CN101604636A - The manufacture method of multilayer ceramic substrate and the e-machine that has used it - Google Patents
The manufacture method of multilayer ceramic substrate and the e-machine that has used it Download PDFInfo
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- CN101604636A CN101604636A CNA200910150344XA CN200910150344A CN101604636A CN 101604636 A CN101604636 A CN 101604636A CN A200910150344X A CNA200910150344X A CN A200910150344XA CN 200910150344 A CN200910150344 A CN 200910150344A CN 101604636 A CN101604636 A CN 101604636A
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- H01L24/93—Batch processes
- H01L24/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
- H01L24/97—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being connected to a common substrate, e.g. interposer, said common substrate being separable into individual assemblies after connecting
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- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
- H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
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- H01L2224/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
- H01L2224/97—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being connected to a common substrate, e.g. interposer, said common substrate being separable into individual assemblies after connecting
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- H01L2924/156—Material
- H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
- H01L2924/15787—Ceramics, e.g. crystalline carbides, nitrides or oxides
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Abstract
A kind of manufacture method of multilayer ceramic substrate, it is characterized in that, have: (a) use the slip of the powder contain ceramic material and organic binder bond to make and to carry out low sintering substrate raw cook, (b) after described substrate has formed electrode on raw cook, stacked and make not sintered multilayer ceramic substrate, (c) forming under the sintering temperature contain at sintered multilayer ceramic substrate not the inorganic particulate of sintering and the constraint raw cook of organic binder bond on the bearing film, should retrain and strip down from bearing film with raw cook, make described constraint with contacting of raw cook with described bearing film the face of a side and described not sintered multilayer ceramic substrate top and/or below be provided with connecting airtight, make the incorporate laminated body that possesses restraint layer, (d) the described laminated body of sintering, (e) with described restraint layer from sintering the surface of the described laminated body operation of removing, the average grain diameter of wherein said inorganic particulate is 0.3～4 times of the average grain diameter of the powder of described ceramic material more than 0.3 μ m.
Description
The application divides an application, the application number of its female case application: PCT/JP2004/015282 (200480005626.6), the applying date: 2004.10.15, denomination of invention: multilayer ceramic substrate and manufacture method thereof and the e-machine that has used it
Technical field
The present invention relates to utilize the multilayer ceramic substrate and the manufacture method thereof that can realize low sintering no contraction process manufacturing and the e-machine of usefulness such as portable phone that has possessed this multilayer ceramic substrate or information terminal device.
Background technology
Now, multilayer ceramic substrate is in field of mobile communication terminal machines such as portable phone etc., in order to constitute multiple electronic units such as antenna switch module, PA module substrate, filter, antenna component, various combiners and be widely used.
Multilayer ceramic substrate is that a plurality of ceramic layers are laminated, and has at the internal electrode that forms on each ceramic layer in inside, runs through perforation (via hole) electrode of ceramic layer for connecting between with internal electrode, and be formed with outer electrode outside.Multilayer ceramic substrate after having carried semiconductor chip or other chip part, is installed in the surface of mother substrate usually.In order to realize multifunction, densification and high performance, distribution electrode and outer electrode are disposed to high-density.
But in the sintering circuit that is used for obtaining multilayer ceramic substrate, pottery approximately shrinks about 10～25%.Because it not is to produce equably on the whole at multilayer ceramic substrate that bigger like this sintering shrinks, and therefore will bring warpage or distortion.This kind warpage or distortion not only can make the characteristic variation of multilayer ceramic substrate, and its fitting operation is also counteracted the densification of impeded electrode.So hope will be made as below 1% by the shrinkage that sintering causes, and the deviation that reduces to shrink, thus warpage being suppressed in every 50mm length is below the 30 μ m.
In addition, owing to bring into use low-resistance Ag class electrode pastes recently, so the sintering of multilayer ceramic substrate carries out under the low temperature about 800～1000 ℃.Thus, bring into use under the temperature below 1000 ℃ the raw cook (green sheet) of LTCC (Low Temperature Co-firedCeramics) that can sintering gradually, especially the glass-ceramic raw cook that is made of ceramic powders, organic binder bond and plasticizer such as glass powder, aluminium oxide, mullite, cordierites adopts the what is called " no contraction process " of integrated ground sintering under the situation of the contraction on the X-Y plane that does not substantially produce multilayer ceramic substrate.
For example, (No. the 5085720th, No. the 5254191st, United States Patent (USP) and United States Patent (USP)) (patent documentation 2) announces that following method is arranged to specially permit No. 2554415 (patent documentation 1) and patent No. 2617643, promptly, preparation is by the ceramic powders that is scattered in the organic binder bond, the substrate raw cook that the mixture of agglutinating property inorganic binder (glass ingredient) constitutes, and be dispersed in the organic binder bond and the constraint that the mixture that obtains forms raw cook by inorganic particulate (aluminium oxide etc.) that can not sintering under with the sintering temperature of raw cook at substrate, stacked many substrates form unsintered multilayer ceramic substrate with raw cook, connect airtight constraint below reaching in the above with behind the raw cook, carried out sintering.According to this method, substrate soaks into to 50 μ m with the raw cook layer to constraint with agglutinating property inorganic binder contained in the raw cook, with two raw cook combinations, but the constraint that constitutes by inorganic particulate with raw cook because sintering not in fact, thereby do not shrink, thereby the substrate that has suppressed to connect airtight the with it contraction of the X-Y plane of raw cook.
Patent No. 3335970 (patent documentation 3) proposes, and is higher than No. the 2554415th, patent (patent documentation 1) in order to make substrate with raw cook and the adhesion that retrains with raw cook, also contains glass ingredient in retraining with raw cook.
Te Kaiping 9-266363 number (patent documentation 4) proposes, partly do not strip down with raw cook with the constraint that will anchor at substrate surface the raw cook by the effect of the glass ingredient that soaks into from substrate, and with its directly utilization of surface as substrate.
Te Kaiping 11-354924 number (patent documentation 5) proposes, and by multilayer ceramic substrate behind the sintering and constraint are located in the given range with the difference of the thermal coefficient of expansion of raw cook, utilizes thermal stress to retrain with raw cook and strips down from multilayer ceramic substrate.
According to described no contraction process, retrain the substrate raw cook by utilizing constraint with raw cook, though substrate shrinks along thickness direction with raw cook, the contraction of X-Y plane is suppressed.But, shown in No. 3335970 (patent documentation 3) middle record of patent, mainly pay close attention to up to now and how to improve substrate is used raw cook with raw cook and constraint adhesion.In the described conventional art, the constraint behind the sintering, thereby can be compared simply and removes owing to become the powder shaped thin slice of the vaporized porous of organic binder bond with raw cook, but in fact often can't remove fully.Thus, just need make the proterties stabilisation on the surface of multilayer ceramic substrate.For example, need to consider to the outer electrode of the top and bottom of multilayer ceramic substrate influence, to the influence of the metalized film of the Ni that externally forms on the electrode behind the sintering or Au.
Here, investigate the behavior of substrate with glass ingredient contained in the raw cook.Glass ingredient softens along with the progress of sintering, to the surperficial stripping of substrate with raw cook.On the other hand, with in the raw cook, can in the vestige of the organic binder bond that has volatilized, produce emptying aperture in constraint.So the aqueous glass of having changed is because capillarity etc. and soaking in the emptying aperture of constraint with raw cook.Though penetration depth is different because of various conditions, typical situation is about 50 μ m.Utilize soaking into of glass, the combination securely of two raw cooks.But,, so just be difficult to keep its precision and quality because simultaneously substrate becomes with the outer electrode on raw cook surface and floats over to substrate with the state on the melten glass of the surperficial stripping of raw cook.In addition, in soak process, have the situation of glass ingredient, thereby become loose contact and the bad reason of plated film attached to the surface of outer electrode.
In addition, when sintering, also can see as constraint and invade substrate with the phenomenon in the raw cook with the aluminium oxide particles of the primary raw material of raw cook.If the aluminium oxide particles that buries dearly will be removed,, because the outer electrode on surface also is removed, therefore also need to form once more the such additional process of outer electrode like this though carry out sandblast or grind getting final product from multilayer ceramic substrate.
As implied above, no contraction process in the past is in being applied to have formed the not sintered multilayer ceramic substrate of outer electrode the time and be not suitable for.Thus, all the time, after behind the sintering of multilayer ceramic substrate restraint layer being removed, print outer electrode, burn till.
Patent documentation 1: specially permit No. 2554415
Patent documentation 2: specially permit No. 2617643
Patent documentation 3: specially permit No. 3335970
Patent documentation 4: the spy opens flat 9-266363 number
Patent documentation 5: the spy opens flat 11-354924 number
Summary of the invention
So, the objective of the invention is to, a kind of manufacture method of multilayer ceramic substrate is provided, described multilayer ceramic substrate is that the not sintered multilayer ceramic substrate that will form outer electrode on the surface does not have the multilayer ceramic substrate that shrinks the ground sintering and get, contraction in the X-Y plane of this multilayer ceramic substrate is suppressed, warpage or distortion are few, do not have the scolder of outer electrode to corrode, and plated film is good.
Another object of the present invention is, provide a kind of not above the sintered multilayer ceramic substrate and/or below on, be provided with that restraint layer carries out sintering and when making multilayer ceramic substrate, bring into play sufficient restraining force and suppressed dysgenic method external electrode surface.Wherein, described not sintered multilayer ceramic substrate has formed outer electrode from the teeth outwards.
Another object of the present invention is, the e-machine that has used this kind multilayer ceramic substrate is provided.
The multilayer ceramic substrate of mode one of the present invention, it is characterized in that, will comprise ceramic material and can carry out not sintered multilayer ceramic substrate that low sintering substrate is laminated with raw cook at least above, form outer electrode, and according to make with under the sintering temperature of sintered multilayer ceramic substrate not the inorganic particulate of sintering as the restraint layer of main component and above the described not sintered multilayer ceramic substrate and/or below the mode of connecting airtight be provided with and form incorporate laminated body, behind described laminated body sintering, described restraint layer removed form, wherein in the face of this multilayer ceramic substrate shrinkage 1% with interior (deviation is in 0.1%).
Described ceramic material preferably contains with Al with the state of oxide respectively as main component
2O
3Be scaled the Al of 10～60 quality %, with SiO
2Be scaled 25～60 quality % Si, with SrO be scaled 7.5～50 quality % Sr and with TiO
2The Ti that is scaled 0～20 quality % is (wherein, with Al
2O
3, SiO
2, SrO and TiO
2Total amount be made as 100 quality %), 700 ℃～850 ℃ down the calcining back pulverize the pulverous materials that form.
In the described ceramic material as auxiliary element preferably with respect to the main component of per 100 mass parts, contain from by with Bi
2O
3Be scaled the Bi of 0.1～10 mass parts, with Na
2O is scaled the Na of 0.1～5 mass parts, with K
2O be scaled 0.1～5 mass parts K and with CoO be scaled select in one group that the Co of 0.1～5 mass parts constitutes at least a, from by be scaled the Cu of 0.01～5 mass parts with CuO, with MnO
2Be scaled select in one group that the Ag of the Mn of 0.01～5 mass parts and 0.01～5 mass parts constitutes at least a.
The multilayer ceramic substrate of mode two of the present invention, it is characterized in that, will comprise ceramic material and can carry out not sintered multilayer ceramic substrate that low sintering substrate is laminated with raw cook at least above, form outer electrode, and according to make with under the sintering temperature of sintered multilayer ceramic substrate not the inorganic particulate of sintering as the restraint layer of main component and above the described not sintered multilayer ceramic substrate and/or below the mode of connecting airtight be provided with and form incorporate laminated body, behind described laminated body sintering, described restraint layer removed form, wherein said substrate has and comprises that with the strontium feldspar be the feldspar group crystal of main component and the tissue of alpha-alumina crystals, shrinkage is in 1% in the face of described multilayer ceramic substrate, its deviation is in 0.1%, and for the described inorganic particulate that remains on the described outer electrode, constitute described inorganic particulate metal with respect to the metal that constitutes described outer electrode and constitute the ratio of total amount of the metal of described inorganic particulate, below 20 quality %.
In general the strontium feldspar has SrAl
2Si
2O
8Composition.At least a portion of the crystal of strontium feldspar is preferably hexagonal crystal.
The feature of the manufacture method of multilayer ceramic substrate of the present invention is, has (a) and uses the slip of the powder that contains ceramic material and organic binder bond to make can to carry out low sintering substrate raw cook,
(b) after described substrate forms electrode on raw cook, stacked and make not sintered multilayer ceramic substrate,
(c) forming under the sintering temperature contain at sintered multilayer ceramic substrate not the inorganic particulate of sintering and the constraint raw cook of organic binder bond on the bearing film, and make described constraint with contacting of raw cook with bearing film the face of a side and described not sintered multilayer ceramic substrate top and/or below be provided with connecting airtight, form incorporate laminated body, (d) the described laminated body of sintering, (e) with described restraint layer from sintering the surface of the described laminated body operation of removing, the average grain diameter of described inorganic particulate is 0.3～4 times of the average grain diameter of the powder of described ceramic material more than 0.3 μ m.
In the manufacture method of described multilayer ceramic substrate, preferably described restraint layer is formed the thickness more than the 50 μ m.
In the manufacture method of above-mentioned multilayer ceramic substrate, described substrate raw cook is with Al
2O
3Be scaled the Al of 10～60 quality %, with SiO
2Be scaled 25～60 quality % Si, with SrO be scaled 7.5～50 quality % Sr and with TiO
2The Ti that is scaled 0～20 quality % as main component (with Al
2O
3, SiO
2, SrO and TiO
2Total amount be made as 100 quality %) ceramic material 700 ℃～850 ℃ down the calcining back pulverize, use contains the calcined body micro mist of gained and the slip of organic binder bond, that makes can carry out low sintering substrate raw cook, wherein with described laminated body at 800 ℃～1000 ℃ following sintering, described restraint layer is removed from described laminated body.
Described substrate preferably contains following auxiliary element with raw cook, that is, with respect to the described main component of per 100 mass parts, contain from by with Bi
2O
3Be scaled the Bi of 0.1～10 mass parts, with Na
2O is scaled the Na of 0.1～5 mass parts, with K
2O be scaled 0.1～5 mass parts K and with CoO be scaled select in one group that the Co of 0.1～5 mass parts constitutes at least a and from by be scaled the Cu of 0.01～5 mass parts with CuO, with MnO
2Be scaled select in one group that the Ag of the Mn of 0.01～5 mass parts and 0.01～5 mass parts constitutes at least a.
In above-mentioned any one method, as described restraint layer, be preferably in and form the constraint raw cook that contains inorganic particulate and organic binder bond on the bearing film, should retrain and stripped down from bearing film with raw cook, make described constraint with contacting of raw cook with described bearing film the face of a side and described not sintered multilayer ceramic substrate top and/or below connect airtight.
Described restraint layer is preferably made the above thickness of 50 μ m.Preferably utilize coating to form first restraint layer of thickness more than 10 μ m in addition, overlap described constraint thereon and as second restraint layer, amount to and form the above restraint layer of 50 μ m with raw cook.
Preferably make described not sintered multilayer ceramic substrate down with the state that can utilize slot segmentation to be divided into the assembly substrate of a plurality of substrate chip, described assembly substrate comprise above the outer electrode and/or below on described restraint layer is set.
E-machine of the present invention can obtain by described multilayer ceramic substrate is carried out mounted on surface on circuit substrate.
According to the present invention, the inorganic particulate that can make restraint layer can be suppressed at shrinkage in the face 1% with interior (deviation is in ± 0.1%) to having the appropriate restraining force of not sintered multilayer ceramic substrate performance of outer electrode.Because the residual inorganic particulate that has pair plated film can not produce dysgenic degree in fact on the electrode externally, so the anti-scolder aggressivity or the intensity of electrode are enhanced.
Description of drawings
Fig. 1 is the profile that expression forms the not sintered multilayer ceramic substrate of the preceding assembly substrate shape of restraint layer.
Fig. 2 is the top stereogram of the not sintered multilayer ceramic substrate of presentation graphs 1.
Fig. 3 is the profile that expression has formed the not sintered multilayer ceramic substrate behind the restraint layer.
Fig. 4 is illustrated in the profile that has carried the module of chip parts such as semiconductor element on the multilayer ceramic substrate of the present invention.
Fig. 5 is the profile of an example that expression has the multilayer ceramic substrate of cavity.
Fig. 6 (a) is the flow chart of an example of the manufacturing process of expression multilayer ceramic substrate of the present invention.
Fig. 6 (b) is the flow chart of another example of the manufacturing process of expression multilayer ceramic substrate of the present invention.
Fig. 6 (c) is the flow chart of another example of the manufacturing process of expression multilayer ceramic substrate of the present invention.
Fig. 7 is the chart that the state x-ray diffractogram of powder down of mixed powder, calcining powder and the sintered body of expression low-temperature sintered ceramics material is composed.
Fig. 8 (a) is the scanning electron microscope photo of the calcined body of low-temperature sintered ceramics material.
Fig. 8 (b) is by the calcined body of low-temperature sintered ceramics material being pulverized the scanning electron microscope photo of the powder that gets.
Fig. 9 (a) be illustrated in 850 ℃ of following sintering the chart of X ray diffracting spectrum of multilayer ceramic substrate.
Fig. 9 (b) be illustrated in 860 ℃ of following sintering the chart of X ray diffracting spectrum of multilayer ceramic substrate.
Fig. 9 (c) be illustrated in 875 ℃ of following sintering the chart of X ray diffracting spectrum of multilayer ceramic substrate.
Figure 10 is the block diagram of a particle of the purposes of the expression high-frequency unit that used multilayer ceramic substrate of the present invention.
Figure 11 is the approximate three-dimensional map of main printed base plate that the portable phone of the high-frequency unit that has used multilayer ceramic substrate of the present invention has been carried in expression.
Embodiment
[1] multilayer ceramic substrate
Multilayer ceramic substrate of the present invention obtains by following operation, promptly, will contain ceramic material can carry out the low sintering substrate not sintered multilayer ceramic substrate stacked with raw cook at least above, form outer electrode, will with under the sintering temperature of sintered multilayer ceramic substrate not the inorganic particulate of sintering be main component restraint layer, with the top of described not sintered multilayer ceramic substrate and/or below with connecting airtight setting form incorporate laminated body, after with described laminated body sintering, remove described restraint layer.Like this, in the face of multilayer ceramic substrate of the present invention shrinkage just 1% with interior (deviation is in 0.1%), to residuing in the inorganic particulate on the outer electrode, constitute the ratio of the metal of described inorganic particulate, below 20 quality % with respect to the total amount of the metal of metal that constitutes described outer electrode and the described inorganic particulate of formation.
Utilization can be carried out the calcining of low sintering ceramic material (below be called " low-temperature sintered ceramics material "), Al
2O
3And TiO
2Composition vitrifying in addition.Some Al
2O
3And TiO
2Just can enter glass.In order to realize with SiO
2Be the uniform vitrifying of main component, need be with the composition fusion under the firing temperature more than 1300 ℃.The residual SiO of having in the calcined body that under 700 ℃～850 ℃, obtains
2Phase, the glassy phase deviation is even.The micro mist flour of the calcined body that is made of ceramic particle and glassy phase has ceramic particle by partly or integrally by glass-faced tissue.When comparing with the low-temperature sintered ceramics material in the past that mixture by glass particle that utilizes the fusion method manufacturing and ceramic particle constitutes, the vitrifying of the glass among the present invention in the employed calcined body powder is insufficient, is in the state that is difficult to flow.When using this kind calcined body powder, glass ingredient is reactive low when formal sintering, is in the state of inertia and high viscosity at the interface upper glass composition of sintered multilayer ceramic substrate and restraint layer not.Promptly, when the sintering behavior of the not sintered multilayer ceramic substrate that constitutes with mixture relatively the time by glass particle and ceramic particle, in the not sintered multilayer ceramic substrate that is made of the micro mist flour of calcined body, the flowability of glass ingredient is suppressed, and is in to be difficult to the state that oozes out to the surface.So, glass ingredient just can outer electrode attached to multilayer ceramic substrate on.In addition, utilize the reduction of the flowability of glass ingredient, can prevent that also inorganic particulates such as aluminium oxide are imbedded in not in the sintered multilayer ceramic substrate.
In the glass-ceramic raw cook that constitutes by the mixture of glass powder and ceramic powders, though if the tendency that separation just is difficult to densification between the glass powder is arranged, but because in the micro mist flour of calcined body, ceramic particle is by glass part ground or covering integrally, therefore the contact between the glass is tight, even also can densification under the sintering temperature of slightly giving softening flowability.
In the manufacture method of the present invention,, also can utilize low-temperature sintering and densification although employed low-temperature sintered ceramics material does not contain Pb and B in the making of described substrate with raw cook.Bi, Na, K and Co in the middle of the auxiliary element play a role as sintering aid, thereby can obtain sintering and the high dielectric property of Q value under the lower temperature.Cu, Mn and Ag have the crystallization facilitation, can realize low-temperature sintering.Utilize the sintering under the low temperature more, the fusion of glass ingredient is suppressed.
Strontium feldspar (the SrAl that Ca that the tissue of the multilayer ceramic substrate behind the sintering comprises the anorthite crystal has been replaced by Sr
2Si
2O
8).Have based on strontium feldspar and Al
2O
3Crystal has good mechanical strength with the ceramic substrate of the tissue that island exists.In addition, when the strontium feldspar was hexagonal crystal, substrate intensity further improved.This is considered to because this kind tissue has used described low-temperature sintered ceramics material.Even in no contraction process, by about sintering more than 850 ℃, the crystal of strontium feldspar also can be separated out from the glassy phase of the calcined body that constitutes raw cook.Like this, it is big that the apparant viscosity of glassy phase becomes, and the mobile of glass ingredient is suppressed.
The average grain diameter that preferably constitutes the inorganic particulate of restraint layer is more than the 0.3 μ m, and is 0.3～4 times of average grain diameter of the powder of low-temperature sintered ceramics material.For example, when substrate was made as about 1～3 μ m with raw cook with the average grain diameter of powder, the average grain diameter of inorganic particulate just was made as 0.3～4 μ m.Like this, just remove the inorganic particulates such as aluminium oxide that remain in external electrode surface easily.The inorganic particulate of minimal residue can be to the substantial influence of plated film generation, on the contrary scolder corrode or the improving of pole strength aspect demonstrate effect.
When the average grain diameter of the powder of ceramic material less than 1 μ m, during particularly less than 0.6 μ m, then be difficult to carry out the shaping of substrate with raw cook, in addition, when surpassing 3 μ m, then be difficult to make being as thin as the following substrate raw cook of 20 μ m.In addition, for the situation of using chippy micro mist flour after with the low-temperature sintered ceramics calcined material, described relation is also set up.The average grain diameter of calcined body comminuted powder is 1～3 μ m more preferably, most preferably 1～1.5 μ m.
The average grain diameter of the inorganic particulate of using when restraint layer is during less than 0.3 μ m, then in order to obtain necessary viscosity under the situation of printing, binder amount is with regard to become too much (filling rate of inorganic particulate becomes too small), the restraining force that can't bring into play equalization with the par and the slot segmentation both sides of raw cook to substrate.On the other hand, when the average grain diameter of inorganic particulate surpasses 4 μ m, then special faint in the restraining force of slot segmentation.The preferred average grain diameter of inorganic particulate is 0.5～2 μ m.
When the thickness of restraint layer is 50 μ m when above, be suppressed at below 1% owing to substrate can be shunk with the sintering of the X-Y plane of raw cook, therefore preferably.When the thickness of restraint layer during, restraining force deficiency, be difficult to suppress substrate and shrink with the sintering of the X-Y plane of raw cook less than 50 μ m.For the situation of printing, when the thickness of restraint layer surpasses 500 μ m, then produce the crack.So when utilizing printing to form restraint layer, the preferred thickness of restraint layer is 50 μ m～500 μ m.On the other hand, when using raw cook shape restraint layer, the upper limit of the thickness of restraint layer is not particularly limited.
In inorganic particulates such as aluminium oxide, contain organic binder bond when utilizing, and the inorganic compositions that has added plasticizer, dispersant and solvent therein is when making restraint layer, be preferably in the constraint raw cook of the given thickness of formation on the bearing film, make constraint with the bearing film contact-making surface of raw cook and sintered multilayer ceramic substrate not comprise the top of outer electrode and/or below overlap with connecting airtight.At this moment, because inorganic particulate and the substrate degree of fixation appropriateness of raw cook, so restraint layer is just removed fully behind the sintering.
Restraint layer constraint substrate can be controlled by the surface state of the thickness of restraint layer, the material that constitutes the inorganic particulate of restraint layer, particle diameter, particle size distribution and content and restraint layer etc. with the power of raw cook.
Among the present invention in the employed low-temperature sintered ceramics material, SiO
2, SrO and auxiliary element generation vitrifying.A certain amount of Al
2O
3And TiO
2Can enter in the glass.But, under 700～850 ℃ calcining heat, because described glass ingredient incomplete fusion, so calcined body just is in incomplete glassy phase and ceramic component mixes the state that exists.And when calcining heat during less than 700 ℃, vitrifying is insufficient, in addition when surpassing 850 ℃, and the fine pulverizing of the calcined body difficulty that just becomes.When with the micro mist flour of this kind calcined body during at 800～1000 ℃ of following sintering, glass ingredient plays a role as sintering aids, with substrate raw cook densification, and and Al
2O
3Reaction and separate out SrAl
2Si
2O
8Crystal is given Q (1/tan δ) high dielectric property to substrate with raw cook.That is, sintered base plate has by the SrAl that separates out from glass ingredient
2Si
2O
8The tissue that the remainder of crystal, the alpha-alumina crystals that drops into as raw material, the remainder of glass ingredient constitute, glass ingredient does not soak into restraint layer basically.
Among Fig. 1, sintered multilayer ceramic substrate 10 is not that a plurality of substrates that will utilize pastel based on Ag to print internal electrode 2 are laminated with raw cook 8.The internal electrode 2 of each layer connects by the perforated electrodes 3 of having filled conductor in the through hole on being located at raw cook 8.On (and the side that comprises as required), be formed with outer electrode 4 below on substrate 10, reaching.Though in being connected of boarded parts and circuit substrate the situation that side electrode is set is arranged also, with below the perforated electrodes 3 guiding substrates 10, the BGA or the LGA that carry out connecting with the ball bonding material connect recently.In any case, the outer electrode 4 as input and output terminal that need below substrate 10, be formed for being connected with grounding electrode or circuit substrate.On substrate 10, as shown in Figure 4, form as the outer electrode 4 of island (land) electrode that chip parts such as chip capacitor 7a, PIN diode 7b, semiconductor element 7c and internal electrode 2 are electrically connected or as the outer electrode 4 of the distribution that is used for being connected with other element.
Because 1 multilayer ceramic substrate is at most several microns square sizes, therefore as a rule, form the square large-scale assembly substrate in 100～200mm left and right sides that a plurality of multilayer ceramic substrates are had as chip, in final operation, be divided into each chip.So the situation that is called " multilayer ceramic substrate " in this specification not only comprises each multilayer ceramic substrate, also comprise the assembly substrate before cutting apart.
Not sintered multilayer ceramic substrate 10 as shown in Figure 3, in the above and/or following formed restraint layer 6,6 after, sintering is removed restraint layer.Chip part such as lift-launch PIN diode 7b or chip capacitor 7a on multilayer ceramic substrate, constituted module substrate 1 after, be divided into each multilayer ceramic substrate along slot segmentation 5.Module substrate 1 is installed on the circuit substrate with other electronic unit, uses this circuit substrate to constitute e-machines such as portable phone.
Fig. 5 represents to have the multilayer ceramic substrate 21 of cavity 20.Though substrate 21 also is that a plurality of raw cooks 28 are laminated, and is formed with the cavity 20 that is used for semiconductor element mounted thereon 7c on top.On each raw cook 28, be printed with internal electrode 22, connect by perforated electrodes 23.On substrate 21 and below be formed with that chip part carries the outer electrode 24 of usefulness or as the outer electrode 25 of input and output terminal.Externally electrode 24,25 around suitably be formed for preventing the cover layer 31 that flows of scolder.In cavity 20, be formed with the electrode 26 that mounting semiconductor element is used, use soldering paste 32 7c such as semiconductor element mounted thereon such as grade thereon.Connected by bonding wire 27 between the input and output electrode of this semiconductor element 7c and the terminal electrode 25.Form the passage of heat (thermalvias) 35 of extending in the bottom surface of cavity 20, be connected with the rear terminal 36 of substrate to the rear side of substrate.Rear terminal 36 be used for substrate 21 self to other more massive installation base plate for example with the inside of carried terminal etc. as the main first-class installation of PCB substrate that constitutes, the splicing ear of electrical connection, by with approximate clathrate configuration.And, to the outer electrode at the table back side that is formed at laminated base plate 21, implement plating Ni, plating Au etc. at last.
[2] manufacture method of multilayer ceramic substrate
(A) the substrate material of raw cook
The formation substrate for example is that as main component, the state with oxide contains with Al respectively with the composition of the low-temperature sintered ceramics material of raw cook
2O
3Be scaled the Al of 10～60 quality %, with SiO
2Be scaled 25～60 quality % Si, with SrO be scaled 7.5～50 quality % Sr and with TiO
2The Ti that is scaled 0～20 quality % is (wherein, with Al
2O
3, SiO
2, SrO and TiO
2Total amount be made as 100 quality %).The low-temperature sintered ceramics material, also can contain with Bi as auxiliary element with respect to the main component of per 100 mass parts
2O
3Be scaled the Bi of 0.1～10 mass parts.For the situation about forming that only is made of main component, substrate is sintered in the temperature below 1000 ℃ with raw cook.In addition, for the situation of the composition that also contains auxiliary element, even substrate also can be sintered in the temperature below 900 ℃ with raw cook.Like this, just the metal of high conductivity of silver, copper and gold and so on can be used with conductor as electrode, with substrate with raw cook and integrated ground of electrode sintering.
Auxiliary element is preferably with respect to 100 mass parts main components, contains from by with Bi
2O
3Be scaled the Bi of 0.1～10 mass parts, with Na
2O is scaled the Na of 0.1～5 mass parts, with K
2O is scaled the K of 0.1～5 mass parts and is scaled select in one group that the Co of 0.1～5 mass parts constitutes at least a with CoO.These auxiliary elements have make utilize calcining and the effect that reduces of the softening point of glass, can obtain the ceramic material of sintering under low temperature more.In addition, can make under the sintering temperature below 1000 ℃ and to obtain the high dielectric property of Q.
In addition, auxiliary element is with respect to 100 mass parts main components, contain from by be scaled the Cu of 0.01～5 mass parts with CuO, with MnO
2Be scaled select in one group that the Ag of the Mn of 0.01～5 mass parts and 0.01～5 mass parts constitutes at least a.Therefore these auxiliary elements add in order to realize low-temperature sintering owing to mainly have the effect that promotes crystallization in sintering circuit.
(1) Al:10～60 mass parts are (with Al
2O
3Convert)
When Al with Al
2O
3Conversion is during more than 60 quality %, because sintered density can not rise fully in the low-temperature sintering below 1000 ℃, so substrate becomes porous matter, and can't obtain good characteristic because of moisture absorption etc.In addition, when Al with Al
2O
3Conversion is during less than 10 quality %, and substrate does not have good high strength.The preferred content of Al is that 40～55 quality % are (with Al
2O
3Convert).
(2) Si:25～60 quality % are (with SiO
2Convert)
When Si with SiO
2Conversion is less than 25 quality % or when surpassing 60 quality %, then since in the low-temperature sintering below 1000 ℃ sintered density can not rise fully, so ceramic substrate becomes porous matter.The preferred content of Si is that 31～45 quality % are (with SiO
2Convert).
(3) Sr:7.5～50 quality % (converting) with SrO
When Sr converted less than 7.5 quality % with SrO or surpasses 50 quality %, then owing to sintered density in the low-temperature sintering below 1000 ℃ can not rise fully, so ceramic substrate became porous matter.The preferred content of Sr is 7.5～17.5 quality % (converting with SrO).
(4) Ti:0～20 quality % are (with TiO
2Convert)
When Ti with TiO
2Conversion is during more than 20 quality %, then since in the low-temperature sintering below 1000 ℃ sintered density can not rise fully, so substrate becomes porous matter.In addition, the temperature coefficient of the resonance frequency of pottery also content increase and the change along with Ti is big, can't obtain good characteristic.The temperature coefficient τ f of resonance frequency that does not contain the pottery of Ti is-20～-40ppm/ ℃, but along with the cooperation quantitative change of Ti is many, τ f increases.So, the use level of utilizing Ti with τ f be adjusted into 0ppm/ ℃ very easy.The preferred content of Ti is that 0～10 quality % is (with TiO
2Convert).
(5) Bi:0.1～10 mass parts
Bi has makes the softening point of the glass that utilizes the calcination process generation reduce the effect that sintering temperature is reduced.Bi can also make and obtain the high dielectric property of Q under the sintering temperature below 1000 ℃.But, when with Bi
2O
3During more than 10 mass parts, then the Q value diminishes conversion Bi with respect to 100 mass parts main components.Thus, below preferred 10 mass parts of Bi, more preferably below 5 mass parts.On the other hand, when Bi is less than 0.1 mass parts, then there is not the effect of low-temperature sinteringization in fact.So, more than preferred 0.1 mass parts of Bi, more preferably more than 0.2 mass parts.
(6) Na, K and Co:0.1～5 mass parts
When Na, K and Co with respect to 100 mass parts main components, respectively with Na
2O, K
2When O and CoO converted less than 0.1 mass parts, then the reduction effect of the softening point of glass was insufficient.On the other hand, when surpassing 5 mass parts separately, then dielectric absorption becomes excessive.Thus, all preferred 0.1～5 mass parts of Na, K and Co.
(7) Cu and Mn:0.01～5 mass parts
Cu and Mn have the crystallization that promotes ceramic dielectric in sintering circuit, realize low sintering effect.As Cu and Mn all less than 0.01 mass parts (with CuO or MnO
2Convert) time, because additive effect is insufficient, therefore just can't in the sintering below 900 ℃, obtain the high substrate of Q value.In addition, when surpassing 5 mass parts, then low-temperature sintering is compromised.So, preferred 0.01～5 mass parts of Cu and Mn.
(8) Ag:0.01～5 mass parts
Ag has softening point that reduces glass and the effect that promotes crystallization, can realize low-temperature sintering.But when Ag was 0.01 mass parts, then additive effect was insufficient.On the other hand, when surpassing 5 mass parts, then dielectric absorption becomes excessive.Thus, preferred 0.01～5 mass parts of Ag.Ag is more preferably below 2 mass parts.
(9) Zr:0.01～2 mass parts
In addition, when with ZrO
2When conversion contained the Zr of 0.01～2 mass parts, then the mechanical strength of substrate improved.
(10) Pb and B
Employed low-temperature sintered ceramics material does not contain Pb and the B that contains among the present invention in material in the past.Because PbO is a harmful substance, therefore in the processing of the discarded object that contains PbO, to spend many expenses, in addition, also need very careful in the processing of the PbO in production process.In addition, B
2O
3Have and in manufacturing process, be dissolved in water and the alcohol, segregation when drying, or when sintering and the electrode material reaction, or make the problems such as degradation of binding agent with the organic binder bond reaction.Therefore employed low-temperature sintered ceramics material among the present invention is favourable aspect environment owing to do not contain the harmful element of this kind.
(B) the substrate making of raw cook
The powder of described main component and auxiliary element is carried out wet mixed in ball mill.And after making water evaporates, with its fragmentation, 700～850 ℃ of calcinings down with the slip heat drying of gained.Preferred 1～3 hour of calcination time.Calcined body is dropped into ball mill, case of wet attrition 10～40 hours, forming average grain diameter is the micro mist of 0.6～2 μ m.Calcined body micro mist flour is that ceramic particle is partly or integrally by glass-faced particle.
Organic binder bond is suitably selected for the intensity of adjusting raw cook, perforate, crimping, dimensional stability etc.Preferred organic binder bond for example is polyvinyl butyral resin and polymethacrylate resin.The addition of organic binder bond is more than the 5 quality % of raw cook integral body, preferred 10～20 quality %.
Preferably add BPBG (BPBG), two-n-butyl phthalate etc. as plasticizer, in addition, preferably add ethanol, butanols, toluene, isopropyl alcohol etc. as solvent.By these raw materials are mixed with ball mill, make the slip of calcined body micro mist flour.In order to improve the uniformity of slip, add dispersant as required, then also very effective.
With slip deaeration under reduced pressure, and solvent is partly evaporated and after having adjusted viscosity, utilize and scrape the skill in using a kitchen knife in cookery shape of on bearing film, laminating.As bearing film, consider mechanical intensity, surface smoothing etc., the film of preferred PETG (PET).The substrate of gained is cut to given size with raw cook according to bearing film.
(C) the not making of sintered multilayer ceramic substrate
Described substrate fully after the drying, is being provided with perforation with raw cook, is that the conductor pastel of main body is filled perforation in order to Ag, uses the conductor pastel printing internal electrode pattern 2 as main body with Ag then.On lay respectively at and below substrate with on the raw cook formation outer electrode 4 pattern.After using raw cook stacked these substrates, carry out thermo-compressed.Though in general the thickness of raw chip laminating body preferably be made as 1.0～2.0mm by the module decision as object.
The temperature that the thermo-compressed condition optimization is 50～95 ℃ and 50～200kg/cm
2(4.9～19.6MPa) pressure.The pattern of outer electrode 4 also can form after thermo-compressed.Thereafter, as shown in Figure 2, according to the size formation slot segmentation 5 of substrate chip 1A～4A, 1B～4B, 1C～4C (whole symbols is all not shown).When forming slot segmentation 5, the inorganic paste of restraint layer also enters in the groove, and it is big that restraining force becomes.
(D) the constraint making of pastel
The average grain diameter Dc of inorganic particulate preferably is adjusted into and constitutes substrate 0.3～4 times with the average grain diameter Ds of the powder of the ceramic material of raw cook or calcined body micro mist.Particularly in order to prevent that inorganic particulate from remaining on the outer electrode of sintered multilayer ceramic substrate not, the average grain diameter Dc of inorganic particulate is preferably more than the average grain diameter Ds of ceramic powders or calcined body micro mist.Specifically, Dc/Ds is preferred 1～4, and more preferably 1.5～4.
The selected condition of the organic binder bond in the restraint layer is stricter with the situation of raw cook unlike substrate, and its addition also can be less in addition.Fiber-like resin that the preferred pyrolytic of organic binder bond is good or polymethacrylate resin etc.In addition, as the preferred BPBG of plasticizer (BPBG), two-n-butyl phthalate etc.As solvent, the alcohols of preferred alcohol, butanols, isopropyl alcohol and terpinol and so on.When utilizing printing to form restraint layer, in order to ensure the connecting airtight property between the powder in necessary viscosity and the pastel in the printing and with the connecting airtight property of substrate, preferred 1.5～4 quality % of the addition of organic binder bond.
(E) the constraint making of raw cook
When using raw cooks, utilize and scrape the skill in using a kitchen knife in cookery and on bearing film, form the thin slice that has added the inorganic compositions of the organic binder bond of 8～15 weight portions and solvent with respect to inorganic particulate 100 weight portions as restraint layer 6.Also can add plasticizer and a spot of dispersant of 4～8 weight portions.Inorganic particulate, organic binder bond, plasticizer and solvent are mixed with ball mill, make the constraint slip.
With slip deaeration under reduced pressure, solvent is partly evaporated and after having adjusted viscosity, utilize and scrape the skill in using a kitchen knife in cookery shape of on bearing film, laminating.The constraint of gained is cut to given size with raw cook according to bearing film.
(F) formation of restraint layer on sintered multilayer ceramic substrate not
Not above the sintered multilayer ceramic substrate 10 and/or below during formation restraint layer 6, (a) described inorganic compositions pastel be not printed as desired thickness (printing repeatedly as required and drying) on the sintered multilayer ceramic substrate, or (b) from inorganic compositions, make the constraint raw cook of desired thickness in advance, make it to overlap with sintered multilayer ceramic substrate not, or (c) on the restraint layer after the printing, overlap constraint and use raw cook, or (d) they are made up.
The thickness of restraint layer is more than the 50 μ m on the single face of sintered multilayer ceramic substrate not.When the thickness of restraint layer during less than 50 μ m, restraining force is insufficient, and the sintering that can't suppress fully in the X-Y plane of sintered multilayer ceramic substrate not shrinks.When restraint layer when 50 μ m are above, just the sintering of the X-Y plane of sintered multilayer ceramic substrate not can be shunk and be suppressed at below 1%.When using raw cook,, when the printing restraint layer, in surpassing the printed layers of 500 μ m thickness, can crack though on the upper limit of thickness, be not particularly limited as restraint layer.So for utilizing printing to form the situation of restraint layer, suitable thickness is 50 μ m～500 μ m.
When using constraint use raw cook, according to making and the contact-making surface of bearing film and the surface of the sintered multilayer ceramic substrate mode of connecting airtight not, stacked, be crimped on sintered multilayer ceramic substrate not comprise the top of outer electrode and/or below.When making with the contact-making surface of bearing film and the sintered multilayer ceramic substrate does not connect airtight, removing of the restraint layer behind the sintering is just very easy.Its reason is inferred as follows.That is, with the contact-making surface of bearing film on, concentrating has constraint with the binding agent in the raw cook.Thus, with the contact-making surface of bearing film on restraining force to sintered multilayer ceramic substrate not very big, and the situation that inorganic particulate anchors on the sintered multilayer ceramic substrate is not relaxed (cushioning effect).So,, will when keeping restraining force fully, behind sintering, easily remove inorganic particulate when making constraint with raw cook and contact-making surface bearing film and when does not connect airtight on the surface of sintered multilayer ceramic substrate.
Though constraint does not have theoretic restriction with raw cook on thickness, when utilizing printing to make thicker restraint layer, in practicality, need more printing drying process.But the pastel of employed high fluidity enters the recess of the slot segmentation etc. of sintered multilayer ceramic substrate not in the print process, obtains higher binding effect.So, preferably utilize print process to form first restraint layer of thickness to a certain degree, thereon as the raw cook of the overlapping required thickness of second restraint layer.At this moment, preferably utilize printing to form the first above restraint layer of thickness 10 μ m, form second restraint layer by overlapping constraint with raw cook thereon, add up to form the above restraint layer of 50 μ m.
To retrain with the raw cook thermo-compressed on sintered multilayer ceramic substrate not.Constraint is 50～90 ℃ temperature and 50～200kg/cm with the condition of the thermo-compressed of raw cook on sintered multilayer ceramic substrate not
2(4.9～19.6MPa) pressure.
(G) possessed the sintering of the not sintered multilayer ceramic substrate of restraint layer
After having carried out taking off binding agent,, carry out sintering 400～650 ℃ of maintenances 2～10 hours by keeping 1～4 hour at 800～1000 ℃.When sintering temperature during less than 800 ℃, even prolong sintering time, also be difficult to realize the densification of substrate, in addition, and when surpassing 1000 ℃, the formation of the Ag class electrode material difficulty that becomes then, the multilayer ceramic substrate that can't obtain to have desirable dielectric property in addition.
(H) restraint layer removes
Behind the sintering, will remove attached to the aluminium oxide particles on the surface of multilayer ceramic substrate (particularly outer electrode).This is by the multilayer ceramic substrate behind the sintering being put into the water of ultrasonic cleaner, being applied ultrasonic wave and carry out.Though utilize ultrasonic waves for cleaning can remove most aluminium oxide particles, the aluminium oxide particles on the outer electrode (for example Ag pad) can't utilize ultrasonic waves for cleaning to remove fully.Thus, as required, utilize the blasting treatment of the impact that is controlled to be the degree that can not damage outer electrode that aluminium oxide particles is removed.As sand material, can use aluminium oxide, glass, zircon, resin particle etc.And after ultrasonic waves for cleaning, even what residually have an aluminium oxide particles, plated film is also relatively better.Particularly when moderately residual when aluminium oxide particles is arranged, the anti-scolder aggressivity of the outer electrode of being made by Ag improves.
(I) lift-launch of parts and assembly substrate cuts apart
Utilize the electroless plating embrane method to form Ni plated film and Au plated film etc. on the Ag pad of aluminium oxide particles having removed.On the outer electrode that Ni and Au have been metallized with scolder pattern screen printing after, parts such as semiconductor element mounted thereon, utilizing refluxes connects.For the situation of wire-bonded, engage connection at the laggard line lead of reflow treatment with semiconductor element.At last, by assembly substrate is cut off along slot segmentation, just obtain each multilayer ceramic substrate.
The manufacturing process of the multilayer ceramic substrate when Fig. 6 (a) expression forms restraint layer by the inorganic particulate pastel is printed on the sintered multilayer ceramic substrate not, Fig. 6 (b) expression will be by retraining the manufacturing process that is layered in the multilayer ceramic substrate when forming restraint layer on the sintered multilayer ceramic substrate not with raw cook, Fig. 6 (c) is illustrated in and the inorganic particulate pastel is printed on not on the sintered multilayer ceramic substrate and after having formed first restraint layer, by retraining the manufacturing process that is layered in the multilayer ceramic substrate when forming second restraint layer on the sintered multilayer ceramic substrate not with raw cook.
Though the present invention utilizes following embodiment to illustrate that in more detail the present invention is not limited to these embodiment.
Use the Al of purity 99.9% and average grain diameter 0.5 μ m
2O
3Powder, purity reach the following SiO of average grain diameter 0.5 μ m more than 99.9%
2The SrCO of powder, purity 99.9% and average grain diameter 0.5 μ m
3The TiO of powder, purity 99.9% and average grain diameter 0.5 μ m
2Powder and be respectively purity 99.9% and average grain diameter is the Bi of 0.5～5 μ m
2O
3Powder, Na
2CO
3Powder, K
2CO
3Powder, CuO powder, Ag powder, MnO
2Powder and Co
3O
4Powder has been made the low-temperature sintered ceramics material of the composition shown in the table 1.In sample No., do not have
*Mark be sample in the scope of the present invention, have
*Mark be extraneous sample of the present invention (following identical).
(B) the substrate making of raw cook
The mixed-powder that will have the composition shown in the table 1 drops in the polyethylene system ball mill, and then with the medium ball and the pure water input of zirconia system, carries out 20 hours wet mixed.Slip to gained has carried out behind the heat drying, with mortar (the ラ イ カ イ) crusher machine of automation, puts into oxidation aluminum crucible, calcines 2 hours down at 800 ℃.The calcined body of gained is dropped in the described ball mill, in case of wet attrition dry after 17 hours, obtained the micro mist of average grain diameter 1 μ m.
In 100 weight portion calcined body micro mists; add the polyvinyl butyral resin of 15 weight portions as organic binder bond; add the BPBG (BPBG) of 7.5 weight portions as plasticizer, and add ethanol as solvent, with the ball mill mixing manufacture slip.And dispersant does not add.
With slip deaeration under reduced pressure, and ethanol is partly evaporated, be adjusted into the viscosity of about 7Pas.The skill in using a kitchen knife in cookery shape of laminating is scraped in the slip utilization on PET system bearing film, drying has obtained the substrate raw cook of thickness 0.15mm.It is square that substrate is cut into 180mm with raw cook according to the carrying thin slice.
With substrate with raw cook fully after the drying, be that the conductor pastel of main body has formed internal electrode pattern and outer electrode pattern in order to Ag.With the substrate that formed electrode with raw cook piecewise at 60 ℃ temperature and 30kg/cm
2Interim crimping under the pressure (2.8MPa) is then at 85 ℃ temperature and 110kg/cm
2Thermo-compressed under the pressure (10.8MPa).The thickness of the not sintered multilayer ceramic substrate (assembly substrate) of gained is 1.3mm.
Blade is leaned on sintered multilayer ceramic substrate (assembly substrate) not, formed the slot segmentation 5 of section shape of isosceles triangle of the degree of depth of width with 0.15mm and 0.1mm with the interval of 10mm * 15mm.
Alumina powder 100 weight portions with respect to average grain diameter 0.5 μ m, with ball mill mix polyvinyl butyral resin as 10.2 weight portions of organic binder bond, as the BPBG and the ethanol of 6.2 weight portions of plasticizer, made the slip that does not add dispersant.With slip deaeration under reduced pressure, solvent is partly evaporated after, be adjusted into the viscosity of about 5Pas.Then, the skill in using a kitchen knife in cookery is scraped in this slip utilization make the shape of laminating on the bearing film, make it dry, obtained the constraint raw cook of thickness 0.15mm at PET.To retrain that to be cut into 180mm with raw cook according to the carrying thin slice square.
According to the mode that connect airtight on the surface that makes bearing film contact-making surface and assembly substrate, overlap constraint below on assembly substrate, reaching and use raw cook, at 85 ℃ temperature and 110kg/cm
2Thermo-compressed under the pressure (10.8MPa) has formed incorporate laminated body.
In the batch furnace of air atmosphere, laminated body after having carried out taking off binding agent, is warming up to 900 ℃ with 3 ℃/minute speed 500 ℃ of maintenances 4 hours, by under this temperature, keeping 2 hours and sintering natural cooling in stove.
From sintering laminated body utilize ultrasonic waves for cleaning to remove aluminium oxide particles.To the assembly substrate of gained, utilize following method to estimate the shrinkage in the X-Y plane and the state of deviation, compactness, high frequency characteristics and outer electrode thereof.Evaluation result is illustrated in the table 1.
(1) shrinkage in the X-Y plane
Select to form 8 small pieces of total (chip) portion of the central authorities that are in four jiaos and four limits in the middle of the assembly substrate before the restraint layer, utilize the three-dimensional coordinate detecting device to measure 2 the cornerwise X-directions of each small pieces portion and the distance of Y direction respectively, obtained X-Y coordinate figure X
0, Y
0Similarly to the assembly substrate behind the sintering, measure 2 the cornerwise X-directions of each small pieces portion and the distance of Y direction respectively, tried to achieve X-Y coordinate figure X
n, Y
nTo the average X of 8 small pieces portions (n=1～8)
n/ X
0Y when
n/ Y
0Ratio, as the sintering shrinkage that forms the assembly substrate of sintering behind the restraint layer.In addition, with these than deviation as the deviation of shrinkage.
(2) compactness
According to thickness (Z-direction) D with respect to the assembly substrate before the formation restraint layer
0Sintering after the thickness D of assembly substrate
1, obtain the sintering shrinkage (D of Z-direction
1/ D
0), the compactness of having utilized following benchmark evaluation.
D
1/ D
0Below 60%: good
D
1/ D
0Surpass 60%: bad
(3) high frequency characteristics
Under 2GHz, measure the dielectric loss angle tangent tan δ of the assembly substrate behind the sintering, the high frequency characteristics of having utilized following benchmark evaluation.
Tan δ is below 0.01: good
Tan δ surpasses 0.01: bad
(4) state of outer electrode (plated film)
To utilizing ultrasonic waves for cleaning to remove each sample of restraint layer behind the sintering, use commercially available electroless plating Ni liquid and plating Au liquid, implemented the plating Ni of average film thickness 5 μ m and the plating Au of average film thickness 0.4 μ m.Observe outer electrode behind the plated film with SEM, according to area occupation ratio attached to the plated film on the outer electrode, with following benchmark evaluation the state of outer electrode.
The area occupation ratio of plated film is 100%: excellent
The area occupation ratio of plated film is less than 100% and more than 90%: good
The area occupation ratio of plated film is less than 90%: bad
Table 1
| Sample No. | ??Al 2O 3 | ??SiO 2 | ??SrO | ??TiO 2 | ??Bi 2O 3 | ??Na 2O | ??K 2O | ??CoO | ??CuO | ??MnO 2 | ??Ag |
| ?? *1 | ??10 | ??50 | ??40 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- |
| ??2 | ??15 | ??50 | ??35 | ??- | ??2 | ??1 | ??0.5 | ??- | ??0.3 | ??- | ??0.5 |
| ??3 | ??20 | ??50 | ??30 | ??- | ??2 | ??1 | ??0.5 | ??- | ??0.3 | ??- | ??0.5 |
| ??4 | ??25 | ??35 | ??40 | ??- | ??3 | ??0.1 | ??- | ??- | ??- | ??- | ??- |
| ??5 | ??25 | ??35 | ??40 | ??- | ??1 | ??- | ??- | ??0.5 | ??- | ??- | ??- |
| ?? *6 | ??25 | ??35 | ??40 | ??- | ??0.2 | ??- | ??- | ??6 | ??- | ??- | ??- |
| ??7 | ??51.5 | ??31 | ??17.5 | ??- | ??2 | ??1 | ??0.5 | ??- | ??0.3 | ??- | ??0.5 |
| ?? *8 | ??51.5 | ??31 | ??17.5 | ??- | ??12 | ??1 | ??0.5 | ??- | ??0.3 | ??- | ??0.5 |
| ??9 | ??51.5 | ??31 | ??17.5 | ??- | ??3 | ??1 | ??0.5 | ??- | ??0.3 | ??- | ??- |
| ??10 | ??51.5 | ??31 | ??17.5 | ??- | ??3 | ??1.5 | ??0.5 | ??- | ??0.3 | ??- | ??- |
| ?? *11 | ??51.5 | ??31 | ??17.5 | ??- | ??3 | ??7 | ??0.5 | ??- | ??0.3 | ??- | ??0.5 |
| ??12 | ??51.5 | ??31 | ??17.5 | ??- | ??3 | ??1 | ??1 | ??- | ??0.3 | ??- | ??0.5 |
| ?? *13 | ??51.5 | ??31 | ??17.5 | ??- | ??3 | ??1 | ??7 | ??- | ??0.3 | ??- | ??0.5 |
| ??14 | ??51.5 | ??31 | ??17.5 | ??- | ??3 | ??1 | ??0.5 | ??- | ??0.5 | ??- | ??0.5 |
| ?? *15 | ??51.5 | ??31 | ??17.5 | ??- | ??3 | ??1 | ??0.5 | ??- | ??7 | ??- | ??0.5 |
| ??16 | ??55 | ??32.5 | ??12.5 | ??- | ??2 | ??1 | ??0.5 | ??- | ??0.3 | ??- | ??0.5 |
| ??17 | ??30 | ??45 | ??15 | ??10 | ??3 | ??1.5 | ??0.5 | ??- | ??0.5 | ??- | ??0.5 |
| ??18 | ??30 | ??45 | ??15 | ??10 | ??2 | ??1 | ??0.5 | ??- | ??0.3 | ??- | ??0.5 |
| ??19 | ??30 | ??45 | ??15 | ??10 | ??3 | ??1 | ??0.5 | ??- | ??0.5 | ??- | ??- |
| ?? *20 | ??35 | ??50 | ??5 | ??10 | ??3 | ??1.5 | ??0.5 | ??- | ??0.5 | ??- | ??- |
| ??21 | ??40 | ??35 | ??15 | ??10 | ??2 | ??1 | ??0.5 | ??- | ??0.3 | ??- | ??0.5 |
| ??22 | ??43.27 | ??38.46 | ??14.42 | ??3.85 | ??2 | ??2 | ??0.5 | ??- | ??0.3 | ??- | ??- |
| ??23 | ??43.27 | ??38.46 | ??14.42 | ??3.85 | ??2 | ??2 | ??0.5 | ??0.2 | ??0.3 | ??- | ??- |
| ??24 | ??43.27 | ??38.46 | ??14.42 | ??3.85 | ??2 | ??2 | ??0.5 | ??0.4 | ??0.3 | ??- | ??- |
| ??25 | ??43.27 | ??38.46 | ??14.42 | ??3.85 | ??2 | ??2 | ??0.5 | ??- | ??0.3 | ??0.2 | ??- |
| ??26 | ??43.27 | ??38.46 | ??14.42 | ??3.85 | ??2 | ??2 | ??0.5 | ??- | ??0.3 | ??0.4 | ??- |
| ??27 | ??48.08 | ??36.06 | ??12.02 | ??3.84 | ??2 | ??2 | ??0.5 | ??- | ??0.3 | ??- | ??- |
| ??28 | ??46 | ??38 | ??12 | ??4 | ??2.5 | ??2 | ??0.5 | ??- | ??0.3 | ??- | ??- |
| ??29 | ??48 | ??38 | ??10 | ??4 | ??2.5 | ??2 | ??0.5 | ??- | ??0.3 | ??0.5 | ??- |
| ??30 | ??50 | ??36 | ??10 | ??4 | ??2.5 | ??2 | ??0.5 | ??- | ??0.3 | ??0.5 | ??- |
| ??31 | ??50.5 | ??38 | ??7.5 | ??4 | ??2.5 | ??2 | ??0.5 | ??- | ??0.3 | ??0.5 | ??- |
| ??32 | ??48 | ??36 | ??12 | ??4 | ??2.5 | ??2 | ??0.5 | ??- | ??0.3 | ??- | ??0.5 |
| ??33 | ??48 | ??36 | ??12 | ??4 | ??2.5 | ??2 | ??0.5 | ??- | ??0.3 | ??0.5 | ??- |
| ??34 | ??50 | ??32.5 | ??12.5 | ??5 | ??2 | ??1 | ??0.5 | ??- | ??0.3 | ??- | ??0.5 |
Table 1 (continuing)
Annotate: (1) is with absolute value representation.
Can see that from table 1 sintering shrinkage in the X-Y plane of multilayer ceramic substrate of the present invention is below 1%, the deviation of sintering shrinkage is in ± 0.07%.In addition, for any one of the state of compactness, high frequency characteristics and outer electrode, multilayer ceramic substrate of the present invention all is good.
Use the Al of purity 99.9% and average grain diameter 0.5 μ m
2O
3Powder, purity reach the following SiO of average grain diameter 0.5 μ m more than 99.9%
2The SrCO of powder, purity 99.9% and average grain diameter 0.5 μ m
3Powder and respectively purity be 99.9% and average grain diameter be the Bi of 0.5～5 μ m
2O
3Powder, Na
2CO
3Powder, K
2CO
3Powder, CuO powder and MnO
2Powder has been made the low-temperature sintered ceramics material (the sample No.29 that is equivalent to table 1) of the auxiliary element that contains the main component that is made of Al, Si, Sr and Ti and be made of Bi, Na, K, Cu and Mn as follows.
Main component
% is (with Al for the Al:48 quality
2O
3Convert)
% is (with SiO for the Si:38 quality
2Convert)
Sr:10 quality % (converting) with SrO
% is (with TiO for the Ti:4 quality
2Convert)
Auxiliary element (with respect to 100 mass parts main components)
The Bi:2.5 mass parts is (with Bi
2O
3Convert)
The Na:2 mass parts is (with Na
2O converts)
The K:0.5 mass parts is (with K
2O converts)
Cu:0.3 mass parts (converting) with CuO
The Mn:0.5 mass parts is (with MnO
2Convert)
Identical with embodiment 1, calcine this low-temperature sintered ceramics material, be the average grain diameter of about 1 μ m and about 3 μ m with the fine respectively pulverizing of calcined body of gained, made the substrate raw cook.
Using average grain diameter is the aluminium oxide particles of 0.2～5 μ m, utilizes print process and/or raw cook method, forms the restraint layer of the thickness that adds up to 30～550 μ m.In the sample beyond the No.44, formed slot segmentation.The laminated body of being made by the not sintered multilayer ceramic substrate that is provided with restraint layer is sintering under the condition identical with embodiment 1 all.From sintering laminated body utilize ultrasonic waves for cleaning to remove the aluminium oxide particles of restraint layer, obtained assembly substrate.To each assembly substrate, estimate shrinkage and deviation and the plated film in the X-Y plane in the same manner with embodiment 1, utilized following method to estimate residual quantity and particle diameter, the warpage of substrate and the scolder erosion state of outer electrode of the aluminium oxide particles on the outer electrode in addition.Evaluation result is illustrated in the table 2.
(1) residual quantity of the aluminium oxide on the outer electrode
Utilize FE-SEM (S-4500 of Hitachi, accelerating voltage 15kV), the Ag-K α of external electrode surface and Al-K α are carried out EDX analyze impurity such as (except) oxygen, utilize the standardless method to try to achieve the quality % of Ag and Al from the peak intensity of Ag and Ag.Because the residual quantity of the quality % of Al and the aluminium oxide of electrode surface is proportional, therefore the residual quantity of aluminium oxide is used the quality %[Al/ (Al+Ag) * 100 (%) of Al] expression.
(2) number of aluminium oxide particles
Externally in the zone that has aluminium oxide particles in the FE-SEM photo of electrode surface (3000～5000 times), at random draw length and be equivalent to the straight line of 20 μ m, choose intersection aluminium oxide particles (be limited to have with restraint layer in the particle of the suitable particle diameter of the particle diameter of employed aluminium oxide particles) 2 more straight lines of number, obtained the mean value of the number of the aluminium oxide particles that has intersected with these straight lines.And evaporation carbon on each sample has carried out the EDX analysis under the accelerating voltage of 15kV.
(3) warpage
When measuring shrinkage, utilize the three-dimensional coordinate detecting device to try to achieve difference of height (Z-direction) between the diagonal of 1 small pieces portion arbitrarily of mensuration, as warpage.The feasible value of warpage is about 40 μ m.
(4) scolder erosion state
To remove each sample of restraint layer at the Sn that remains 245 ℃ with ultrasonic wave
3.5After having flooded 1 minute in the-Ag solder bath, the outer electrode that utilized observation by light microscope.According to the area occupation ratio of the metal on the outer electrode (scolder that Ag+ adheres to), the scolder erosion state of each sample that utilized following benchmark evaluation.
The area occupation ratio of the metal of outer electrode is more than 95%: excellent
The area occupation ratio of the metal of outer electrode is less than 95% and more than 85%: good
The area occupation ratio of the metal of outer electrode is less than 85%: bad
Table 2
Annotate: the ceramic particle of (1) substrate in the raw cook
(2) face of the restraint layer that connects airtight with the surface of sintered multilayer ceramic substrate not
(3) constraint with raw cook with the contact-making surface of PET film and not the sintered multilayer ceramic substrate connect airtight.
Table 2 (continuing)
Annotate: (1) is with absolute value representation
(2) restraint layer cracks after the printing drying
(3) a little less than the restraining force.
Used the mixed powder of glass powder and ceramic powders in raw cook at matrix.That is the Al in the middle of the material powder that will use with the low-temperature sintered ceramics material of embodiment 2 same compositions,
2O
3The mixture of the ceramic powders (oxide or carbonate) beyond the powder is put into alumina crucible, under 1400 ℃, carries out 2 hours heat treatment in electric furnace, has obtained transparent glass blocks.After this glass blocks is cut out with slicing machine, utilize disintegrating machine and ball mill to pulverize average grain diameter respectively into about 1 μ m and 3 μ m.Be about among the glass powder 52 quality % of 1 μ m in average grain diameter, mix alumina powder 48 quality %, organic binder bond, plasticizer and the solvent that average grain diameter is about 1 μ m, made the substrate raw cook by the slip of gained with ball mill.Similarly, by being about in average grain diameter in the glass powder of 3 μ m, mix the slip that alumina powder, organic binder bond, plasticizer and solvent that average grain diameter is about 3 μ m form, made the substrate raw cook.With embodiment 1 in the same manner, substrate with raw cook stacked and thermo-compressed, has been formed slot segmentation as required.
Use the aluminium oxide particles of average grain diameter 0.2～5 μ m, utilize print process and/or raw cook method, formed the restraint layer of the thickness that adds up to 30～550 μ m.Behind each laminated body sintering, utilize ultrasonic waves for cleaning to remove the aluminium oxide particles of restraint layer with gained.And the condition except described is identical with embodiment 1.
To each multilayer ceramic substrate of gained, shrinkage and deviation, the warpage of substrate, the scolder erosion state of outer electrode and the residual form of the aluminium oxide on plated film and the outer electrode in the X-Y plane of having used the condition evaluating identical with embodiment 1 and 2.Evaluation result is illustrated in the table 3.
Table 3
Annotate: the face of the restraint layer that connect airtight on (1) and the surface of sintered multilayer ceramic substrate not
(2) constraint with raw cook with the contact-making surface of PET film and not the sintered multilayer ceramic substrate connect airtight.
Table 3 (continuing)
Annotate: the ceramic particle of (1) substrate in the raw cook
Table 3 (continuing)
| Sample No. | Shrinkage (%) in the X-Y plane | Deviation (1)??(±％) | Warpage (μ m) | Scolder corrodes | Plated film |
| ??65 | ??0.6 | ??0.05 | ??17 | Excellent | Very |
| ??66 | ??0.5 | ??0.05 | ??16 | Excellent | Very |
| ??67 | ??0.6 | ??0.05 | ??20 | Excellent | Very |
| ??68 | ??0.5 | ??0.05 | ??16 | Excellent | Very |
| ??69 | ??0.5 | ??0.05 | ??16 | Excellent | Excellent |
| ??70 | ??0.7 | ??0.05 | ??18 | Excellent | Excellent |
| ??71 | ??1 | ??0.07 | ??23 | Excellent | Excellent |
| ??72 | ??0.6 | ??0.04 | ??17 | Excellent | Very |
| ??73 | ??0.5 | ??0.05 | ??16 | Excellent | Very |
| ??74 | ??0.5 | ??0.04 | ??16 | Excellent | Very |
| ??75 | ??0.5 | ??0.05 | ??16 | Excellent | Very |
| ??76 | ??0.6 | ??0.05 | ??16 | Excellent | Very |
| ??77 | ??0.8 | ??0.06 | ??19 | Excellent | Very |
| ??78 | ??0.6 | ??0.05 | ??17 | Excellent | Very |
| ??79 | ??0.5 | ??0.05 | ??16 | Excellent | Very |
| ??80 | ??0.5 | ??0.04 | ??14 | Excellent | Very |
| ??81 | ??0.5 | ??0.05 | ??16 | Excellent | Excellent |
| ??82 | ??0.5 | ??0.05 | ??16 | Excellent | Excellent |
| ??83 | ??0.6 | ??0.04 | ??14 | Excellent | Very |
| ??84 | ??0.5 | ??0.05 | ??16 | Excellent | Very |
| ??85 | ??0.5 | ??0.03 | ??13 | Excellent | Very |
| ??86 | ??0.5 | ??0.04 | ??15 | Excellent | Excellent |
| ??87 | ??0.5 | ??0.04 | ??15 | Excellent | Excellent |
| ?? *88 (2) | ??- | ??- | ??- | ??- | ??- |
| ?? *89 (3) | ??16 | ??0.34 | ??30 | Excellent | Excellent |
| ?? *90 (2) | ??- | ??- | ??- | ??- | ??- |
| ?? *91 (3) | ??14 | ??0.29 | ??35 | Excellent | Excellent |
| ??92 | ??1 | ??0.09 | ??22 | Excellent | Excellent |
| ??93 | ??0.6 | ??0.08 | ??20 | Excellent | Excellent |
Annotate: (1) is with absolute value representation.
(2) restraint layer cracks after the printing drying.
(3) a little less than the restraining force.
Can see from table 2 and table 3, the average grain diameter of the aluminium oxide particles of formation restraint layer is more than 0.3 μ m and be in substrate with in the sample in 0.3～4 times the scope of the average grain diameter of the ceramic particle of raw cook, shrinkage in the X-Y plane of the multilayer ceramic substrate behind the sintering 1% with interior (deviation is in ± 0.1%), in permissible range.In contrast, when having used the aluminium oxide particles of described extraneous average grain diameter, can't obtain enough restraining forces, can not suppress sintering and shrink, on multilayer ceramic substrate, see the generation of crackle.
In addition, in the sample in the scope of the present invention, the aluminium oxide particles that remains in external electrode surface is below the 20 quality % (Al benchmark), particularly below the 12 quality %, can not cause that also scolder corrodes, and plated film is also good.For the number of remaining aluminium oxide particles, in the sample in the scope of the present invention all in 10.In the time will being compared with raw cook with raw cook with by the substrate that the mixture of calcined body comminuted powder+glass dust flour is made by the substrate that the calcined body comminuted powder is made, generally speaking the former side's aluminium oxide is still less residual.
For the situation of the restraint layer that has printed,, find to have crackle to produce when its thickness below 50 μ m or when surpassing 500 μ m.In contrast, for the situation of the restraint layer that utilizes raw cook to form, owing to can guarantee thickness fully, therefore good aspect the reduction of shrinkage and warpage.Find that aluminium oxide surplus on electrode further reduce when being used as containment surfaces when the PET face side with the constraint raw cook this moment.If though there is not slot segmentation, all very good aspect shrinkage and warpage, in the method for the present invention, even having under the situation of slot segmentation, the deviation of shrinkage and warpage are also all very good.In addition, do not see all that in any one sample scolder corrodes.
For plated film, though sample No.35,36,55 and 59 good inadequately (the bad part of some plated films is arranged in the bight of electrode), electrode surface be formed with plated film more than 90%, thereby in fact do not have problem.
Even as the restraint layer ceramic particle, replace aluminium oxide particles, use at least a of magnesia particle, Zirconia particles, Titanium particles and mullite particle, also can obtain identical effect.In addition, even outer electrode is carried out blasting treatment, also can obtain identical result to be controlled to be abundant low impulsive force (for example projection pressure of 0.4MPa) according to the mode of not damaging outer electrode.
Crystalline phase to employed low temperature calcination ceramic material among the embodiment 2 is analyzed with X-ray diffraction method.Target adopts Cu, has used its K alpha ray in the diffraction x-ray source.With the x-ray diffractogram of powder spectral representation of mixed powder, calcining powder and sintered body in Fig. 7.Seen the crystalline phase of raw material in the mixed powder.Confirmed Al in the calcining powder
2O
3, TiO
2And SiO
2The existence of crystalline phase, and the existence of from 20 ° to 30 ° haloing pattern (hallow pattern), having confirmed glassy phase.In addition, in sintered body, confirm to have new SrAl
2Si
2O
8(strontium feldspar) separates out.Think that the influence reduction to electrode is suitable for not having contraction process owing to the effect of this kind tissue.
The scanning electron microscope photo of described calcined body and crushed material thereof is illustrated among Fig. 8.
In the calcined body shown in 8 (a), the particle of white is Al
2O
3, the part of black is a pore, continuous phase is glassy phase.Like this, in the calcined body, Al
2O
3Particle partly or is integrally covered by glassy phase.In the comminuted powder of the calcined body shown in Fig. 8 (b), Al
2O
3Particle also partly or is integrally covered by glassy phase.
In addition, in order to test the sintering under the low temperature, to respect to by with Al
2O
3Be scaled the Al of 49 quality %, with SiO
2Be scaled 34 quality % Si, with SrO be scaled the Sr of 8.2 quality %, with TiO
2Be scaled main component 100 mass parts of the Ti formation of 3 quality %, contain with Bi as auxiliary element
2O
3Be scaled the Bi of 2.5 mass parts, with Na
2O is scaled the Na of 2 mass parts, with K
2O be scaled 0.5 mass parts K, with CuO be scaled the Cu of 0.3 mass parts, with Mn
3O
4The composition that is scaled the Mn of 0.5 mass parts is calcined down at 800 ℃, utilizes and has made sample with described identical method.Among this embodiment, under 850 ℃, 860 ℃, 875 ℃, carried out 2 hours sintering respectively.For these samples, carried out utilizing the Alpha-ray X-ray diffraction of Cu-K to measure.Fig. 9 (a)～(c) represent 850 ℃, 860 ℃ and 875 ℃ following sintering respectively the X-ray diffraction intensity collection of illustrative plates of sample.Among the figure, white circle expression Al
2O
3Crystal, black triangle is represented hexagonal crystal SrAl
2Si
2O
8Crystal, white triangle is represented monoclinic crystal SrAl
2Si
2O
8Crystal.
During Fig. 9 (a) reaches (b), at Al
2O
3Crystal, TiO
2Crystal and SiO
2All confirmed hexagonal crystal SrAl in the crystal
2Si
2O
8Separating out of crystal.Along with firing temperature improves, monoclinic crystal SrAl
2Si
2O
8Crystal is separated out, and diffraction peak intensity also increases.Carried out the three-point bending result of experiment for these samples, with bending strength with hexagonal crystal SrAl
2Si
2O
8(b), (a) that the separating out of crystal increased, the order of (c) increase.Consider from the viewpoint of intensity, though hexagonal crystal SrAl
2Si
2O
8Separating out of crystal is desirable, but preferably suppresses monoclinic crystal SrAl
2Si
2O
8Separating out of crystal.
Use the Al of purity 99.9% and average grain diameter 0.5 μ m
2O
3Powder, purity reach the following SiO of average grain diameter 0.5 μ m more than 99.9%
2The SrCO of powder, purity 99.9% and average grain diameter 0.5 μ m
3The TiO of powder, purity 99.9% and average grain diameter 0.5 μ m
2Powder and be respectively purity 99.9% and average grain diameter is the Bi of 0.5～5 μ m
2O
3Powder, Na
2CO
3Powder, K
2CO
3Powder, CuO powder and MnO
2Powder is according to respect to by with Al
2O
3Be scaled the Al of 48 quality %, with SiO
2Be scaled 38 quality % Si, with SrO be scaled 10 quality % Sr and with TiO
2Be scaled main component 100 mass parts of the Ti formation of 4 quality %, feasible becoming as auxiliary element contains with Bi
2O
3Be scaled the Bi of 2.5 mass parts, with Na
2O is scaled the Na of 2 mass parts, with K
2O be scaled 0.5 mass parts K, with CuO be scaled 0.3 mass parts Cu and with MnO
2The mode that is scaled the composition (the sample No.29 that is equivalent to table 1) of the Mn of 0.5 mass parts is mixed.Use the ceramic mixture of gained, utilize the method identical, made the substrate raw cook of the thickness of 15 μ m, 50 μ m, 100 μ m and 200 μ m respectively with embodiment 1.Calcination condition is 800 ℃ * 2 hours, and the average grain diameter of calcined body comminuted powder is about 1 μ m.
Each substrate respectively is cut into the approximate square of 180mm with raw cook, on each raw cook of given thickness, forms perforation, and printed the high-frequency circuit pattern that filter, duplexer and channel-splitting filter are used.In the printing of high-frequency circuit pattern, used the electrode material as main body with Ag.Circuit block diagram is illustrated among Figure 10.To print 9 of the sheet lamination crimping of the given thickness of circuit pattern, the printing outer electrode is separated out slot segmentation in top and bottom, has made the incorporate assembly substrate that can be divided into a plurality of multilayer ceramic substrate chips.Each multilayer ceramic substrate chip is approximately the quadrangle of 8mm * 8mm, and the thickness before the sintering is about 1.3mm, and on the assembly substrate of about 180mm * 180mm, folder disposes 400 multilayer ceramic substrate chips every slot segmentation with clathrate.
Select sample No.51 from embodiment 2, the aluminium oxide restraint layer is printed on upper and lower surface, calcine in the same manner with embodiment 2, remove restraint layer, carry out coating film treatment, it is dry to clean the back.
Then, use metal mask, the given part printing on assembly substrate does not contain the soldering paste of Pb, carries chip part, has carried out the immersed solder operation in reflow ovens.In addition, carry semiconductor device, carried out connecting and sealing.Along slot segmentation assembly substrate is divided into each multilayer ceramic substrate at last.Shrinkage is 0.5% with interior (deviation is in ± 0.05%) in the face of the approximate foursquare assembly substrate of each 180mm, and the difference of height of thickness direction (Z-direction) is also little of 50 μ m.Thus, in operation, all do not have problems to the printing with paste of 400g multilayer ceramic substrate chip or component mounting.In contrast, in the method in the past, because the contraction of sintering causes the dimensional accuracy of substrate to reduce, therefore the number as the multilayer ceramic substrate chip that no problem product is selected in scolding tin or component mounting is few to about 250.
As shown in figure 11, the multilayer ceramic substrate 11,11 ' with the function with high frequency filter or duplexer of gained carries on the printed base plate 13 of portable phone.In addition, signal processing function or the submounts of circuit function or module or parts, the semiconductor device 12 etc. that will have other also carry on printed base plate 13, have implemented necessary connection.Multilayer ceramic substrate of the present invention is because the dimensional accuracy height, and quality is also stable, has therefore used the main printed base plate of its portable phone just can high-quality and the manufacturing of highly productive ground.
Claims (9)
1. the manufacture method of a multilayer ceramic substrate, it is characterized in that, have: (a) use the slip of the powder contain ceramic material and organic binder bond to make and to carry out low sintering substrate raw cook, (b) after described substrate has formed electrode on raw cook, stacked and make not sintered multilayer ceramic substrate, (c) forming under the sintering temperature contain at sintered multilayer ceramic substrate not the inorganic particulate of sintering and the constraint raw cook of organic binder bond on the bearing film, should retrain and strip down from bearing film with raw cook, make described constraint with contacting of raw cook with described bearing film the face of a side and described not sintered multilayer ceramic substrate top and/or below be provided with connecting airtight, make the incorporate laminated body that possesses restraint layer, (d) the described laminated body of sintering, (e) with described restraint layer from sintering the surface of the described laminated body operation of removing, the average grain diameter of wherein said inorganic particulate is 0.3～4 times of the average grain diameter of the powder of described ceramic material more than 0.3 μ m.
2. the manufacture method of multilayer ceramic substrate according to claim 1 is characterized in that, described restraint layer is made thickness more than the 50 μ m.
3. the manufacture method of multilayer ceramic substrate according to claim 1, it is characterized in that, for described restraint layer, utilize coating to form first restraint layer of thickness more than 10 μ m, overlapping constraint thereon, amounts to and forms the above restraint layer of 50 μ m as second restraint layer with raw cook.
4. the manufacture method of multilayer ceramic substrate according to claim 1, it is characterized in that, make described not sintered multilayer ceramic substrate with the state that can utilize slot segmentation to be divided into the assembly substrate of a plurality of substrate chip, on described assembly substrate and/or below on described restraint layer is set.
5. the manufacture method of multilayer ceramic substrate according to claim 1 is characterized in that, as main component with Al
2O
3, SiO
2, SrO and TiO
2Total amount when being made as 100 quality %, will be with Al
2O
3Be scaled the Al of 10～60 quality %, with SiO
2Be scaled 25～60 quality % Si, with SrO be scaled 7.5～50 quality % Sr and with TiO
2The Ti that is scaled 0～20 quality % is that ceramic material micro mist after the calcining under 700 ℃～850 ℃ of main component is broken, use contains the calcined body micro mist of gained, the slip of organic binder bond, making can be carried out low sintering substrate raw cook, wherein with described laminated body at 800 ℃～1000 ℃ following sintering, described restraint layer is removed from described laminated body.
6. the manufacture method of multilayer ceramic substrate according to claim 5 is characterized in that, described substrate contains following auxiliary element with raw cook, that is, with respect to per 100 mass parts of described main component, contain from by with Bi
2O
3Be scaled the Bi of 0.1～10 mass parts, with Na
2O is scaled the Na of 0.1～5 mass parts, with K
2O be scaled 0.1～5 mass parts K and with CoO be scaled select in one group that the Co of 0.1～5 mass parts constitutes at least a and from by be scaled the Cu of 0.01～5 mass parts with CuO, with MnO
2Be scaled select in one group that the Ag of the Mn of 0.01～5 mass parts and 0.01～5 mass parts constitutes at least a.
7. the manufacture method of multilayer ceramic substrate according to claim 5 is characterized in that, described restraint layer is made thickness more than the 50 μ m.
8. the manufacture method of multilayer ceramic substrate according to claim 11, it is characterized in that, utilize coating to form first restraint layer of thickness more than 10 μ m, overlap described constraint thereon and as second restraint layer, amount to and form the above restraint layer of 50 μ m with raw cook.
9. the multilayer ceramic substrate that will utilize the described method of claim 1 to obtain has been installed in the e-machine on the surface of circuit substrate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109076709A (en) * | 2016-04-28 | 2018-12-21 | 株式会社村田制作所 | Multilayer ceramic substrate |
| CN110683856A (en) * | 2018-07-05 | 2020-01-14 | 脉科技股份有限公司 | Conductive porous ceramic substrate and method for producing same |
| CN113912272A (en) * | 2021-11-05 | 2022-01-11 | 广东南星玻璃有限公司 | Machining device and machining method for plane-concave integrated glass panel |
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| JP6006474B2 (en) * | 2011-04-25 | 2016-10-12 | 日本特殊陶業株式会社 | Wiring board, multi-cavity wiring board, and manufacturing method thereof |
| CN103050280A (en) * | 2011-10-12 | 2013-04-17 | 李文熙 | Sintering inhibition of multilayer ceramic capacitor for improving capacitance temperature characteristic and reliability |
| CN103050281A (en) * | 2011-10-12 | 2013-04-17 | 李文熙 | Shrinkage sintering inhibition for improving electrode continuity of multilayer ceramic assembly |
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| CN115557795A (en) * | 2022-09-07 | 2023-01-03 | 广东环波新材料有限责任公司 | Sintering method of low-temperature co-fired ceramic substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000159577A (en) * | 1998-09-22 | 2000-06-13 | Tdk Corp | Production of ceramic substrate |
| JP3771099B2 (en) * | 1999-01-27 | 2006-04-26 | 松下電器産業株式会社 | Green sheet and manufacturing method thereof, manufacturing method of multilayer wiring board, manufacturing method of double-sided wiring board |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109076709A (en) * | 2016-04-28 | 2018-12-21 | 株式会社村田制作所 | Multilayer ceramic substrate |
| CN110683856A (en) * | 2018-07-05 | 2020-01-14 | 脉科技股份有限公司 | Conductive porous ceramic substrate and method for producing same |
| CN113912272A (en) * | 2021-11-05 | 2022-01-11 | 广东南星玻璃有限公司 | Machining device and machining method for plane-concave integrated glass panel |
| CN113912272B (en) * | 2021-11-05 | 2022-05-24 | 广东南星玻璃有限公司 | Machining device and machining method for plane-concave integrated glass panel |
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| CN101604636B (en) | 2011-08-31 |
| CN100556244C (en) | 2009-10-28 |
| CN1757272A (en) | 2006-04-05 |
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