, softening agent and dispersion agent.Each weight percentage formed can be: solvent 30～50wt%, binding agent 4～8wt%, softening agent 3～5wt%, dispersion agent 1～3wt%.
Wherein, described solvent is pure-ester mixed solvent, and the weight percentage of alcohol in mixed solvent is 20～70wt%, is preferably 40～60wt%.The present invention has selected pure-ester mixed solvent in the casting slurry of preparation ceramic green band, and cost is relatively low, environmental friendliness; And in the present invention's mixed solvent used, the content of alcohol is higher, good to the solvability of binding agent, be conducive to improve in slurry solid load and can reduce viscosity, be conducive to flow casting molding.
In the present invention, the alcohol in described mixed solvent can be one or more the mixture in ethanol, propyl alcohol, Virahol, ethylene glycol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, phenylethyl alcohol and diacetone alcohol; Ester in described mixed solvent can be one or more the mixture in methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butylacetate and isobutyl acetate.Alcohol and ester in the present invention's mixed solvent used, source is abundant, cheap and easy to get, has reduced production cost.
In the present invention, described binding agent can be polyvinyl butyral acetal, and described softening agent can be the mixture of phthalic ester and polyoxyethylene glycol, and described dispersion agent can be triolein.Wherein, in described softening agent, the weight ratio of phthalic ester and polyoxyethylene glycol can be 1:1～3:2, and described phthalic ester can be for example dibutyl phthalate.But should be understood that and the invention is not restricted to this, described binding agent can also be mixture of β-dimethyl-aminoethylmethacrylate and methacrylic acid etc., and described softening agent can also be only phthalic ester etc., and described dispersion agent can also be the castor-oil plant wet goods.
The present invention provides above-mentioned LTCC to give birth to the preparation method of carrying material on the other hand.As example, can comprise the following steps.
(1) by CaO-Al
2o
3-B
2o
3-SiO
2in glass, each oxide raw material mixes in the aluminum oxide mortar according to compositing formula, then the raw material mixed is moved in quartz crucible.
(2) quartz crucible that will fill raw material is put into high-temperature smelting pot, rise to 1300～1500 ℃ from room temperature with 5～10 ℃/min, be incubated 1～2 hour, to guarantee to obtain uniform glass metal, then the glass metal melted is directly poured in cold deionized water, formed the glass cullet particle.
(3) by glass cullet particle wet ball grinding, can be for example to put into ball grinder with abrading-ball, dehydrated alcohol together with a certain amount of weight percent, in planetary ball mill ball milling 24～36 hours, obtaining median size after oven dry was the borosilicate glass powder of 0.3～1 μ m.Wherein abrading-ball can be for example steel ball, zirconium ball or agate ball.
(4) press each matched in the casting slurry system, take borosilicate glass powder, the alumina ceramic powder of above-mentioned gained, add described mixed solvent, dispersion agent, binding agent and softening agent to carry out disposable ball milling 24～48 hours, after vacuum defoamation, flow casting molding, obtain described LTCC and give birth to carrying material.
Referring to Fig. 1, it illustrates and adopts the rolling LTCC that preparation method of the present invention makes to give birth to band, and it is smooth that this LTCC is given birth to belt surface as can be seen from Figure, even thickness.
The present invention has also carried out the sintering character test to prepared living carrying material.By described living carrying material cut into slices, the wire mark conductive silver paste, lamination, and (for example pressure is 40～50MPa to adopt hot isostatic pressing, temperature is 60～80 ℃) moulding, then be warming up to 400～500 ℃ with 1～2 ℃/min and be incubated 40～80 minutes to get rid of the organism in sample, be warming up to 850～900 ℃ of insulations 15～30 minutes with 5～10 ℃/min again, finally sintered sample carried out to performance test.Test result is referring to the table 4 in following embodiment 1.Therefrom known, LTCC of the present invention is given birth to carrying material and is had excellent sintering character, and in this example, they can be at 850～900 ℃ of densified sintering products, and sintered density reaches 3.1g/cm
3, agglomerated material is adjustable between 10%～20% in the shrinking percentage of X, Y, Z axis, has low specific inductivity (under 1MHZ, being low to moderate 7.0) and loss (under 1MHZ, being low to moderate 0.003), and low thermal expansivity (is low to moderate 6.2 * 10
-6and higher physical strength (bending strength is high to 174MPa)/K).
In addition, Fig. 4 illustrates the living band of LTCC of an example and photo in kind and the XPS collection of illustrative plates that the silver surface electrode burns altogether.Wherein, LTCC1 represents the product after the living band of the LTCC that does not contain CuO in the borosilicate glass powder burns altogether with the silver surface electrode, and LTCC3 represents the product after the living band of the LTCC that contains a small amount of CuO in the borosilicate glass powder and silver surface electrode burn altogether.As seen from the figure, yellow pollution trace has all appearred in the surface of LTCC1, this is mainly that the silver x-ray photoelectron power spectrum (XPS) that the diffusion in mutually causes at borosilicate glass is analyzed and further confirmed, in the yellow strain trace, silver-colored existence is arranged, and the pattern contour of LTCC3 surface silver is clear, yellow pollution trace does not appear, this may be that interpolation due to CuO has stoped silver ions diffusion in mutually at borosilicate glass, and x-ray photoelectron power spectrum (XPS) analysis also finds no silver-colored existence.Can find out, in borosilicate glass, add a small amount of CuO can stop the diffusion phenomena in silver-colored burning process altogether.Hence one can see that, adopts borosilicate glass formula after optimization of the present invention can solve LTCC and give birth to the carrying material silver-colored diffusion problem in the burning process altogether, realizes that LTCC gives birth to carrying material and silver-colored matching co-firing.
One side more of the present invention also provides described LTCC to give birth to the application of carrying material in preparing low-temperature co-fired ceramic substrate.The rolling LTCC prepared is given birth to carrying material and be cut into the living band of individual layer LTCC that size is identical, and print required electrode pattern at the living belt surface cut by silk-screen printing technique, then, multi-disc (for example 20) individual layer LTCC is given birth to band location lamination, and employing hot isostatic pressing (for example pressure is 40～50MPa, and temperature is 60～80 ℃) moulding.Then, the ltcc substrate biscuit of hip moulding is put into to retort furnace, be warming up to 400～500 ℃ with 1～2 ℃/min and be incubated 40～80 minutes to get rid of the organism in sample, be warming up to 850～900 ℃ of insulations 15～30 minutes with 5～10 ℃/min again, can obtain low-temperature co-fired ceramic substrate.Its outward appearance as shown in Figure 3.
Preparation method's technical process of the present invention is simple, and controllability is high, reproducible, has Environmental compatibility preferably, is applicable to scale production.The present invention has selected pure-ester mixed solvent in the casting slurry of preparation ceramic green band, and cost is relatively low, environmental friendliness; And in the present invention's mixed solvent used, the content of alcohol is higher, good to the solvability of binding agent, be conducive to improve in slurry solid load and can reduce viscosity, be conducive to flow casting molding.The living belt surface of the LTCC that adopts the inventive method to prepare is smooth, even thickness.Sample after lamination can be at 850～900 ℃ of densified sintering products, and can realize good matching co-firing with silver.In addition, the shrinking percentage of sintered sample is adjustable, has low specific inductivity and loss, and low thermal expansivity, and higher physical strength meet the application requiring of low-temperature co-fired ceramic substrate, have fabulous application prospect.The present invention, for the over-all properties that promotes low-temperature co-fired ceramic substrate material, promotes the autonomous production of low-temperature co-burning ceramic material and research and development that positive effect is arranged.
Below further for example embodiment to describe the present invention in detail.Should understand equally; following examples only are used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention., those skilled in the art can do in suitable scope by the explanation of this paper and select, and not really want to be defined in the hereinafter concrete numerical value of example the temperature that following example is concrete, time etc. are only also examples in OK range.
Comparative Examples 1
At first, the raw materials by weight for preparing the borosilicate glass powder is taken respectively to 25wt%CaO, 15wt%Al
2o
3, 20wt%B
2o
3, 40wt%SiO
2, mix rear immigration quartz crucible, then put into high-temperature smelting pot, rise to 1400 ℃ from room temperature with 8 ℃/min, be incubated 2 hours, to guarantee to obtain uniform glass metal.Then the glass metal melted is directly poured in cold deionized water, form the glass cullet particle, again glass cullet particle, abrading-ball and dehydrated alcohol are put into to ball grinder together with a certain amount of weight percent, in planetary ball mill ball milling 24 hours, obtaining median size after oven dry was No. 1 borosilicate glass powder of 0.5 μ m.
Secondly, give birth to each component content preparation casting slurry of carrying material by two kinds of LTCC that provide in table 1.Take the above-mentioned No. 1 borosilicate glass powder prepared, alumina ceramic powder, add mixed solvent, dispersion agent, binding agent and softening agent to carry out disposable ball milling 48 hours, obtains the LTCC casting slurry after vacuum defoamation.Wherein, above-mentioned mixed solvent consist of dehydrated alcohol and ethyl acetate, both weight ratios are 1:1.Binding agent is polyvinyl formal, and binding agent is dissolved in to above-mentioned mixed solvent, obtains the solution of 30wt%, and dispersion agent is triglyceride, and softening agent is butyl benzyl phthalate and poly(oxyethylene glycol) 400, and both ratios are 1:1.By the LTCC casting slurry flow casting molding on full-automatic casting machine prepared, can prepare LTCC and give birth to carrying material LTCC1 and LTCC2.It is well wetting with the pet vector film that the LTCC that employing a process for preparing gives birth to band, gives birth to band density and reach 3.5g/cm
3, there is good snappiness.
Finally, to prepared living carrying material cut into slices, the wire mark conductive silver paste, lamination, and employing hot isostatic pressing (45MPa, 70 ℃) moulding, then be warming up to 450 ℃ with 1.5 ℃/min and be incubated 60 minutes to get rid of the organism in sample, then be warming up to 850 ℃ of insulations 15 minutes with 10 ℃/min, then sintered sample is carried out to performance test.The LTCC that table 2 has provided in this Comparative Examples is given birth to the sintering character of being with.
Table 1 LTCC is given birth to each component concentration of carrying material
Table 2 LTCC is given birth to the band sintering character
Embodiment 1
At first, the raw materials by weight for preparing the borosilicate glass powder is taken respectively to 25wt%CaO, 15wt%Al
2o
3, 19wt%B
2o
3, 40wt%SiO
2, 1wt%CuO, mix rear immigration quartz crucible, then puts into high-temperature smelting pot, from room temperature, with 8 ℃/min, rises to 1400 ℃, is incubated 2 hours, to guarantee to obtain uniform glass metal.Then the glass metal melted is directly poured in cold deionized water, form the glass cullet particle, again glass cullet particle, abrading-ball and dehydrated alcohol are put into to ball grinder together with a certain amount of weight percent, in planetary ball mill ball milling 24 hours, obtaining median size after oven dry was No. 2 borosilicate glass powders of 0.5 μ m.
Secondly, give birth to each component content preparation casting slurry of carrying material by two kinds of LTCC that provide in table 3.Take above-mentioned No. 2 borosilicate glass powders that prepare, alumina ceramic powder, add mixed solvent, dispersion agent, binding agent and softening agent to carry out disposable ball milling 48 hours, obtains the LTCC casting slurry after vacuum defoamation.Wherein, above-mentioned mixed solvent consist of dehydrated alcohol and ethyl acetate, both weight ratios are 1:1.Binding agent is polyvinyl formal, and binding agent is dissolved in to above-mentioned mixed solvent, obtains the solution of 30wt%, and dispersion agent is triglyceride, and softening agent is butyl benzyl phthalate and poly(oxyethylene glycol) 400, and both ratios are 1:1.By the LTCC casting slurry flow casting molding on full-automatic casting machine prepared, can prepare LTCC and give birth to carrying material LTCC3 and LTCC4.It is well wetting with the pet vector film that the LTCC that employing a process for preparing gives birth to band, gives birth to band density and reach 3.5g/cm
3, there is good snappiness.
Finally, to prepared living carrying material cut into slices, the wire mark conductive silver paste, lamination, and employing hot isostatic pressing (45MPa, 70 ℃) moulding, then be warming up to 450 ℃ with 1.5 ℃/min and be incubated 60 minutes to get rid of the organism in sample, then be warming up to 850 ℃ of insulations 15 minutes with 10 ℃/min, then sintered sample is carried out to performance test.Table 4 has provided the LTCC in the present embodiment and has given birth to the sintering character of being with.
Table 3 LTCC is given birth to each component concentration of carrying material
Table 4 LTCC is given birth to the band sintering character
Do not add CuO in No. 1 borosilicate glass powder adopted in Comparative Examples 1, yellow pollution trace has all appearred in the sample LTCC1 after silver burns altogether and the surface of LTCC2, mainly that at borosilicate glass, the diffusion in mutually causes silver, x-ray photoelectron power spectrum (XPS) analysis has further confirmed, in the yellow strain trace, silver-colored existence is arranged, and result as shown in Figure 4.Added the CuO of 1wt% in No. 2 borosilicate glass powders that adopt in embodiment 1, the pattern contour of the sample LTCC3 after silver burns altogether and LTCC4 surface silver is clear, yellow pollution trace does not all appear, may be that interpolation due to CuO has stoped silver ions diffusion in mutually at borosilicate glass, x-ray photoelectron power spectrum (XPS) analysis also finds no silver-colored existence.Burn altogether photo in kind and the contrast of XPS result of sample by the silver of the LTCC3 in the LTCC1 in Comparative Examples 1 and embodiment 1, can find out, in borosilicate glass, add a small amount of CuO can stop the diffusion phenomena in silver-colored burning process altogether.Therefore, adopt borosilicate glass formula after optimization of the present invention can solve LTCC and give birth to the carrying material silver-colored diffusion problem in the burning process altogether, realize that LTCC gives birth to carrying material and silver-colored matching co-firing.
In above-mentioned two embodiment, although the mixed solvent used in casting slurry only illustrates ethanol as the example alcohols, take ethyl acetate as example ester class, but should understand, the alcohols that other are suitable and ester class also are suitable for, also can be one or more the mixture in propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, phenylethyl alcohol and diacetone alcohol etc. such as alcohols, the ester class also can be one or more the mixture in methyl acetate, butylacetate and isobutyl acetate etc.
Embodiment 2
Living carrying material for the preparation of ltcc substrate can adopt the method described in embodiment 1 to make.The rolling LTCC prepared is given birth to carrying material and be cut into the living band of individual layer LTCC that size is identical, and give birth to belt surface at LTCC and print required electrode pattern by silk-screen printing technique, then, 20 individual layer LTCC are given birth to band location lamination, and employing hot isostatic pressing (45MPa, 70 ℃) moulding.Then, the ltcc substrate biscuit of hip moulding is put into to retort furnace, be warming up to 450 ℃ with 1.5 ℃/min and be incubated 60 minutes to get rid of the organism in sample, then be warming up to 850 ℃ of insulations 15 minutes with 10 ℃/min, can obtain ltcc substrate sample as shown in Figure 3.
Industrial applicability: the present invention has selected pure-ester mixed solvent in the casting slurry of preparation ceramic green band, and cost is relatively low, environmental friendliness; In addition, the optimization by the borosilicate glass formula has solved the silver-colored diffusion problem in common burning process, has realized that LTCC gives birth to carrying material and silver-colored matching co-firing, at electronic ceramics baseplate material and manufacture field thereof, has a good application prospect.
Claims (10)
1. a LTCC is given birth to carrying material, it is characterized in that, the component that described LTCC is given birth to carrying material comprises that inorganic phase composition and weight percentage that weight percentage is 35～50 wt% are 50～65 wt% organic phase compositions, wherein,
Described inorganic phase composition comprises borosilicate glass powder and the alumina ceramic powder that weight ratio is 2:3～3:2,
Described borosilicate glass powder contains CuO, CuO in this powder weight percentage below 3wt%,
Described organic phase composition comprises solvent, binding agent, softening agent and dispersion agent,
Described solvent is pure-ester mixed solvent, and the weight percentage of alcohol in mixed solvent is 20～70 wt%.
2. LTCC according to claim 1 is given birth to carrying material, it is characterized in that, by weight, described borosilicate glass powder also contains 15～25 wt% CaO, 5～20 wt% Al
2o
3, 5～25 wt% B
2o
3, and 30～45 wt% SiO
2.
3. LTCC according to claim 1 and 2 is given birth to carrying material, it is characterized in that, the weight percentage that each in described organic phase composition forms is: solvent 30～50 wt%, binding agent 4～8 wt%, softening agent 3～5 wt%, dispersion agent 1～3 wt%.
4. give birth to carrying material according to the described LTCC of any one in claims 1 to 3, it is characterized in that, the alcohol in described mixed solvent is one or more the mixture in ethanol, propyl alcohol, Virahol, ethylene glycol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, phenylethyl alcohol and diacetone alcohol; Ester in described mixed solvent is one or more the mixture in methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butylacetate and isobutyl acetate.
5. give birth to carrying material according to the described LTCC of any one in claim 1 to 4, it is characterized in that, described binding agent is polyvinyl butyral acetal, the mixture that described softening agent is phthalic ester and polyoxyethylene glycol, described dispersion agent is triolein, wherein, in described softening agent, the weight ratio of phthalic ester and polyoxyethylene glycol is 1:1～3:2.
6. in a claim 1 to 5, the described LTCC of any one is given birth to the preparation method of carrying material, it is characterized in that, comprising:
Formula by described borosilicate glass powder takes raw materials of Ca O, Al
2o
3, B
2o
3, SiO
2, CuO and ground and mixed even;
By the raw materials melt after mixing, be that uniform glass metal pour in cold water forms wet ball grinding after the glass cullet particle, drying obtains the borosilicate glass powder; And
Each matched of giving birth in carrying material by described LTCC takes described borosilicate glass powder, alumina ceramic powder, add described mixed solvent, dispersion agent, binding agent and softening agent to carry out disposable mixing and ball milling 24～48 hours, after vacuum defoamation, flow casting molding, obtain described LTCC and give birth to carrying material.
7. preparation method according to claim 6, is characterized in that, the median size of described borosilicate glass powder is 0.3～1 μ m.
8. according to the described preparation method of claim 6 or 7, it is characterized in that, described melting is to rise to 1300～1500 ℃ and be incubated 1～2 hour from room temperature with 5～10 ℃/min.
9. one kind according to the application of the described low-temperature co-fired ceramic substrate of any one in claim 1 to 5 in preparing low-temperature co-fired ceramic substrate, it is characterized in that, at first, described LTCC is given birth to the carrying material section, and print required electrode pattern at the living belt surface cut by silk-screen printing technique, then above-mentioned LTCC is given birth to the band lamination, adopt hip moulding to form biscuit; Finally, described biscuit is warming up to 400～500 ℃ of insulations with 1～2 ℃/min and within 15～30 minutes, carries out sintering to make described low-temperature co-fired ceramic substrate after the eliminating organism, to continue being warming up to 850～900 ℃ of insulations with 5～10 ℃/min in 40～80 minutes.
10. application according to claim 9, is characterized in that, the pressure of described hot isostatic pressing is 40～50 MPa, and temperature is 60～80 ℃.
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