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WO2012067253A1 - Substrat en céramique et son procédé de production - Google Patents

Substrat en céramique et son procédé de production Download PDF

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Publication number
WO2012067253A1
WO2012067253A1 PCT/JP2011/076745 JP2011076745W WO2012067253A1 WO 2012067253 A1 WO2012067253 A1 WO 2012067253A1 JP 2011076745 W JP2011076745 W JP 2011076745W WO 2012067253 A1 WO2012067253 A1 WO 2012067253A1
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Prior art keywords
ceramic substrate
layer
substrate layer
alumina
green sheet
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PCT/JP2011/076745
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English (en)
Japanese (ja)
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雄治 後藤
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パナソニック株式会社
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Publication of WO2012067253A1 publication Critical patent/WO2012067253A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • H05K3/4629—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials laminating inorganic sheets comprising printed circuits, e.g. green ceramic sheets

Definitions

  • the present invention relates to a ceramic substrate and a manufacturing method thereof. More particularly, the present invention relates to a ceramic substrate obtained through firing of a green sheet, and also relates to a method for manufacturing such a ceramic substrate.
  • the ceramic substrate is excellent in heat resistance and moisture resistance, and has good frequency characteristics in a high frequency circuit. Accordingly, the ceramic substrate is used as an RF (Radio Frequency) module of a mobile device, a substrate for a power LED (Light Emitting Diode) utilizing heat dissipation, and a substrate for an LED for a liquid crystal backlight. It is also used as a substrate for electronic control circuits mounted on automobiles.
  • RF Radio Frequency
  • the ceramic substrate itself is a substrate obtained from a large number of green sheets. That is, a ceramic multilayer substrate can be obtained by subjecting a laminate composed of a large number of green sheets to a heat treatment.
  • a state in which a “constraint layer” is arranged outside the green sheet laminate in order to prevent the shrinkage in the plane direction / horizontal direction is obtained. That is, a conventional method for manufacturing a ceramic substrate using a constraining layer includes the following steps: -A step of stacking a number of green sheets on the upper and lower surfaces of the alumina substrate portion to obtain a laminate; -Disposing a constraining layer (i.e.
  • constraining sheet on the outer surface of the laminate so that the laminate is sandwiched by the constraining layer; -A step of heat-treating and baking the laminated body sandwiched between the constraining layers; -The process of removing a constrained layer from a laminated body fired product.
  • the constraining layer used for manufacturing the ceramic substrate is a sheet that does not sinter at the firing temperature of the green sheet. Therefore, the constraining layer (constraining sheet) suppresses shrinkage in the planar direction of the laminate during firing, and the ceramic substrate obtained without using the constriction layer becomes an “irregular sintered body”. This means that a constraining layer is indispensable for firing a green sheet, that is, for producing a ceramic substrate.
  • the main object of the present invention is to provide a substrate structure and a substrate manufacturing method capable of obtaining a desired ceramic substrate without using a constraining layer considered to be an essential element.
  • An alumina substrate layer, and a single ceramic substrate layer provided on at least one main surface of the upper and lower sides of the alumina substrate layer A single ceramic substrate layer is composed of a fired body formed by firing a green sheet containing an alumina component and a glass component, and the thickness of the single ceramic substrate layer is 0 times the thickness of the alumina substrate layer. % (Excluding 0%) to 35% is provided.
  • the ceramic substrate of the present invention has a substrate configuration suitable for manufacturing without using a “constraint layer (constraint sheet)”, and in particular, a single substrate is formed on the main surface of the alumina substrate.
  • the thickness of the single ceramic substrate layer is 0% (not including 0%) to 35% of the thickness of the alumina substrate layer.
  • the term “single ceramic substrate layer” means an embodiment in which only one ceramic layer is provided on at least one side of the alumina substrate layer (that is, the main surface of the alumina substrate layer). There are no multiple ceramic layers on top to increase the thickness). More specifically, the “single ceramic substrate layer” is formed by providing only one ceramic layer formed of a green sheet disposed on at least one side of the alumina substrate layer on the alumina substrate layer. The embodiment is substantially meant.
  • the surface portion of the single ceramic substrate layer (the surface portion forming the outer surface of the substrate) is in a glass-rich state. That is, many glass components exist in the surface part of a ceramic substrate layer.
  • glass-rich state substantially means that there are more glass components than “in the case of the surface portion of the ceramic substrate layer obtained by a conventional production method using a constraining layer”, Specifically, the content of at least silicon element (Si) among elements (Si, Ca, O, Na, Mg, K, etc.) constituting the glass component is 6.0% by weight or more. I mean.
  • the content of silicon element (Si) in the surface portion of the ceramic substrate layer is 8.0 wt% to 16.0 wt%.
  • the content of calcium element (Ca) in the surface portion of the ceramic substrate layer is also increased, and the content of calcium element in the surface portion is 0.7 wt% or more, for example, 0.8 wt. % To 2.6% by weight.
  • the “surface portion” refers to a local region portion from the surface to a certain depth, and particularly from the surface of the ceramic substrate layer (that is, the outer surface of the ceramic substrate). It refers to a local surface area of up to 1 ⁇ m.
  • the single ceramic substrate layer includes anorthite crystals, and the weight ratio of elements constituting the anorthite crystals is substantially the same between the surface portion and the inside of the ceramic substrate layer.
  • a single ceramic substrate layer has a crystal structure composed of elements having a substantially uniform weight ratio as a whole.
  • the weight ratio of an aluminum element, a silicon element, a calcium element, and an oxygen element constituting the anorthite crystal Al—Si—Ca—O
  • Al—Si—Ca—O oxygen element constituting the anorthite crystal
  • the content ratio of the elements constituting the anorthite crystal is substantially the same between the surface portion and the inside of the ceramic substrate layer
  • the surface roughness Rmax of the single ceramic substrate layer is 3 ⁇ m to 7 ⁇ m. That is, in the ceramic substrate of the present invention, the surface of the ceramic substrate layer, that is, the outer surface of the ceramic substrate is rough to some extent.
  • Yet another preferred embodiment comprises a single ceramic substrate layer on both the upper and lower major surfaces of the alumina substrate layer. That is, “a single ceramic substrate layer having a thickness of 35% or less of the thickness of the alumina substrate layer” is provided on each of the upper main surface and the lower main surface so as to sandwich the alumina substrate layer.
  • the present invention also provides a method for manufacturing the above-described ceramic substrate.
  • a production method of the present invention comprises: (I) A single green sheet containing an alumina component and a glass component is disposed on at least one main surface of an upper side and a lower side of an alumina substrate used as a core layer of a ceramic substrate, and alumina substrate-green A step of forming a sheet laminate, and (ii) subjecting the alumina substrate-green sheet laminate to a heat treatment without using a constraining sheet (that is, subjecting the laminate to a heat treatment without being sandwiched between constraining layers) And a step of forming a single ceramic substrate layer from the green sheet,
  • the thickness of the single green sheet in step (i) is set to 0% (excluding 0%) to 65% of the thickness of the alumina substrate.
  • a ceramic substrate is formed without using a “constraint layer / constraint sheet”. Instead of using a constraining layer / constraint sheet, a “single” green sheet is provided on the alumina substrate, and the thickness of the single green sheet is 0% (0%) of the thickness of the alumina substrate.
  • the “alumina substrate-green sheet laminate” is subjected to a heat treatment under conditions such that it is 65%. According to such a manufacturing method, the shrinkage in the plane direction of the sheet is suppressed during the heat treatment in the step (ii), and the green sheet shrinks only in the thickness direction.
  • the thickness of the ceramic substrate layer may be 0% (excluding 0%) to 35% of the thickness of the alumina substrate layer.
  • the surface portion of the “single ceramic substrate layer” formed from the green sheet can be in a glass-rich state. That is, in the step (ii), a ceramic substrate layer having a large amount of glass component on the surface portion can be formed.
  • the content of silicon element (Si) in the surface portion of a ceramic substrate layer obtained by a conventional method using a constraining layer / constraint sheet is as low as 1 to 3% by weight, whereas no constraining layer is used.
  • the content of silicon element (Si) in the surface portion of the ceramic substrate layer obtained by the production method of the present invention is increased to 8.0 wt% to 16.0 wt%.
  • the content of calcium element (Ca) in the surface portion of the ceramic substrate layer obtained by the conventional method using a constraining layer / constraint sheet is as low as about 0.2 wt% to 0.75 wt%
  • the content of calcium element (Ca) in the surface portion of the ceramic substrate layer obtained by the production method of the present invention without using the constraining layer is as high as 0.8 wt% to 2.6 wt%.
  • anorthite crystals are preferably precipitated in the “single ceramic layer” formed from the green sheet, and the content ratio of elements constituting the anorthite crystals
  • the surface portion and the inside of the ceramic substrate layer are substantially the same. That is, in the step (ii), a “single ceramic substrate layer” having a crystal structure composed of elements having a substantially uniform weight ratio is formed as a whole layer.
  • the weight ratio of the aluminum element, silicon element, calcium element, and oxygen element constituting the anorthite crystal Al—Si—Ca—O
  • Al—Si—Ca—O aluminum element, silicon element, calcium element, and oxygen element constituting the anorthite crystal
  • a single green sheet is provided on each of the upper and lower main surfaces of the alumina substrate.
  • the upper and lower main surfaces of the alumina substrate are sandwiched between “0% (excluding 0%) to 65% of the thickness dimension of the alumina substrate.
  • a single ceramic substrate layer is arranged.
  • “a single ceramic substrate layer having a thickness of 0% (excluding 0%) to 35% of the thickness of the alumina substrate layer” is finally formed on the upper main surface and the lower surface of the alumina substrate layer.
  • a ceramic substrate disposed on the side main surface can be obtained.
  • a desired ceramic substrate can be obtained without using a constraining layer. That is, even if there is no constraining layer, a ceramic substrate can be obtained without becoming an “irregular sintered body”.
  • a substrate configuration in which the thickness of the single ceramic substrate layer is 0% (not including 0%) to 35% of the thickness of the alumina substrate layer If the thickness of a single green sheet is set to 0% (excluding 0%) to 65% of the thickness of the alumina substrate sheet ”, the plane direction during firing without using a constraining layer / constraint sheet Sheet shrinkage can be suppressed, and preferably the sheet shrinkage in the plane direction can be made substantially zero.
  • the substrate configuration and lamination conditions in the present invention can be suitably related to the material characteristics of the ceramic substrate layer as described below.
  • the surface portion of the ceramic layer can be in a glass rich state as compared with the substrate of the prior art. Therefore, the ceramic substrate of the present invention is desirable in terms of light reflection, and can be suitably used as an LED mounting substrate or the like. More specifically, the surface portion of the ceramic layer obtained by the conventional manufacturing method using a constrained layer has few glass components such as silicon element and calcium element, while aluminum element (in general, aluminum is desirable in terms of light reflection). On the other hand, in the surface portion of the ceramic substrate layer in the present invention, there are many glass components such as silicon element and calcium element and less aluminum element. Therefore, it can be said that the ceramic substrate of the present invention is a desirable substrate in terms of light reflection.
  • the ceramic substrate of the present invention may have a crystal structure composed of elements with a substantially uniform weight ratio as a whole layer than the prior art substrate. Therefore, the ceramic substrate of the present invention is structurally relatively strong and can be suitably used as various mounting substrates. More specifically, in the surface portion of the ceramic layer obtained by the conventional manufacturing method using a constraining layer / constraint sheet, silicon elements and calcium elements among elements constituting anorthite crystals (Al—Si—Ca—O) are particularly selected.
  • the content of is less than the inside of the layer (that is, the weight ratio of the aluminum element, silicon element, calcium element and oxygen element constituting the anorthite crystal is different between the surface portion and the inside of the ceramic substrate layer), Therefore, the surface portion of the ceramic substrate in the prior art is structurally relatively fragile.
  • the content of the elements constituting the anorthite crystal is not substantially different from that in the inside of the layer. It is not less than the content. That is, the surface portion of the ceramic substrate of the present invention is not “crumbly” and is structurally relatively strong.
  • the ceramic substrate of the present invention is formed without using a constraining layer / constraining sheet, and therefore the surface of the ceramic substrate layer is relatively rough. Therefore, the ceramic substrate of the present invention is desirable for forming an external electrode layer and the like. Specifically, since the outer surface of the ceramic substrate is rough, the “anchor effect” is preferably exhibited, and the external electrode layer can be firmly provided on the substrate.
  • the ceramic substrate of the present invention has a denser ceramic substrate layer than the prior art substrate. Therefore, the ceramic substrate of the present invention has excellent heat dissipation characteristics, and can be suitably used as an LED mounting substrate. (If the substrate has excellent heat dissipation characteristics, the light emission efficiency of the LED will increase and a higher brightness LED product will be realized. can do). More specifically, in the present invention, the pores in the ceramic layer portion are reduced as compared with the conventional production method using a constraining layer / constraint sheet. For example, the pore volume is preferably reduced by 10 to 30 vol% compared with the conventional production method.
  • FIG. 1 is a cross-sectional view schematically showing an embodiment of the ceramic substrate of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing an aspect (thickness dimension) of the ceramic substrate of the present invention.
  • 3 is a cross-sectional view schematically showing an embodiment of the ceramic substrate of the present invention (particularly including a partially enlarged view for explaining “glass rich” of the surface portion).
  • 4 is a cross-sectional view schematically showing an embodiment of the ceramic substrate of the present invention (particularly including a partially enlarged view for explaining “anorsite crystal of uniform weight ratio”). .
  • Fig. 5 (Fig. 1) is a cross-sectional view schematically showing an embodiment of the ceramic substrate of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing an aspect (thickness dimension) of the ceramic substrate of the present invention.
  • 3 is a cross-sectional view schematically showing an embodiment of the ceramic substrate of the present invention (particularly including a partially enlarged view for explaining “glass rich” of
  • FIG. 5 is a schematic diagram for explaining the surface roughness of the ceramic substrate of the present invention (Fig. 5 (a): substrate surface roughness of the present invention, Fig. 5 (b): prior art). Substrate surface roughness).
  • Fig. 6 is a cross-sectional view schematically showing an embodiment of the ceramic substrate of the present invention (Fig. 6 (a): a single ceramic substrate layer is provided only on the upper principal surface of the alumina substrate layer. 6 (b): an embodiment in which a single ceramic substrate layer is provided only on the lower main surface of the alumina substrate layer.
  • FIG. 7 (FIG. 7) is a cross-sectional view schematically showing the substrate and the green sheet prepared in step (i).
  • Fig. 8 (Fig.
  • FIG. 8 is a cross-sectional view schematically showing an aspect of forming an alumina substrate-green sheet laminate.
  • Fig. 9 (Fig. 9) is a cross-sectional view schematically showing a mode of temporary adhesion of the laminated body.
  • FIG. 10 (FIG. 10) is a cross-sectional view schematically showing firing in the present invention.
  • Fig. 11 (Fig. 11) is a cross-sectional view schematically showing a modification of the ceramic substrate of the present invention (Fig. 11 (a): a single ceramic substrate layer having a predetermined thickness includes a plurality of layers (2 11 (b): an example in which a single ceramic substrate layer having a predetermined thickness is composed of a plurality of layers (three layers)). 12 (FIG.
  • FIG. 12 is a schematic diagram for explaining a test mode of “confirmation test of XMA detection element and quantitative value and surface observation”.
  • FIG. 13 is an SEM image and XMA element spectrum (surface A) of the ceramic layer (surface region) of the comparative construction method product.
  • FIG. 14 is an SEM image and an XMA element spectrum of the ceramic layer (cross-sectional area) of the comparative construction product (surface B1).
  • 15 is an SEM image and an XMA element spectrum of the ceramic layer (cross-sectional area) of the comparative construction method product (surface B2).
  • FIG. 16 (FIG.
  • FIG. 16 is an SEM image and an XMA element spectrum of the ceramic layer (cross-sectional area) of the comparative construction product (surface B3).
  • Fig. 17 is an SEM image and XMA element spectrum (surface C) of the ceramic layer (surface region) of the new construction method product.
  • 18 is an SEM image and XMA element spectrum of the ceramic layer (cross-sectional area) of the new construction method product (surface D1).
  • FIG. 19 (FIG. 19) is an SEM image and an XMA element spectrum of the ceramic layer (cross-sectional area) of the new construction method product (surface D2).
  • FIG. 20 (FIG.
  • FIG. 20 is an SEM image and XMA element spectrum of the ceramic layer (cross-sectional area) of the new construction method product (surface D3).
  • FIG. 21 is an SEM image and an XMA element spectrum of an alumina sheet alone product (surface / cross-sectional area) (surface / cross-section E).
  • FIG. 22 is a table summarizing XMA detection elements and quantitative values in the comparative construction method product and the new construction method product.
  • FIG. 23 (FIG. 23) is a substrate cross-sectional image of the comparison method product taken in the “substrate cross-section confirmation test”. 24 (FIG.
  • FIG. 24 is a substrate cross-sectional image of the new method product taken in the “substrate cross-section confirmation test”.
  • FIG. 25 (FIG. 25) is a surface profile obtained by the “surface roughness confirmation test”.
  • FIG. 26 (FIG. 26) is a schematic diagram for explaining the surface roughness of the comparative construction method.
  • FIG. 27 (FIG. 27) is a schematic diagram for explaining the surface roughness of the new construction method.
  • FIG. 28 (FIG. 28) is a schematic diagram for explaining the mode and conditions of the “strength confirmation test”.
  • FIG. 29 (FIG. 29) is a photographic diagram for explaining the mode of the “strength confirmation test”.
  • FIG. 30 (FIG. 30) is a graph showing the results of the “strength confirmation test”.
  • FIG. 31 (FIG. 31) is a schematic diagram for explaining the characteristics of the substrate according to the present invention when compared with a single alumina substrate.
  • reference numbers refer to the following elements: 10 Alumina substrate layer / alumina substrate 10A Upper main surface of alumina substrate layer (alumina substrate) 10B Lower main surface of alumina substrate layer (alumina substrate) 14 Internal circuit pattern 14 'Precursor of internal circuit pattern 16 Via 16' Via precursor Body 20A Ceramic substrate layer (upper side) 20A 'Green sheet for ceramic substrate layer (upper side) 20B Ceramic substrate layer (lower side) 20B 'Green sheet for ceramic substrate layer (lower side) 26A, 26B Via 26A ', 26B' Via precursor 50 Quartz glass plate or SUS plate used for temporary adhesion of laminate 55 Pedestal 70 Firing furnace 100 Ceramic substrate 100 'Alumina substrate-green sheet laminate (precursor of ceramic substrate ) 102A, 102B Circuit pattern wiring section 104A, 104B External electrode
  • the ceramic substrate 100 of the present invention includes an alumina substrate layer 10 and ceramic substrate layers 20A and 20B provided on the upper main surface 10A and the lower main surface 10B of the alumina substrate layer 10, respectively. It consists of As can be seen from the illustrated embodiment, the ceramic substrate layers 20A and 20B provided on the respective principal surfaces of the alumina substrate layer 10 are only “single”, and the thickness thereof is larger than the thickness of the alumina substrate layer 10. It is considerably thinner.
  • the alumina substrate layer 10 is a layer containing alumina, and preferably has an alumina content of 80% by weight or more, more preferably 90% by weight or more, further preferably 95% by weight or more.
  • the alumina substrate layer 10 itself is a substrate sintered at a temperature higher than the “sintering temperature of the green sheet for obtaining the ceramic substrate layer” (for example, a temperature 90 ° C. or more higher than the sintering temperature of the green sheet, More preferably, the substrate is sintered at a temperature higher than 100 ° C., more preferably higher than 110 ° C., and may correspond to a substrate portion fired in advance prior to the formation of the ceramic substrate layers 20A and 20B. .
  • the alumina substrate layer 10 (particularly its surface portion) is preferably provided with an internal circuit pattern 14 such as an internal electrode layer and / or an internal wiring layer.
  • an internal circuit pattern 14 such as an internal electrode layer and / or an internal wiring layer.
  • vias 16 and the like electrically connected to the internal circuit pattern 14 are provided.
  • the dimensions and materials of the internal circuit pattern 14 and the via 16 are not particularly limited as long as they are conventionally used and adopted in the electronic equipment field (for example, an LED mounting board).
  • Each of the ceramic substrate layers 20A and 20B is made of a fired body formed by firing a green sheet containing an alumina component and a glass component.
  • the green sheet itself for obtaining the ceramic substrate layer may be a sheet-like member containing an alumina component, a glass component, and an organic binder component, and the ceramic substrate layers 20A and 20B are obtained by subjecting it to firing. be able to.
  • vias 26A and 26B are preferably provided in each of the “single” ceramic substrate layers 20A and 20B.
  • circuit pattern wiring portions 102A and 102B, external electrodes 104A and 104B, and the like are preferably provided on the surfaces of the single ceramic substrate layers 20A and 20B, that is, the outer surfaces 100A and 100B of the ceramic substrate 100.
  • the circuit pattern wiring portion 102A, the external electrode 104B, and the like may be electrically connected to the vias 26A and 26B of the ceramic substrate layer.
  • the ceramic substrate of the present invention has a substrate configuration suitable for manufacturing without using a “constraint layer”.
  • the ceramic substrate layers 20A and 20B provided on each main surface of the alumina substrate layer 10 are "single" to the last, and the thickness T2 is 0% of the thickness T1 of the alumina substrate layer ( It is as thin as ⁇ 35% (not including 0%) (see FIG. 2).
  • the thickness of the single ceramic substrate layer 20A or 20B can basically be a substrate configuration suitable for manufacturing without using a “constraint layer”, but if it is too thin, the alumina substrate layer 10 The internal circuit pattern 14 provided above is exposed. Accordingly, each of the single ceramic substrate layers 20A and 20B has a thickness T2 of preferably about 3% to 30% of the thickness T1 of the alumina substrate layer, more preferably about 4% to 25% of T1. Preferably, it is about 5% to 20% of T1 (see FIG. 2). For example, it may be about 10% to 30%.
  • the ceramic substrate 100 of the present invention has a single ceramic substrate while the thickness T1 of the alumina substrate layer 10 is about 0.3 mm.
  • the thickness T2 of the layer 20A is about 0.1 mm, and the thickness T2 of the single ceramic substrate layer 20B is also about 0.1 mm.
  • the thickness T1 of the alumina substrate layer 10 is about 400 ⁇ m, whereas the thickness T2 of the single ceramic substrate layer 20A is about 96 ⁇ m.
  • the thickness T2 of the ceramic substrate layer 20B is about 96 ⁇ m.
  • the surface portion of the single ceramic substrate layer (the surface portion forming the outer surface of the substrate) is preferably glass-rich (see FIG. 3). That is, the surface portion of the single ceramic substrate layer is at least selected from the group consisting of Si (silicon), Ca (calcium), O (oxygen), Na (sodium), Mg (magnesium), and potassium (K).
  • the surface portion of the single ceramic substrate layer is at least selected from the group consisting of Si (silicon), Ca (calcium), O (oxygen), Na (sodium), Mg (magnesium), and potassium (K).
  • One or more glass components are in a “glass-rich state”.
  • the content of silicon element (Si) among the elements constituting the glass component is 6.0 wt% or more, for example, 8.0 wt% to 16.0 wt%.
  • the content of elemental calcium (Ca) is preferably 0.7% by weight or more, for example 0.8% to 2.6% by weight.
  • the “glass-rich state” according to the present invention is a matter that can be clearly understood as compared with a ceramic layer obtained by a conventional manufacturing method using a constraining layer / constraint sheet. More specifically, referring to Table 1 obtained in the examples described later (“XMA detection element and quantitative value confirmation test and surface observation”), a ceramic layer obtained by a conventional manufacturing method using a constraining layer / constraining sheet Whereas the silicon element content in the surface portion (local surface region from the surface to a depth of 1 ⁇ m) is as low as 1 to 3% by weight, the surface of the ceramic substrate layer of the ceramic substrate of the present invention The silicon element content in the portion (local surface region from the surface to a depth of 1 ⁇ m) is as high as 8.0 wt% to 16.0 wt%.
  • the content of calcium element in the surface portion (local surface region from the surface to a depth of 1 ⁇ m) of the ceramic layer obtained by the conventional method using a constraining layer / constraint sheet is 0.2 wt% to 0.
  • the content of calcium element in the surface portion of the ceramic substrate layer of the ceramic substrate of the present invention is 0.8% by weight. 2.6% by weight.
  • the ceramic substrate layer according to the present invention not only the surface portion but also the inside is in a “glass-rich state”, whereas a conventional method using a constraining layer / constraint sheet is used.
  • the content of the glass component is different between the surface portion and the inside, and the surface portion is not in a “glass-rich state”, but rather in a state in which the aluminum element is rich.
  • aluminum is generally not high in light reflectivity in terms of material. Therefore, it can be said that the ceramic substrate of the present invention is more desirable in terms of light reflection than the conventional ceramic substrate.
  • a single ceramic substrate layer includes anorthite crystals (Al-Si-Ca-O), and the content ratio of elements constituting the anorthite crystals is the same as that of the ceramic substrate layer.
  • the surface portion and the inside are substantially the same. That is, a single ceramic substrate layer has a crystal structure composed of elements having a substantially uniform weight ratio as a whole (see FIG. 4).
  • the weight ratio of the aluminum element, silicon element, calcium element, and oxygen element constituting the anorthite crystal is substantially the same between the surface portion and the inside of the ceramic substrate layer.
  • the weight ratio (weight% ratio) is as follows.
  • Table 1 shows the following:
  • the weight ratio of the aluminum element, silicon element, calcium element, and oxygen element constituting the anorthite crystal is different between the surface portion and the inside of the ceramic layer.
  • the content and elemental calcium content are low. Therefore, it can be said that the ceramic substrate in the prior art is structurally relatively fragile, especially the surface portion of the substrate.
  • the weight ratio of the aluminum element, silicon element, calcium element and oxygen element constituting the anorthite crystal is substantially the same as the surface portion and the inside of the ceramic layer, In the part, the silicon element content and calcium element content are relatively high as in the interior. Therefore, it can be said that the ceramic substrate in the present invention has a particularly strong surface portion of the substrate.
  • the “anorsite crystal” in this specification means that when the green sheet is fired to become a ceramic, the glass component contained in the green sheet reacts with the alumina component.
  • it means a crystal having at least Al, Si, Ca and O as components constituting the crystal structure (crystal structure that so-called anorthite may have) that becomes the main crystal of this ceramic.
  • the surfaces of the ceramic substrate layers 20A and 20B are rough to some extent.
  • the surface roughness Rmax of the single ceramic substrate layer is preferably about 3 ⁇ m to 8 ⁇ m, more preferably about 4 ⁇ m to 6 ⁇ m.
  • the surface roughness Rmax of the thickness of the ceramic substrate obtained from the conventional method using the constraining layer / constraint sheet is about 2 ⁇ m (see FIG.
  • the ceramic substrate 100 of the present invention is It can be said that the surface is about 1.5 to 4 times rougher than the conventional substrate. Since the substrate surface is moderately rough in this way, the so-called “anchor effect” is suitably exhibited, and the circuit pattern wiring portions 102A, 102B, the external electrodes 104A, 104B, etc. can be firmly provided on the substrate without peeling. It has become.
  • the ceramic substrate layer provided on the main surface of the alumina substrate layer 10 is “single”, and the thickness thereof is considerably smaller than the thickness of the alumina substrate layer. Therefore, as shown in FIG. 6A, a mode in which a single ceramic substrate layer 20A is provided only on the upper main surface 10A of the alumina substrate layer 10 may be employed. Even in this case, the thickness of the single ceramic substrate layer 20A is preferably about 3% to 30% of the thickness of the alumina substrate layer 10, more preferably about 4% to 25%, and still more preferably. Is about 5% to 20%. Similarly, in the ceramic substrate 100 of the present invention, as shown in FIG.
  • a single ceramic substrate layer 20B is provided only on the lower main surface 10B of the alumina substrate layer 10. Also good.
  • the thickness of the single ceramic substrate layer 20B is also preferably about 3% to 30% of the thickness of the alumina substrate layer, more preferably about 4% to 25%, and further preferably about 5% to 20%. is there.
  • a method for producing a ceramic substrate of the present invention will be described. As a representative example, a method for manufacturing a ceramic substrate 100 as shown in FIG.
  • step (i) is performed in the manufacturing method of the present invention. That is, an “alumina substrate-green sheet laminate” is arranged by arranging “a green sheet containing an alumina component and a glass component” on at least one main surface of an upper side and a lower side of an alumina substrate used as a core layer of a ceramic substrate. Form.
  • the alumina substrate 10 is a substrate obtained by subjecting a precursor sheet to firing, for example, and is preferably obtained by sintering at a temperature higher than the sintering temperature of the green sheets 20A ′ and 20B ′.
  • Such an alumina substrate precursor sheet itself is at least selected from the group consisting of an alumina component (eg, alumina powder) and an organic binder component (eg, polyvinyl butyral resin, acrylic resin, vinyl acetate copolymer, polyvinyl alcohol, and vinyl chloride resin). It may be a sheet-like member comprising an organic binder component containing one or more components.
  • an NC punch press Numerical Control punch press
  • a carbon dioxide laser Prior to firing to obtain an alumina substrate, holes are formed in the precursor sheet by an NC punch press (Numerical Control punch press) or a carbon dioxide laser, and the via precursor 16 ′ is filled with a conductive paste material. Is preferably formed (see FIG. 7A).
  • veer 16 can be obtained after baking (refer FIG. 1).
  • a precursor 14 ′ of an internal wiring portion having a desired pattern by supplying a conductive paste by a screen printing method or the like (see FIG. 7 (a)).
  • the precursor material for the via and the internal wiring part is not particularly limited as long as it is a conductive paste that is conventionally used and adopted in a package wiring board of a semiconductor integrated circuit LSI.
  • the conductive paste may comprise Ag powder, glass frit for obtaining adhesive strength, and an organic vehicle (for example, an organic mixture of ethyl cellulose and terpineol).
  • the “upper arrangement green sheet 20A ′” and the “lower arrangement green sheet 20B ′” may be a sheet-like member including an alumina component, a glass component, and an organic binder component.
  • the alumina component may be alumina powder (average particle size: about 0.5 to 10 ⁇ m)
  • the glass component may be borosilicate glass powder (average particle size: about 1 to 20 ⁇ m).
  • the organic binder component may be at least one component selected from the group consisting of polyvinyl butyral resin, acrylic resin, vinyl acetate copolymer, polyvinyl alcohol and vinyl chloride resin, for example.
  • the green sheet for obtaining the ceramic substrate layer may be 40 to 50 wt% alumina powder, 30 to 40 wt% glass powder, and 10 to 30 wt% organic binder component (of the green sheet). Based on total weight).
  • each of the green sheets 20A ′ and 20B ′ includes a solid component (alumina powder 50 to 60 wt% and glass powder 40 to 50 wt%: based on the weight of the solid component) and an organic binder component.
  • the weight ratio, that is, the solid component weight: organic binder component weight may be about 80 to 90:10 to 20.
  • the green sheet component may contain other components as required.
  • a plasticizer that imparts flexibility to a green sheet such as phthalate ester or dibutyl phthalate, or a dispersant for ketones such as glycol. Or an organic solvent.
  • holes are formed by, for example, an NC punch press or a carbon dioxide laser, and the holes are filled with a conductive paste material that is a raw material for vias, and via precursors 26A ′ and 26B ′. Is preferably formed.
  • the conductive paste as a raw material for the via precursor is not particularly limited as long as it is conventionally used and adopted as a package wiring board of a semiconductor integrated circuit LSI.
  • it may be a conductive paste comprising Ag powder, glass frit for obtaining adhesive strength, and an organic vehicle (for example, an organic mixture of ethyl cellulose and terpineol).
  • the thickness dimension of each of the green sheets 20A ′ and 20B ′ needs to be about 65% or less of the thickness dimension of the alumina substrate.
  • the value (%) of “T2 ′ / T1 ⁇ 100” is preferably 0 (0 In the range of about 65 to 65, more preferably about 5 to 55, and still more preferably about 9 to 35.
  • the thickness T2 of the single ceramic substrate layer is the thickness of the alumina substrate layer.
  • the substrate structure is preferably about 3% to 30% of the thickness T1, more preferably about 4% to 25% of T1, and further preferably about 5% to 20% of T1 (see FIG. 2).
  • the alumina substrate 10 As shown in FIG. 8, the alumina substrate 10, the upper green sheet 20A 'and the lower green sheet 20B' are arranged so as to be stacked on each other to form an "alumina substrate-green sheet laminate 100 '". Specifically, the upper green sheet 20A 'and the lower green sheet 20B' are arranged so as to sandwich the alumina substrate 10.
  • a quartz glass plate or a SUS plate 50 is disposed on the upper principal surface / lower principal surface of the alumina substrate-green sheet laminate 100 ′, disposed on the pedestal 55, and then pressurized and heated from above. .
  • the alumina substrate 10, the upper green sheet 20A ', and the lower green sheet 20B' are temporarily bonded to each other in the laminate 100 '.
  • the pressure applied from above the quartz glass plate / SUS plate 50 disposed on the upper side of the laminate 100 ′ may be about 10 to 20 MPa, and the heating temperature of the laminate may be about 75 ° C. to 95 ° C. .
  • step (ii) is performed. That is, the alumina substrate-green sheet laminate 100 ′ is subjected to heat treatment without using a constraining sheet, and a single ceramic layer is formed from each of the green sheets 20 A ′ and 20 B ′.
  • the “restraint sheet (restraint layer)” herein refers to a sheet that is conventionally used at the time of firing particularly in the technical field of manufacturing ceramic substrates.
  • a constraining sheet (constraining layer) is a sheet formed by mixing alumina powder with the same organic material as a green sheet, and has substantially the same outer size as the green sheet (its thickness dimension is about 100 to 350 ⁇ m). It is what has.
  • the “alumina substrate-green sheet laminate” is subjected to firing without being sandwiched between such “restraint sheets (constraint layers)”.
  • the alumina substrate-green sheet laminate 100 ′ is preferably subjected to a decomposition and desorption process (binder burnout process) of organic substances such as a debinding process prior to firing.
  • a decomposition and desorption process binder burnout process
  • heat treatment may be performed for 20 to 50 hours under a temperature condition of 500 ° C. to 700 ° C.
  • the laminate is preferably heated for about 0.1 to 3 hours under a temperature condition of, for example, 800 ° C. to 1000 ° C. (preferably 850 ° C. to 950 ° C.).
  • the heat treatment itself may be performed by subjecting the alumina substrate-green sheet laminate 100 ′ to a firing furnace such as a mesh belt furnace 70 (see FIG. 10).
  • the surface portion of the single ceramic substrate layer formed from the green sheet can be preferably glass-rich (see FIG. 3). That is, the surface portion of each single ceramic substrate layer 20A, 20B is made of Si (silicon), Ca (calcium), O (oxygen), Na (sodium), Mg (magnesium), and potassium (K). It becomes a glass-rich state for at least one kind of glass component selected from.
  • the content of silicon element (Si) among the elements constituting the glass component can be 6.0 wt% or more, for example, 8.0 wt% to 16.0 wt%, Further, the content of calcium element (Ca) can be 0.7 wt% or more, for example, 0.8 wt% to 2.6 wt%.
  • anorthite crystals (Al—Si—Ca—O) are preferably precipitated in a single ceramic substrate layer formed from a green sheet, and the content of elements constituting the anorthite crystals
  • the ratio can be substantially the same between the surface portion and the inside of the ceramic substrate layer. That is, each of the single ceramic substrate layers 20A and 20B can have a crystal structure composed of elements having a substantially uniform weight ratio as a whole.
  • the weight ratio of the aluminum element, silicon element, calcium element and oxygen element constituting the anorthite crystal is different between the surface portion and the inside of the ceramic substrate layer. It can be almost the same.
  • the manufacturing method of the present invention provides a “substrate configuration in which the thickness of the single ceramic substrate layer is 0% (not including 0%) to 35% of the thickness of the alumina substrate layer”.
  • “The lamination condition in which the thickness of the single green sheet provided on the alumina substrate sheet is 0% (excluding 0%) to 65% of the thickness of the alumina substrate” is adopted. Therefore, the sheet contraction in the planar direction at the time of firing (shrinkage of the green sheet fired body) can be suppressed without using a constraining layer, and preferably the sheet shrinkage in the planar direction can be made substantially zero.
  • the desired ceramic substrate 100 can be obtained without forming an “irregular sintered body” without being sandwiched between the constraining layers.
  • the substrate can be obtained with the ceramic substrate layers 20A and 20B having a somewhat rough surface.
  • the surface roughness Rmax of the single ceramic substrate layer is preferably about 3 ⁇ m to 8 ⁇ m, more preferably about 4 ⁇ m to 6 ⁇ m.
  • the so-called “anchor effect” is preferably exhibited, and subsequently, the circuit pattern wiring portions 102A and 102B, the external electrodes 104A and 104B, and the like are firmly provided on the substrate without peeling. it can.
  • the ceramic substrate layer is a single layer.
  • the present invention is not limited to this, and it may be composed of a plurality of layers (see FIGS. 11A and 11B).
  • the manufacturing method of the present invention if the thickness dimension of a single green sheet is about 0% (excluding 0%) to 65% of the thickness dimension of the alumina substrate, the single green sheet May be composed of a plurality of sub-sheets.
  • the ceramic substrate layer has a thickness T2 that is about 0% (not including 0%) to 35% of the thickness T1 of the alumina substrate layer.
  • the upper limit value of the thickness T2 of the ceramic substrate layer is larger than “35% of the thickness T1 of the alumina substrate layer” (for example, alumina Even when the thickness is about 40% of the thickness T1 of the substrate layer, it may be assumed that a desired ceramic substrate can be obtained without becoming an “irregular sintered body”.
  • the present invention has the following aspects.
  • 1st aspect It is a ceramic substrate, Comprising : An alumina substrate layer, and a single ceramic substrate layer provided on at least one main surface of the upper and lower sides of the alumina substrate layer,
  • the single ceramic substrate layer is composed of a fired body formed by firing a green sheet containing an alumina component and a glass component, and the thickness dimension of the single ceramic substrate layer is 0 of the thickness dimension of the alumina substrate layer.
  • % (Excluding 0%) to 35% for example, the thickness dimension of the ceramic substrate layer is one third or less of the thickness dimension of the alumina substrate layer).
  • the surface portion of the single ceramic substrate layer is made of Si (silicon), Ca (calcium), O (oxygen), Na (sodium), Mg (magnesium), and potassium (K).
  • Third Aspect In the first aspect or the second aspect, the content of silicon element in the surface portion of the single ceramic substrate layer is 8.0 wt% to 16.0 wt% (for example, 9.0 wt% to 15. 0% by weight or 10.0% by weight to 14.0% by weight).
  • the content of calcium element in the surface portion of the single ceramic substrate layer is 0.8 wt% to 2.6 wt% (for example, 1.2 wt%). ⁇ 2.6 wt% or 1.6 wt%-2.6 wt%, etc.).
  • Fifth aspect In any one of the first to fourth aspects, the single ceramic substrate layer comprises anorthite crystals, and the content ratio of elements constituting the anorthite crystals is different from the surface portion of the ceramic substrate layer. A ceramic substrate characterized by being substantially the same inside.
  • Sixth aspect The ceramic substrate according to any one of the first to fifth aspects, wherein the surface roughness Rmax of the ceramic substrate layer is 3 ⁇ m to 7 ⁇ m.
  • a single ceramic substrate layer is provided on each of the upper and lower main surfaces of the alumina substrate layer so that the alumina substrate layer is sandwiched therebetween.
  • a ceramic substrate characterized by comprising: Eighth aspect : The ceramic substrate according to any one of the first to seventh aspects, wherein the single ceramic substrate layer is composed of a plurality of sub-ceramic substrate layers.
  • Ninth aspect A method for producing a ceramic substrate, comprising: (I) A single green sheet containing an alumina component and a glass component is disposed on at least one main surface of an upper side and a lower side of an alumina substrate used as a core layer of a ceramic substrate.
  • a step of forming a sheet laminate, and (ii) without using a constraining layer (more specifically, without providing a “constraint sheet that does not sinter at the sintering temperature of the green sheet” outside the laminate), Subjecting the alumina substrate-green sheet laminate to a heat treatment to form a single ceramic substrate layer from the green sheet,
  • the thickness of the single green sheet in step (i) is 0% (not including 0%) to 65% of the thickness of the alumina substrate (for example, the thickness of the green sheet is The thickness is less than half of the thickness dimension).
  • the surface portion of the single ceramic substrate layer is made glass-rich, particularly Si (silicon), Ca (calcium), Glass rich per at least one glass component selected from the group consisting of O (oxygen), Na (sodium), Mg (magnesium) and potassium (K) (in particular, Si element component and / or Ca element component)
  • a method for producing a ceramic substrate characterized in that Twelfth aspect :
  • a single green sheet is disposed on each of the upper and lower main surfaces of the alumina substrate.
  • a method for manufacturing a ceramic substrate is provided.
  • the element component ratio varies greatly between the surface region and the internal region.
  • the Si element component and the Ca element component that can constitute the anorthite crystal are reduced in the surface region.
  • ⁇ Compared with the alumina sheet alone, there is of course a difference from the elemental component in the surface area of the ceramic substrate layer of the new method.
  • ⁇ Surface roughness check test> In order to grasp the material characteristics of the substrate surface from another viewpoint, the surface roughness of the ceramic substrate obtained by the new method and the surface roughness of the ceramic substrate obtained by the comparative method were examined. Specifically, a surface profile as shown in FIG. 25 was obtained by using Tokyo Seimitsu Co., Ltd. (equipment name: surfcom). Based on the results of the surface profile, the following matters could be grasped. -The ceramic layer of the new construction method has a rougher surface than in the comparative construction method.
  • the surface of the ceramic substrate layer of the new method is about 4 ⁇ m to 6 ⁇ m in Rmax, whereas the surface of the ceramic layer in the comparative method is about 1.5 to 2.5 ⁇ m (about 2 ⁇ m) in Rmax.
  • the “surface roughness” of the new method is that the gap region (gap / binder resin region) between the raw material particles that existed at the time of the green sheet is natural when firing. This is considered to be caused by the thickness shrinkage performed in such a form that it disappears (see FIGS. 26 and 27).
  • the hybrid substrate according to the present invention is suitably used as an RF module for mobile devices, a power LED substrate utilizing heat dissipation, and an LED substrate for a liquid crystal backlight, and for an electronic control circuit mounted in an automobile. It is also suitably used as a substrate.
  • the present invention can reduce the manufacturing time and manufacturing cost of a ceramic substrate, and is therefore suitably used as a substrate for an LED for a backlight for a liquid crystal television and a liquid crystal screen of a mobile phone, which has recently been popularized. It is highly expected.
  • the ceramic substrate according to the present invention is more suitable for forming a metal layer such as an external electrode layer when compared with a single alumina substrate (that is, a portion constituting the substrate core portion of the present invention). It is desirable not only in terms of “plating deposition” but also in terms of “light reflectance” (for example, the reflectance of light having a wavelength of about 460 nm is about 90 to 99%). It should be noted that it can be particularly suitably used as an LED mounting board or the like (see FIG. 31). Cross-reference of related applications

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention porte sur un substrat en céramique comprenant une couche de substrat en alumine et une unique couche de substrat en céramique qui est disposée sur la surface principale supérieure et/ou la surface principale inférieure de la couche de substrat en alumine. De façon spécifique, l'unique couche de substrat en céramique de ce substrat en céramique est constituée d'un corps cuit qui est formé par cuisson d'une feuille crue qui contient un composant alumine et un composant verre. L'épaisseur de l'unique couche de substrat en céramique représente 0-35% de l'épaisseur de la couche de substrat en alumine.
PCT/JP2011/076745 2010-11-17 2011-11-15 Substrat en céramique et son procédé de production WO2012067253A1 (fr)

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TWI728775B (zh) * 2019-04-10 2021-05-21 南韓商Ｄｉｔ股份有限公司 多層陶瓷基板及其製造方法

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JPS63202994A (ja) * 1987-02-18 1988-08-22 富士通株式会社 多層セラミツク回路基板の製造方法
JPH034594A (ja) * 1989-05-31 1991-01-10 Kyocera Corp コンデンサー内蔵複合回路基板
JPH0368195A (ja) * 1989-08-05 1991-03-25 Nippondenso Co Ltd セラミック積層基板およびその製造方法
JPH0521931A (ja) * 1991-07-11 1993-01-29 Sumitomo Metal Mining Co Ltd ガラスセラミツク基板の製造方法
JPH07330445A (ja) * 1994-06-10 1995-12-19 Sumitomo Metal Ind Ltd セラミックス基板の製造方法
JP2001135933A (ja) * 1999-11-04 2001-05-18 Murata Mfg Co Ltd 多層セラミック基板

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JPS60260465A (ja) * 1984-06-01 1985-12-23 鳴海製陶株式会社 低温焼成セラミツクス
JPS63202994A (ja) * 1987-02-18 1988-08-22 富士通株式会社 多層セラミツク回路基板の製造方法
JPH034594A (ja) * 1989-05-31 1991-01-10 Kyocera Corp コンデンサー内蔵複合回路基板
JPH0368195A (ja) * 1989-08-05 1991-03-25 Nippondenso Co Ltd セラミック積層基板およびその製造方法
JPH0521931A (ja) * 1991-07-11 1993-01-29 Sumitomo Metal Mining Co Ltd ガラスセラミツク基板の製造方法
JPH07330445A (ja) * 1994-06-10 1995-12-19 Sumitomo Metal Ind Ltd セラミックス基板の製造方法
JP2001135933A (ja) * 1999-11-04 2001-05-18 Murata Mfg Co Ltd 多層セラミック基板

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI728775B (zh) * 2019-04-10 2021-05-21 南韓商Ｄｉｔ股份有限公司 多層陶瓷基板及其製造方法

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