CN1611458A - Composite material for package - Google Patents

Composite material for package Download PDF

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Publication number
CN1611458A
CN1611458A CN200410086583.0A CN200410086583A CN1611458A CN 1611458 A CN1611458 A CN 1611458A CN 200410086583 A CN200410086583 A CN 200410086583A CN 1611458 A CN1611458 A CN 1611458A
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glass
composite material
package
powder
glass powder
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CN200410086583.0A
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CN100453485C (en
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菊谷武民
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron

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

Abstract

The invention provided a composite material for sealing which is substantially free of lead components for the sake of reduction of environmental load and is excellent in the required low-expansion characteristic, flow property and adhesion to a substrate. The composite material for sealing contains a lead-free phosphate glass powder and a filler powder comprising Zr<SB>2</SB>WO<SB>4</SB>(PO<SB>4</SB>)<SB>2</SB>. As the lead-free phosphate glass powder, a tin phosphate-based glass powder containing, by mol, 30-70% SnO, 20-45% P<SB>2</SB>O<SB>5</SB>, 0-20% ZnO, 0-10% Al<SB>2</SB>O<SB>3</SB>, 0-10% SiO<SB>2</SB>and 0-25% B<SB>2</SB>O<SB>3</SB>or a silver phosphate-based glass powder containing, by mol, 15-85% Ag<SB>2</SB>O+AgI, 10-55% P<SB>2</SB>O<SB>5</SB>, 0-20% Ga<SB>2</SB>O<SB>3</SB>, 0-60% TeO<SB>2</SB>, 0-50% ZnO, 0-30% Nb<SB>2</SB>O<SB>5</SB>, 0-15% B<SB>2</SB>O<SB>3</SB>and 0-30% WO<SB>3</SB>can be used.

Description

Composite material for package
Technical field
The present invention relates to a kind of composite material for package, relate to a kind of composite material for package that can be used as typotrons such as plasma panel (PDP), fluorescent display tube (VFD), FED with the packaged material of encapsulation such as the packaged material of panels or semiconductor integrated circuit, quartz crystal unit, SAW spectral filter etc. specifically.
Background technology
Packaged material as various materials such as glass, pottery, metals, be known that and use the material of encapsulation with glass, and at typotrons such as plasma panel (PDP), fluorescent display tube (VFD), FED with the encapsulation of panel with carried in the level Hermetic Package of high reliability packaging of elements such as semiconductor integrated circuit, quartz crystal unit, SAW spectral filter, in order to improve physical strength and to adjust thermal expansivity, in encapsulation hybrid ceramic filler powder in the glass.
If obtain firmly to encapsulate, need to be heated to sufficiently high temperature, so that encapsulation is with the glass gluing of surfaces of wetting material to be encapsulated fully.Yet, in the encapsulation of electronic component, must keep alap package temperature.In this purposes, widely used was the material that adopts lead borate class low melting glass in the past.
In recent years, consider, require from packaged material, to remove lead from environmental.Therefore proposed to replace the method for lead borate class glass with phosphoric acid class crown glasss such as phosphoric acid tin class glass, Trisilver phosphate class glass.
As the lead-free filler powder good with the matching of phosphoric acid class crown glass, known have a disclosed NbZr (PO in JP 2000-290007 communique 4) 3Filler powder, in JP 2002-37644 communique disclosed basic zirconium phosphate ((ZrO) 2P 2O 7) filler powder, disclosed niobium pentaoxide (Nb in JP 2001-19472 communique 2O 5) filler powder.
But, when these filler powder and phosphoric acid class crown glass are used in combination, forming with the difference of glass, the tendency towards devitrification of glass strengthens to some extent, hinders mobile factor thereby become sometimes, can't obtain sufficient cohesive with material to be encapsulated.And except above-mentioned filler powder, as not containing plumbous filler powder, it is also conceivable that and use trichroite, tindioxide, beta-eucryptite, mullite, silicon-dioxide, β-quartz solid solution, aluminium titanates, zircon, willemite etc., but all exist its coefficient of expansion can not fully descend or lack problems such as flowability in any filler powder.
Summary of the invention
The object of the present invention is to provide a kind of composite material for package,, wherein do not contain lead composition in fact in order to reduce carrying capacity of environment, and desired low expansion character and mobile and be good with the binding property of substrate.
Composite material for package of the present invention is characterised in that, contains phosphoric acid class leadless glass powder and by Zr 2WO 4(PO 4) 2The filler powder that forms.
Composite material for package of the present invention is characterised in that in addition, by Zr 2WO 4(PO 4) 2The unit volume containing ratio of the filler powder that forms is 5～50% of composite material for package integral body.
Composite material for package of the present invention is characterised in that in addition, by Zr 2WO 4(PO 4) 2The average grain diameter of the filler powder that forms is in the scope of 1～30 μ m.
Composite material for package of the present invention in addition is characterised in that phosphoric acid class leadless glass powder is a phosphoric acid tin class glass powder.
Composite material for package of the present invention is characterised in that in addition, in the phosphoric acid class leadless glass powder, contains 30～70%SnO, 20～45%P in mole % 2O 5, 0～20%ZnO, 0～10%Al 2O 3, 0～10%SiO 2, 0～25%B 2O 3
Composite material for package of the present invention in addition is characterised in that phosphoric acid class leadless glass powder is a Trisilver phosphate class glass powder.
Composite material for package of the present invention is characterised in that in addition, and in the phosphoric acid class leadless glass powder, % contains 15～85%Ag in mole 2O+AgI, 10～55%P 2O 5, 0～20%Ga 2O 3, 0～60%TeO 2, 0～50%ZnO, 0～30%Nb 2O 5, 0～15%B 2O 3, 0～30%WO 3
If use material of the present invention, then can reduce or all eliminate typotrons such as PDP, VFD, FED with the carrying capacity of environment material in the electronic components such as panel, the encapsulation of having loaded elements such as semiconductor integrated circuit, quartz crystal unit, SAW spectral filter, magnetic head.Also have, because material of the present invention is desired low expansion character and mobile and the material good with the cohesive of substrate, so the encapsulating material that is suitable as in the aforesaid various uses uses.
Embodiment
The Zr that in composite material for package of the present invention, uses 2WO 4(PO 4) 2Filler powder has the low-down coefficient of expansion.
In addition by using Zr 2WO 4(PO 4) 2Filler powder can obtain mobile and the good encapsulating material of cohesive.This reason can be presumed as follows.Generally speaking, if filler powder is burnt till with glass powder, then filler becomes branch to be melted in the glass and produces product with glass.This can become makes the glass crystallization, hinders the mobile factor.Yet, Zr 2WO 4(PO 4) 2The reaction product of filler and phosphoric acid class glass can not cause the crystallization of phosphoric acid class glass.And then the meeting elution goes out the tungsten (W) as the filler composition in glass, can improve the bounding force of glass thus.Also have, when in glass forms, containing a large amount of tungsten because of same purpose, produce sometimes the devitrification problem, so should be noted that.
In addition in the present invention, Zr 2WO 4(PO 4) 2The unit volume containing ratio of filler powder is preferably 5～50% of composite material for package integral body, is particularly preferably 10～30%.The general main reason of in encapsulating material, using filler powder, the firstth, only can't reach the low coefficient of expansion that is suitable for material to be encapsulated with the packaged glass composition, so obtain the low coefficient of expansion by adding filler powder.By adjusting kind or the combined amount of filler powder, can obtain at an easy rate the object expansion coefficient.Also have, the shared unit volume containing ratio of filler powder is roughly proportional in the coefficient of expansion of packaged material and the material monolithic.The secondth, only can't guarantee necessary mechanical strength, so give sufficient mechanical by adding filler powder with the packaged glass composition.But mechanical strength improve effect with the difference of filler powder kind difference, so need to adjust its unit volume containing ratio to employed every kind of filler powder.
Zr among the present invention 2WO 4(PO 4) 2The unit volume containing ratio consider above-mentioned situation and determine.Work as Zr 2WO 4(PO 4) 2The unit volume containing ratio be less than encapsulating material integral body 5% the time, although the good fluidity in when encapsulation, it is too high that thermal coefficient of expansion can become, inconsistent with the coefficient of expansion of material to be encapsulated, might produce distortion and be stripped from.Physical strength also becomes not enough easily in addition, might crack after encapsulation etc.On the other hand, work as Zr 2WO 4(PO 4) 2The unit volume containing ratio surpass encapsulating material integral body 50% the time, encapsulating material lacks mobile, probably can't encapsulate under desired firing temperature.Even perhaps for guarantee that flowability encapsulates after improving firing temperature, because glass ingredient is few, the airtight reliability of packed part also can descend.
In addition among the present invention, Zr 2WO 4(PO 4) 2The median size of filler powder is preferably 1～30 μ m, is preferably 5～20 mu m ranges especially.Work as Zr 2WO 4(PO 4) 2Average grain diameter when 1 μ m is following, micronizing can take place in filler powder, causes the coefficient of expansion to rise, the result will die down as the effect of low-expansion material.Its result if will obtain the object expansion coefficient, needs more filler powder, and this can make the mobile variation of encapsulating material when burning till.Encapsulating material normally uses with the pasty state state with mixed with resin in addition, if the particle diameter of filler powder is too small, sticking with paste viscosity during then with mixed with resin can uprise, and becoming is difficult to mix with resin.If use more resin for fear of this situation, then can produce new problem, the volume after promptly burning till is difficult for adjustment etc.On the other hand, work as Zr 2WO 4(PO 4) 2Average grain diameter when 30 μ m are above, although the effect that reduce to expand increases, the mechanical strength of burning till rear encapsulating material can die down.In addition in the encapsulation of the electronic component material of densification, might produce at packed part and the integrity problem such as to sew.Also have, when measuring granularity, for example can use laser diffraction formula particle size distribution measurement device (Shimadzu Seisakusho Ltd.'s system) to measure.
In the composite material for package of the present invention, both can use separately Zr as filler powder in addition 2WO 4(PO 4) 2Filler powder also can be used with other the lead-free filler powder of using all the time.Lead-free filler powder as other can use filler powder such as trichroite, tindioxide, beta-eucryptite, mullite, silicon-dioxide, β-quartz solid solution, aluminium titanates, zircon, willemite, and these can use a kind of or more than two kinds.And the unit volume containing ratio of other lead-free filler powder is preferably 0～45% of composite material for package integral body, is preferably 0～30% especially.
Then the glass powder that uses in composite material for package of the present invention is described.Glass powder can use so long as be made up of phosphoric acid class crown glass, especially preferably uses phosphoric acid tin class glass and silver orthophosphate class glass.
As the preferred example of phosphoric acid tin class glass, can enumerate in mole % and contain 30～70%SnO, 20～45%P 2O 5, 0～20%ZnO, 0～10%Al 2O 3, 0～10%SiO 2, 0～25%B 2O 3Glass.Narration is defined as the reason of above-mentioned compositing range below.
SnO is the composition that the glass eutectic is revealed.If SnO is less than 30%, then the viscosity of glass can uprise, and can make firing temperature become too high, and if above 70%, then can not carry out vitrifying.If the SnO composition is too much, so easy devitrification when burning till is preferably below 60%.If more than 40%, then good fluidity can obtain high air-tightness in addition, and is therefore preferred.
P 2O 5It is network former.At P 2O 5The stability that is less than glass in 20% the zone is not enough abundant.In 20～45% scope, can obtain the enough stability as glass, and if above 45%, then moisture-proof can variation.Other P 2O 5If more than 25%, then glass is incited somebody to action more stabilisation, if but surpass 35%, then the weather proofing of sintered body can show a little trend of variation, so be preferably 25～35%.
ZnO is an intermidate oxide.ZnO is not a neccessary composition, but makes the effect of stabilizationization better, so preferably contain more than 4%.If but ZnO surpasses 20%, the devitrification phenomenon takes place on glass surface when then burning till easily.In addition, when after burning till, also having the heat treatment step of long-time (for example more than 1 hour), be easy to cause devitrification, so should under the prerequisite that keeps stability, glass, consider its content.Under these circumstances, ZnO content is preferably 5～15%.
Al 2O 3It is intermidate oxide.Al 2O 3Not neccessary composition, but have the effect of the stabilization of making, but also have the effect that reduces thermal coefficient of expansion, so preferably contain this material.But if surpass 10%, then softening temperature will rise, and hinders the flowability when burning till.Therefore, Al 2O 3Content be 0～10%.Also have, when the stability of considering glass and thermal coefficient of expansion and flowability etc., more preferably 1～5% scope.
SiO 2It is network former.Because SiO 2Have the effect that suppresses devitrification in the encapsulation behind the unsticking mixture, be advisable so contain this material.When flowability that is considered as low melting material etc., SiO 2Content be preferably 0～10%.If surpass 10%, then softening temperature can rise, and the flowability when burning till is with obvious variation.
B 2O 3It is network former.B 2O 3Has the effect of being separated the scum silica frost that produces when reducing fusing by glass.Has the effect that makes stabilizationization in addition.If but more than 25%, then the viscosity of glass can become too high, the flowability when burning till is obvious variation, thereby can influence the resistance to air loss of packed part.Also have, because B 2O 3The tendency that improves glass adhesion is remarkable, so when requiring very high flowability and need to reduce softening point significantly, preferably do not contain this material.
R 2O (R is Li, Na, K, Cs) is not neccessary composition, but by in forming, adding R 2At least a among the O composition can strengthen the bonding force with material to be encapsulated.If but total amount surpasses 20%, easy devitrification when then burning till.Also have, when considering surperficial devitrification and flowability, R 2The O total amount is preferably below 10%.In addition at R 2In the O composition, Li 2O is the raising composition the highest with the ability of the bonding force of substrate.
In addition, can also add various compositions in the above-mentioned glass.For example can contain total amount at the WO below 35% 3, MoO 3, Nb 2O 5, TiO 2, ZrO 2, CuO, MnO, R ' O (R ' be Mg, Ca, Sr, Ba) etc. make the composition of stabilizationization.The reason that the content of these stabilization compositions is defined as below 35% is, if surpass 35%, then glass can become unstable and easy devitrification when being shaped on the contrary.In order to obtain more stable glass, be preferably below 25%.In order to improve weather proofing and moisture-proof, can also contain In in addition 2O 3Deng.
The content of stabilization composition and qualification thereof be the reasons are as follows described.
WO 3And MoO 3Content all be preferably 0～20%, be preferably 0～10% especially.If these compositions surpass 20% respectively, then the viscosity of glass uprises easily.Particularly, WO 3Also be contained in the filler composition of the present invention, so match very much with filler.
Nb 2O 5, TiO 2, and ZrO 2Content all be preferably 0～15%, especially preferably respectively be 0～10%.If these compositions surpass 15% respectively, then the tendency towards devitrification of glass becomes big easily.
The content of CuO and MnO all is preferably 0～10%, especially preferably respectively is 0～5%.If these compositions surpass 10% respectively, then glass becomes unstable easily.
The content of R ' O is preferably 0～15% in total amount, is preferably 0～5% especially.R ' is if O surpasses 15%, and then glass becomes unstable easily.
In the situation of not considering cost, if will obtain height weather proofing and moisture-proof, can use In 2O 3In 2O 3Content be preferably 0～5%.
Also have, in typotron purposes such as VFD, FED, CRT, PDP, halogens such as F, Cl might bring detrimentally affect to electronic discharge etc., produce the degradation problem under the display brightness that makes.Therefore when glass of the present invention is used for the display tube purposes, preferably not halogen-containing in the glass.
Glass with above composition has 270～380 ℃ glass transition temperature, can demonstrate good flowability in about 400～600 ℃ temperature range.Under 30～250 ℃, have about 90～150 * 10 in addition -7/ ℃ thermal expansivity.
In addition as the preferred example of silver orthophosphate class glass, can enumerate in mole % and contain 15～85%Ag 2O+AgI, 10～55%P 2O 5, 0～20%Ga 2O 3, 0～60%TeO 2, 0～50%ZnO, 0～30%Nb 2O 5, 0～15%B 2O 3, 0～30%WO 3Glass.Below narrated the restriction reason of above-mentioned compositing range.
AgI and Ag 2O is the main component that glass is used in encapsulation, owing to be insoluble in water, have the effect of the resistance to water that improves glass, but if its total amount is less than 15%, then the viscosity of glass can uprise simultaneously, is difficult to carry out the low temperature encapsulation, and the while resistance to water descends easily.On the other hand, if more than 85%, the easy difficult of vitrifying then.Therefore, Ag 2The content of O+AgI is 15～85%.
P 2O 5Also be encapsulation with the main component of glass, if be less than 10%, vitrifying meeting difficult then is and if more than 55%, then the viscosity of glass uprises easily.Therefore, P 2O 5Content be 10～55%.
Ga 2O 3Not neccessary composition, but have remarkable result aspect the stability that increases glass, raising resistance to water, the reduction thermal coefficient of expansion.In addition, if more than 20%, then the viscosity of glass uprises easily.Therefore, Ga 2O 3Content be 0～20%.
TeO 2Also stability, raising water tolerance, the reduction thermal expansivity that increases glass had certain effect, if but more than 60%, then the viscosity of glass uprises easily.Therefore, TeO 2Content be 0～60%.
ZnO also to the stability that increases glass, improve resistance to water, reduce thermal coefficient of expansion and have certain effect, but if ZnO more than 50%, then the viscosity of glass uprises easily.Therefore, the content of ZnO is 0～50%.
Nb 2O 5The viscosity of glass also stability, raising resistance to water, the reduction thermal coefficient of expansion that increases glass had certain effect, if but more than 30%, then can uprise.Therefore, Nb 2O 5Content be 0～30%.
B 2O 3Effect with the stabilization of making, and B 2O 3If more than 15%, then the viscosity of glass can uprise.Therefore, B 2O 3Content be 0～15%.
WO 3Also stability, raising water tolerance, the reduction thermal expansivity that increases glass being had certain effect, also is the fusible composition that is used to improve glass in addition.If but more than 30%, then the viscosity of glass can uprise.In addition, be easy to devitrification this moment and can make glass become unstable.Therefore, WO 3Content be 0～30%.
Except above-mentioned composition, can also contain the following Li of 5 moles of % in addition 2O, SiO 2, Al 2O 3, MnO 2, In 2O 3, MoO 3, Bi 2O 3, CuO, GeO 2Or the sulfide of the halide (except the AgI) of Li, Si, B, Pb, Al, Mn, In, Mo, Cu, Co, Ge, W, Zn, Te, Ga, P, Ag or Li, Si, B, Pb, Al, Mn, In, Mo, Cu, Co, Ge, W, Zn, Te, Ga, P, Ag.
Also have, so-called halogenide is fluorochemical, muriate, bromide or iodide, when metallic element is identical, compares during with the use oxide compound, and the effect that glass adhesion is reduced is bigger.
Trisilver phosphate class glass with above composition has about 120～250 ℃ second-order transition temperature, has about 130～250 * 10 in addition under 30～150 ℃ -7/ ℃ thermal expansivity.
Below to making the Zr that uses among the present invention 2WO 4(PO 4) 2The method of filler powder describes.When making Zr 2WO 4(PO 4) 2During filler powder, as long as can obtain to have the filler powder of this composition requirement, then its method is not particularly limited.Enumerated the object lesson of making method below.
At first, in order to obtain Zr 2WO 4(PO 4) 2Composition, will be equivalent to respectively the basic zirconium phosphate (ZrP of 1mol% amount 2O 7), zirconium hydroxide (Zr (OH) 4) or zirconia (ZrO 2), tungsten oxide (WO 3) mix, directly or with respect to the total amount of 3 kinds of raw materials add after the magnesia or zinc oxide as the crystallization auxiliary agent of 3wt%, mix with ball mill etc.Then, this mixing raw material of sintering.The agglomerating condition is for example 1400 ℃ of following sintering 15 hours.Behind the sintering, in firing furnace, slowly be cooled to below 200 ℃, from stove, take out then.Afterwards, with the Zr with sintering such as ball mill 2WO 4(PO 4) 2Piece is pulverized.Pulverizing need to be carried out 1～2 hour, afterwards to carrying out classification through pulverizing the powder of making.If can be the sieve of 105 μ m by mesh, then can obtain the Zr that average grain diameter is 10 μ m 2WO 4(PO 4) 2Filler powder.
In addition, except above-mentioned method for making, can also adopt following methods, that is, the filler material that will become the pasty state state sprays in the warm braw air, obtains the powder agglomerate, burns till with method same as described above then, pulverizes in case of necessity again, and carries out classification.
Below, explain the present invention according to embodiment.
The Zr that uses in the present embodiment is at first described 2WO 4(PO 4) 2The preparation method of filler powder.The 265.2g basic zirconium phosphate that will be equivalent to 1mol: ZrP 2O 7, be equivalent to the 159.2g zirconium hydroxide of 1mol: Zr (OH) 4, be equivalent to the 231.8g tungsten oxide of 1mol: WO 3Mix as raw material, adding is equivalent to the 19.7g magnesia of the 3wt% of total amount as the crystallization auxiliary agent, and mixes 1 hour with the alumina balls grinding machine.Then this mixed-powder was burnt till under 1400 ℃ 15 hours in alumina crucible, thus synthetic Zr 2WO 4(PO 4) 2After the cooling, by taking out Zr in the crucible 2WO 4(PO 4) 2Sinter, with the pulverizing of alumina balls grinding machine, classification, and by metal 325 mesh sieves, obtaining average grain diameter is the Zr of 15 μ m 2WO 4(PO 4) 2Filler powder.
Niobium pentaoxide (the Nb that in comparative example, uses in addition 2O 5) filler powder and tin ash (SnO 2) filler powder all uses identical method to make.At first add 3wt% zinc oxide as sintering aid in the material powder and mix, in alumina crucible, under 1400 ℃, burnt till 16 hours then.Then take out agglomerate, after pulverizing with the alumina balls grinding machine, by metal 325 mesh sieves, obtaining average grain diameter is the niobium pentaoxide (Nb of 17 μ m 2O 5) and tin ash (SnO 2) filler powder.
Similarly, the NbZr (PO that in comparative example, uses 4) 3Filler powder is made as described below.At first mix the niobium phosphate that is equivalent to the 1mol amount: NbPO 5Powder and be equivalent to the basic zirconium phosphate of 1mol amount: ZrP 2O 7Powder add the magnesium oxide powder of 2 weight portions (2wt%) as raw material with respect to these mixed-powder 100 weight portions after making mixed-powder.Then with these three kinds of powder mixes, in alumina crucible, under 1400 ℃, carry out 15 hours burn till then.After the cooling, by the NbZr (PO that takes out sintering in the crucible 4) 3, after pulverizing with the alumina balls grinding machine, carry out classification by metal 325 mesh sieves.Having obtained thus average grain diameter is the NbZr (PO of 14 μ m 4) 3Filler powder.
The glass powder sample (sample a-c) of table 1 expression phosphoric acid tin class, the glass specimen (sample d-e) of table 2 expression Trisilver phosphate class.
Table 1
a b c
Glass forms (mol%) SnO P 2O 5La 2O 3CeO 2Gd 2O 3ZnO MgO Al 2O 3SiO 2B 2O 3Li 2O Na 2O 51 22 - - - 5 - 1 - 21 - - 48.5 31.5 0.5 1 1 8 - 1 6.5 - - 2.0 54 30 0.5 1.5 - 11 - 1.5 - - 1.5 -
Fusion temperature (℃) 900 850 850
Glass transition temperature (℃) 334 281 278
Table 2
d e
Glass forms (mol%) Ag 2O AgI P 2O 5Ga 2O 3TeO 2ZnO Nb 2O 3 42 20 20--10- 27 27 22 4 18-2
Fusion temperature (℃) 750 750
Glass transition temperature (℃) 155 142
Modulation and filler powder blended glass powder as follows.Mixing raw material at first, it is had in the table form, the quartz crucible cover lid of phosphoric acid tin class glass is being housed giving afterwards, and be equipped with under the condition of quartz crucible lid of Trisilver phosphate class glass, in air, under the temperature shown in the table 1,2, melted 1～2 hour.Then make molten glass lamellar by being configured as between water cold drum, after pulverizing with ball mill, making itself and filler powder is the sieve of 105 μ m in the same manner by mesh, is the glass powder of 10 μ m thereby obtain average grain diameter.
To the glass powder sample that obtains, estimated second-order transition temperature, obtained the result shown in the table 1,2.Also have, glass transition temperature is to be to utilize the dilatometer of quartzy push rod formula to measure behind the sample of 40 * 10mm φ with forming of glass.
Then glass powder sample a-e is mixed with filler powder, make the matrix material sample, and supply in various evaluations according to the ratio shown in the table 3,4.Also has " ZWP " expression Zr in the table 2WO 4(PO 4) 2Filler powder, " NZP " expression NbZr (PO 4) 3Filler powder." alkali " represents soda-lime glass in addition, the high deformation point glass of " high deformation point " expression.
Thermal expansivity is to measure with the dilatometer of quartzy push rod formula after the matrix material sample is configured as the sample of 40 * 10mm φ.The thermal expansivity of the packaged material that is fit to depends on the thermal expansivity of packed substrate.When using the packaged glass of phosphoric acid class, the thermal expansivity that is suitable for the soda-lime glass substrate is 60 * 10 -7/ ℃～78 * 10 -7/ ℃, preferred 68 * 10 -7/ ℃～75 * 10 -7/ ℃, in high deformation point glass substrate and aluminum oxide, be 55 * 10 -7/ ℃～72 * 10 -7/ ℃, preferred 60 * 10 -7/ ℃～70 * 10 -7/ ℃.
When estimating flowability, with metal pattern density part weight (is equivalent to 1cm 3The weight of glass volume) powder is made into the button-type moulded body that diameter is 20mm, and under the firing condition of table 3 and table 4 it is burnt till, and measures its flow diameter.Under the firing condition of each table, be for the desired suitable flow behavior of encapsulating material more than 20mm, more than the preferred 22mm.
When estimating binding property, for the matrix material sample that is encapsulated on the substrate shown in the table, estimated when with under the situation of curved substrate from the complexity of strippable substrate, and a situation that is not easy to peel off is defined as ◎, being not easy to peel off, but if bending to a certain degree is defined as zero with regard to the situation of being stripped from, and situation about peeling off easily is defined as *.
Table 3
??1 ??2 ??3 ??4 ????5
Purposes The VFD encapsulation The PDP encapsulation The PDP encapsulation The encapsulation of chip shell The encapsulation of chip shell
Blending ratio (volume %) Glass ??a ??80 ??b ??75 ??c ??75 ??d ??60 ????e ????60
Filler ??ZWP ??20 ??ZWP ??25 ??ZWP ??25 ??ZWP ??40 ????ZWP ????40
The firing condition firing temperature (℃) hold-time (℃) ??480 ??10 ??450 ??10 ??450 ??10 ??330 ??10 ????330 ????10
Thermal expansivity (* 10 -7/℃) ??72.4 ??64.9 ??66.3 ??68.5 ????69.9
Flow diameter (mm) ??24.5 ??23.8 ??24.1 ??22.3 ????23.0
Substrate Alkali High deformation point High deformation point Aluminum oxide Aluminum oxide
Binding property ??◎ ??◎ ??◎ ??◎ ????◎
Table 4
??6 ??7 ??8 ??9 ????10
Purposes The VFD encapsulation The PDP encapsulation The PDP encapsulation The encapsulation of chip shell The encapsulation of chip shell
Blending ratio (volume %) Glass ??a ??80 ??b ??75 ??c ??75 ??d ??60 ????e ????60
Filler Columbium pentoxide 20 ??NZP ??25 Trichroite 25 ??NZP ??40 Trichroite 40
The firing condition firing temperature (℃) hold-time (℃) ??480 ??10 ??450 ??10 ??450 ??10 ??330 ??10 ????330 ????10
Thermal expansivity (* 10 -7/℃) ??76.5 ??70.1 ??72.0 ??70.0 ????73.4
Flow diameter (mm) ??23.3 ??22.8 ??21.9 ??21.0 ????21.5
Substrate Alkali High deformation point High deformation point Aluminum oxide Aluminum oxide
Binding property ??◎ ??× ??○ ??× ????○
By table 3,4 as can be known, use Zr 2WO 4(PO 4) 2The embodiments of the invention of filler powder have all obtained good result in the various evaluations such as thermal coefficient of expansion, flowability and bonding force.
Composite material for package of the present invention can be used as the packaged material of fluorescent display tube (VFD), FED, plasma panel typotrons such as (PDP) usefulness panel, carried the level Hermetic Package material of the high reliability packaging of elements such as semiconductor integrated circuit, quartz crystal unit, SAW spectral filter, the jointing material of electronic components such as magnetic head etc.

Claims (7)

1. composite material for package is characterized in that containing phosphoric acid class leadless glass powder and by Zr 2WO 4(PO 4) 2The filler powder that forms.
2. composite material for package as claimed in claim 1 is characterized in that by Zr 2WO 4(PO 4) 2The unit volume containing ratio of the filler powder of forming is 5～50% of a composite material for package integral body.
3. such as claim 1 or 2 described composite material for package, it is characterized in that by Zr 2WO 4(PO 4) 2The average grain diameter of the filler powder that forms is in the scope of 1～30 μ m.
4. composite material for package as claimed in claim 1 is characterized in that phosphoric acid class leadless glass powder is a phosphoric acid tin class glass powder.
5. such as claim 1 or 4 described composite material for package, it is characterized in that containing 30～70%SnO, 20～45%P in mole % in the phosphoric acid class leadless glass powder 2O 5, 0～20%ZnO, 0～10%Al 2O 3, 0～10%SiO 2, 0～25%B 2O 3
6. composite material for package as claimed in claim 1 is characterized in that phosphoric acid class leadless glass powder is a Trisilver phosphate class glass powder.
7. such as claim 1 or 6 described composite material for package, it is characterized in that % contains 15～85%Ag in mole in the phosphoric acid class leadless glass powder 2O+AgI, 10～55%P 2O 5, 0～20%Ga 2O 3, 0～60%TeO 2, 0～50%ZnO, 0～30%Nb 2O 5, 0～15%B 2O 3, 0～30%WO 3
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