CN107001147B

CN107001147B - Ceramic substrate and method for producing same

Info

Publication number: CN107001147B
Application number: CN201580066723.4A
Authority: CN
Inventors: 河野浩; 梅田勇治; 伊藤阳彦
Original assignee: NGK Insulators Ltd
Current assignee: NGK Insulators Ltd
Priority date: 2014-12-16
Filing date: 2015-12-15
Publication date: 2020-07-10
Anticipated expiration: 2035-12-15
Also published as: WO2016098767A1; JP6632995B2; JPWO2016098767A1; CN107001147A

Abstract

The present invention relates to a ceramic substrate and a method for manufacturing the same. Crystalline phase of ceramic matrix with Al₂O₃And ZrO₂Is a main crystal phase and contains Mn in addition to₃Al₂(SiO₄)₃Or MgAl₂O₄And has a flexural strength of 650MPa or more and a Young's modulus of 300GPa or less.

Description

Ceramic substrate and method for producing same

Technical Field

The present invention relates to a ceramic substrate, and more particularly, to a ceramic substrate suitable for use in, for example, a ceramic package in which an element such as a vibrator is mounted, a high-frequency circuit board, and the like, and a method for manufacturing the same.

Background

As a conventional ceramic substrate, for example, alumina (Al) is used₂O₃) And zirconium oxide (ZrO)₂) As ceramic substrates as main components, ceramic substrates described in Japanese patent No. 2883787, Japanese patent No. 3176815, and Japanese patent No. 4717960 are known.

Japanese patent No. 2883787 discloses a ceramic substrate comprising 70 to 90 mass% of alumina and 10 to 30 mass% of zirconia as main components, and further comprising 0.5 to 2.0 mass% of yttrium (Y), 0.5 to 2.0 mass% of calcium (Ca), 0.5 to 2.0 mass% of magnesium (Mg), and 0.5 to 2.0 mass% of cerium (Ce) as additives.

Japanese patent No. 3176815 discloses a ceramic substrate comprising 82 to 97 mass% of alumina and 2.5 to 17.5 mass% of zirconia as main components, and further comprising 0.1 to 2.0 mass% of yttrium (Y), 0.02 to 0.5 mass% of calcium (Ca), and 0.02 to 0.4 mass% of magnesium (Mg) as additives.

Japanese patent No. 4717960 discloses a ceramic substrate containing alumina as a main component, partially stabilized zirconia as a subcomponent, and magnesia. The ceramic matrix contains partially stabilized zirconia in an amount of 1 to 30 wt% based on the total weight of the powder material, magnesia in an amount of 0.05 to 0.50 wt% based on the total weight of the powder material, and yttria in the partially stabilized zirconia in an amount of 0.015 to 0.035 by mole.

Disclosure of Invention

In general, in a ceramic substrate, the young's modulus increases as the bending strength increases. If the Young's modulus is increased, the material is not easily deformed and becomes brittle, and therefore, cracks are likely to occur, and chipping is likely to occur at the time of chip division.

In the case of a package to which a resonator or the like is mounted, a ceramic substrate having an electrode layer and a wiring layer formed thereon can be obtained by simultaneously firing a ceramic molded body and a metal film. In this case, if the young's modulus of the ceramic substrate is increased, cracks are likely to be generated against bending stress in small and thin package applications mounted on wearable devices, IC cards, and the like.

However, although the bending strength is described in japanese patent No. 2883787, japanese patent No. 3176815, and japanese patent No. 4717960, the young's modulus is not considered at all.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a ceramic substrate which is suitable for a high-frequency circuit board, has high bending strength and low young's modulus, and can realize downsizing of a product (such as a ceramic package or a high-frequency circuit board) using the ceramic substrate at low cost, and a method for manufacturing the same.

[1]The ceramic substrate according to the first aspect of the invention is characterized in that the crystal phase is Al₂O₃And ZrO₂Is a main crystal phase and contains Mn in addition to₃Al₂(SiO₄)₃Or MgAl₂O₄And has a flexural strength of 650MPa or more and a Young's modulus of 300GPa or less.

[2] In the first invention, the bending strength is preferably 650MPa to 1100MPa, and the Young's modulus is preferably 240GPa to 300 GPa.

[3]In the first invention, it is preferable that the dielectric loss tangent at 1MHz is 200 × 10^－4The relative dielectric constant is 10 to 15.

[4] In the first invention, the sintering is preferably carried out at a temperature of 1250 to 1500 ℃.

[5]In the first invention, it is preferable that: according to Al₂O₃70.0 to 90.0 mass% Al in terms of ZrO₂10.0 to 30.0 mass% in terms of Zr and Al₂O₃And ZrO₂Contains, when the total of (A) and (B) is 100 mass%: mn in an amount of 2.0 to 7.0 mass% in terms of MnO, and SiO₂Si in an amount of 2.0 to 7.0 mass% in terms of BaO, Ba in an amount of 0.5 to 2.0 mass% in terms of BaO, and Mg in an amount of 0 to 2.0 mass% in terms of MgO. Carbonates may also be used for Mn, Ba and Mg.

[6]A method for manufacturing a ceramic substrate according to a second aspect of the present invention includes: a molding production step of producing a molded article containing Al and a firing step of firing the molded article at 1250 to 1500 DEG C₂O₃70.0 to 90.0 mass% Al in terms of ZrO₂10.0 to 30.0 mass% in terms of Zr and Al₂O₃And ZrO₂When the total of (A) and (B) is 100 mass%, Mn is contained in an amount of 2.0 to 7.0 mass% in terms of MnO, and SiO is contained in an amount of₂Si in an amount of 2.0 to 7.0 mass% in terms of BaO, Ba in an amount of 0.5 to 2.0 mass% in terms of BaO, and Mg in an amount of 0 to 2.0 mass% in terms of MgO.

[7] In the second invention, the method may further comprise a step of forming a conductor layer containing a metal on the molded body after the step of producing the molded body, and the step of firing the molded body on which the conductor layer is formed may be performed.

[8] In the second invention, the firing step may be performed in a forming gas of hydrogen and nitrogen having a hydrogen content of 5% or more.

According to the ceramic substrate and the method for manufacturing the same of the present invention, the following effects are exhibited.

(a) The flexural strength is high and the Young's modulus is low.

(b) It is also suitable for high frequency circuit board.

(c) The incidence of edge chipping is also small when the chip is divided.

(d) When mounted as a package member or the like, the package member is less likely to be broken by bending stress.

(e) Cracks are not easy to generate during brazing.

(f) The yield can be improved, and the size of a product (such as a ceramic package or a high-frequency circuit board) using a ceramic substrate can be reduced at low cost.

Drawings

Fig. 1 is a cross-sectional view showing a first configuration example (first package) using a ceramic substrate according to the present embodiment.

Fig. 2 is a process block diagram showing the method for manufacturing the ceramic substrate according to the present embodiment together with the method for manufacturing the first package.

Fig. 3 is a cross-sectional view showing a second configuration example (second package) using the ceramic substrate according to the present embodiment.

Fig. 4 is a process block diagram showing a method for manufacturing a ceramic substrate according to the present embodiment together with a method for manufacturing a second package.

Detailed Description

Hereinafter, embodiments of the ceramic substrate and the method for manufacturing the same according to the present invention will be described with reference to fig. 1 to 4. In the present specification, "to" indicating a numerical range is used as meaning including numerical values described before and after the range as a lower limit value and an upper limit value.

Ceramics according to the present embodimentThe crystalline phase of the matrix is formed by Al₂O₃And ZrO₂Is a main crystal phase and contains Mn in addition to₃Al₂(SiO₄)₃Or MgAl₂O₄。

Specifically, it preferably contains: according to Al₂O₃70.0 to 90.0 mass% Al in terms of ZrO₂10.0 to 30.0 mass% in terms of Zr and Al₂O₃And ZrO₂Contains, when the total of (A) and (B) is 100 mass%: mn in an amount of 2.0 to 7.0 mass% in terms of MnO, and SiO₂Si in an amount of 2.0 to 7.0 mass% in terms of BaO, Ba in an amount of 0.5 to 2.0 mass% in terms of BaO, and Mg in an amount of 0 to 2.0 mass% in terms of MgO. This improves the bending strength and realizes a low Young's modulus.

The ceramic base is prepared by, for example, containing 70.0 to 90.0 mass% of Al₂O₃Powder, 10.0-30.0 mass% ZrO₂Powder, MnO powder of 2.0 to 7.0 mass%, SiO₂The molded article is produced by sintering a molded article of 2.0 to 7.0 mass% Si, 0.5 to 2.0 mass% BaO powder, and 0 to 2.0 mass% MgO powder in terms of the total weight of the molded article at 1250 to 1500 ℃.

At this time, as shown in Table 1 below, with respect to Al₂O₃The raw material (Al) is preferred₂O₃Powder) has an average particle size of 0.3 to 2.5 μm and Al in the sintered body₂O₃The crystal grain diameter of (B) is 0.7 to 3.0 μm. Further, it relates to ZrO₂Preference is given to starting materials (ZrO)₂Powder) has an average particle size of 0.05 to 1.0 [ mu ] m and ZrO when formed into a sintered body₂The crystal grain diameter of (B) is 0.05 to 1.0 μm.

TABLE 1

The average particle size of the raw material is a particle size obtained by accumulating (cumulative passage fraction) 50% by the amount of passing from the small particle size side in a volume-based particle size distribution measured by a laser diffraction scattering particle size distribution measuring method (manufactured by HORIBA, L a-920).

The crystal grain size when the sintered body was obtained was as follows. That is, when the surface of the sintered body is photographed by a scanning electron microscope, the magnification of the scanning electron microscope is adjusted so that about 500 to 1000 crystal grains are photographed in the entire photographed image. Then, using image processing software, arbitrary 100 or more crystal particles in the captured image are converted into perfect circles, and the average of the particle diameters is used to calculate the crystal particle diameter.

MnO powder and SiO₂The powder is a sintering aid as a main component, and is added to lower the sintering temperature for forming a glass phase. The BaO powder is for suppressing the formation of MnAl whose hardness is increased₂O₄But is added. The MgO powder is intended to form MgAl, which is a spinel crystal phase having chemical resistance and low electrical loss₂O₄As the electrical characteristics, it is preferable that the dielectric loss tangent at 1MHz be 200 × 10^－4Still more preferably 20 × 10^－4The following. Thus, the ceramic substrate can be preferably used for a high-frequency circuit board. The relative dielectric constant is preferably 10 to 15.

If necessary, the colorant may contain 1.0 mass% or less of Mo (molybdenum) oxide, W (tungsten) oxide, or Cr (chromium) oxide.

Thus, the ceramic body can be sintered at a low temperature of 1250 to 1500 ℃, and can have a bending strength of 650MPa or more and a Young's modulus of 300GPa or less. Specifically, a ceramic substrate having a bending strength of 650MPa to 1100MPa and a Young's modulus of 240GPa to 300GPa can be realized.

However, the ceramic substrate according to the present embodiment is also suitable for a high-frequency circuit board, and even if the bending strength is 650MPa or more, the young's modulus is as low as 300GPa or less, and therefore, the incidence of chipping at the time of chip division is small, and when mounted as a package component or the like, breakage due to bending stress is less likely to occur, and when soldered, cracks are less likely to occur, and the yield can be improved, and downsizing of products (ceramic packages, high-frequency circuit boards, and the like) using the ceramic substrate can be achieved at low cost.

The content of Al is adjusted to Al₂O₃70.0 to 90.0 mass% in terms of Al generated₂O₃The amount of (A) is preferably such that Al can be suppressed even when the firing temperature is increased₂O₃The crystal grain size of (2) is increased, and therefore, the bending strength is easily improved.

By making the Zr content according to ZrO₂The amount of the metal oxide is 10.0 to 30.0% by mass in terms of the amount, and the bending strength is easily improved, and the increase in Young's modulus, the increase in dielectric constant, and the decrease in thermal conductivity can be suppressed.

When the content of Mn is 2.0 to 7.0 mass% in terms of MnO, it is possible to suppress a decrease in the amount of a formed glass phase, to facilitate densification at 1250 to 1500 ℃, and to suppress a decrease in the softening temperature and an increase in the porosity of a formed glass. Further, a decrease in bending strength can be suppressed.

By making the content of Si as SiO₂In terms of 2.0 to 7.0 mass%, the amount of the glass phase produced can be suppressed from decreasing, densification at 1250 to 1500 ℃ can be easily achieved, and a decrease in the softening temperature and an increase in the porosity of the glass produced can be suppressed. Further, a decrease in bending strength can be suppressed.

By setting the Ba content to 0.5-2.0 mass% in terms of BaO, MnAl can be easily suppressed₂O₄Can suppress the decrease in strength. Further, the increase in sintering temperature can be suppressed, the grain growth of alumina and zirconia can be suppressed, and the decrease in strength can be suppressed.

By making the Mg content 0 to 2.0 mass% in terms of MgO, it is possible to suppress the increase in sintering temperature, to suppress grain growth of alumina and zirconia, and to suppress a decrease in strength.

Therefore, by containing Al, Zr, Mn, Si, Ba, and Mg in the above-mentioned ratio, the firing temperature of the porcelain can be optimized, the strength of the generated glass phase can be increased, and as a result, the bending strength is increased, the young's modulus is decreased, and the miniaturization of a product (such as a ceramic package) using a ceramic substrate can be promoted. Moreover, the ceramic can be produced at a low firing temperature, which contributes to cost reduction. Further, the incidence of edge chipping can be reduced when the chips are divided by, for example, a squeeze roller, and productivity can be improved. It is also possible to suppress the electrical characteristics (dielectric loss tangent) to a low level. In addition, if (i) MgO is added or (ii) MgAl is present in the crystalline phase₂O₄Without the presence of Mn₃Al₂(SiO₄)3 or (i) and (ii) above, the dielectric loss tangent is low, and is suitable for use in, for example, a high-frequency circuit board.

Here, 2 configuration examples of the ceramic package using the ceramic substrate according to the present embodiment will be described with reference to fig. 1 to 4.

As shown in fig. 1, a ceramic package according to a first configuration example (hereinafter referred to as a first package 10A) includes a multilayer substrate 12 including a ceramic substrate according to the present embodiment and a lid 14 including a ceramic substrate according to the present embodiment.

The laminated substrate 12 is formed by laminating at least a plate-shaped first substrate 16a, a plate-shaped second substrate 16b, and a frame 18 in this order. The laminated substrate 12 further includes: an upper surface electrode 20 formed on the upper surface of the second substrate 16b, a lower surface electrode 22 formed on the lower surface of the first substrate 16a, an inner layer electrode 24 formed inside, a first through-hole 26a electrically connecting the inner layer electrode 24 and the lower surface electrode 22, and a second through-hole 26b electrically connecting the inner layer electrode 24 and the upper surface electrode 20.

In the first package 10A, a crystal resonator 30 is electrically connected to the upper-surface electrode 20 via a conductor layer 32 in the housing space 28 surrounded by the upper surface of the second substrate 16b and the frame 18. Further, in order to protect the crystal resonator 30, the lid 14 is hermetically sealed to the upper surface of the frame 18 via the glass layer 34.

In the first package 10A, the crystal resonator 30 is mounted in the housing space 28, and in addition, at least 1 or more of a resistor, a filter, a capacitor, and a semiconductor element may be mounted, and in the present embodiment, the dielectric loss tangent is 200 × 10 at 1MHz^－4Hereinafter, it is preferably 20 × 10^－4Hereinafter, therefore, the present invention is also suitable as a high-frequency circuit board.

Since the laminated substrate 12 and the lid 14 constituting the first package 10A are made of the ceramic substrate according to the present embodiment, the flexural strength is 650MPa or more and the young's modulus is 300GPa or less. When the flexural strength is 650MPa or less and the Young's modulus is more than 300GPa, the material is not easily deformed and becomes brittle as described above, and therefore chipping is likely to occur during chip separation. In addition, the lid 14 may be damaged by thermal stress applied thereto at the time of sealing and at the time of secondary mounting. Alternatively, the package may be damaged by an impact or the like during handling or after mounting as a package component or the like.

Such a risk of breakage can be avoided if the flexural strength is 650MPa or more and the young's modulus is 300GPa or less. Further, even if the laminated substrate 12 and the lid 14 of the first package 10A are used without polishing the surface of the ceramic substrate, the lid 14 can be prevented from being broken when hermetically sealed, and the manufacturing cost and reliability of the first package 10A can be improved. The "flexural strength" is a 4-point flexural strength, and is a value measured at room temperature based on JISR1601 (method for flexural testing of fine ceramics).

Further, since the ceramic substrate according to the present embodiment has the above composition, it can be sintered at a low temperature of 1250 to 1500 ℃. Therefore, by simultaneously firing the ceramic substrate precursor (the molded body before firing), the electrodes (the upper surface electrode 20, the lower surface electrode 22, and the inner layer electrode 24), and the through-holes 26 (the first through-holes 26a and the second through-holes 26b), the laminated substrate 12 can be produced, and the production process can be simplified.

Next, a method for manufacturing a ceramic substrate will be described with reference to fig. 2, for example, according to a method for manufacturing the first package 10A.

First, in step S1a of FIG. 2, a composition containing 70.0 to 90.0 mass% of Al is prepared₂O₃Powder, 10.0-30.0 mass% ZrO₂Powder, MnO powder of 2.0 to 7.0 mass%, SiO₂In terms of a mixed powder of 2.0 to 7.0 mass% of Si, 0.5 to 2.0 mass% of BaO powder, and 0 to 2.0 mass% of MgO powder, an organic component (binder) is prepared in step S1b, and a solvent is prepared in step S1 c.

Al₂O₃The average particle size of the powder is preferably 0.3 to 2.5. mu.m. ZrO (ZrO)₂The average particle size of the powder is preferably 0.05 to 1.0. mu.m. Within this range, it is preferable to obtain a uniform porcelain, and the strength can be improved by densification, so that Al can be realized₂O₃And ZrO₂The self-sinterability is improved.

The average particle size of MnO powder is preferably 0.5 to 4.0 μm. SiO 2₂The average particle size of the powder is preferably 0.1 to 2.5. mu.m. The average particle size of the BaO powder is preferably 0.5 to 4.0 μm. The average particle size of the MgO powder is preferably 0.1 to 1.0. mu.m.

For these MnO powders, SiO₂If the powder, BaO powder, and MgO powder are within the preferred ranges, the dispersibility of the particles can be improved, the composition can be made uniform, and the strength can be improved.

Examples of the organic component (binder) prepared in step S1b include a resin, a surfactant, and a plasticizer. Examples of the resin include polyvinyl butyral, examples of the surfactant include tertiary amines, and examples of the plasticizer include phthalates (e.g., diisononyl phthalate: DINP).

Examples of the solvent to be prepared in step S1c include an alcohol solvent and an aromatic solvent. The alcohol solvent may be, for example, IPA (isopropyl alcohol), and the aromatic solvent may be, for example, toluene.

Then, in the next step S2, the organic component and the solvent are mixed and dispersed in the mixed powder, and then, in step S3, a ceramic molded body (also referred to as a ceramic tape) as a ceramic matrix precursor is produced by a known molding method such as an extrusion method, a doctor blade method, a rolling method, or an injection method. For example, a slurry is prepared by adding an organic component and a solvent to the mixed powder, and then a ceramic tape having a predetermined thickness is produced by the doctor blade method. Alternatively, a ceramic tape having a predetermined thickness is produced by adding an organic component to the mixed powder, and performing extrusion molding, calender molding, or the like.

In step S4, the ceramic tape is cut and processed into a desired shape to produce a first large-area tape for the first substrate, a second large-area tape for the second substrate, a third tape for the frame, and a fourth tape for the lid, and further through holes for forming the first through holes 26a and the second through holes 26b are formed by punching using a die, micro-drilling, laser processing, or the like.

Next, in step S5, the first tape and the second tape produced as described above are printed and applied with a conductor paste for forming the upper surface electrode 20, the lower surface electrode 22, and the inner layer electrode 24 by a method such as screen printing or gravure printing, and the conductor paste is filled into the through hole as necessary.

The conductor paste preferably contains, as a conductor component, at least 1 kind of high-melting-point metal such as W (tungsten) and Mo (molybdenum), and Al is added thereto in a proportion of, for example, 1 to 20 mass%, particularly 8 mass% or less₂O₃Powder, or SiO₂A conductive paste of a powder or the same powder as the ceramic substrate. This can improve the adhesion between the alumina sintered body and the conductor layer while maintaining the on-resistance of the conductor layer at a low level, and can prevent defects such as plating layer defects from occurring.

Then, in step S6, the first tape and the second tape on which the conductor paste is printed and the third tape for the frame are aligned, laminated and pressure bonded, and a laminate is produced.

Then, in step S7, dividing grooves for dividing the chips are formed on both surfaces of the laminated body by, for example, knife cutting.

In the next step S8, the laminate and the fourth tape are placed in a forming gas atmosphere of hydrogen and nitrogen having a hydrogen content of 5% or more, for example, H₂/N₂＝30％/7Firing is carried out in a 0% forming gas atmosphere (at a humidifier temperature of 25-47 ℃) at a temperature of 1250-1500 ℃. In this way, a laminated body and a laminated raw plate (multi-electronic component substrate) in which the conductor paste is simultaneously fired are produced. By this firing, Al as the crystal phase can be produced₂O₃And ZrO₂Is a main crystal phase and contains Mn in addition to₃Al₂(SiO₄)₃Or MgAl₂O₄The ceramic substrate of (3), namely, a multiple electronic component substrate.

Since the atmosphere in which firing is performed is the forming gas atmosphere as described above, oxidation of the metal in the conductor paste can be prevented. The firing temperature is preferably within the above-mentioned range. Densification can be promoted, and the bending strength can be improved. Further, the variation in the shrinkage rate of the first tape, the second tape, and the third tape constituting the laminate can be reduced, and the dimensional accuracy and the cost efficiency can be improved. Since the firing temperature does not need to be increased, the cost of equipment for the firing is not required to be increased.

Further, Al in the case of forming a sintered body₂O₃The crystal grain diameter of (2) is preferably 0.7 to 3.0 μm, and ZrO when formed into a sintered body₂The crystal grain size of (2) is preferably 0.05 to 1.0 μm. If the content is within this range, a uniform porcelain can be obtained, and preferably, the strength can be improved by densification to realize Al₂O₃And ZrO₂The self-sinterability is improved.

Next, in step S9, the multi-electronic component substrate is subjected to plating treatment, a plating layer made of at least 1 of Ni, Co, Cr, Au, Pd, and Cu is formed on the conductor layer formed on the surface of the multi-electronic component substrate, and the plurality of upper surface electrodes 20 and the plurality of lower surface electrodes 22 are formed on the surface of the multi-electronic component substrate.

Then, in step S10, the multiple electronic component substrate is divided into a plurality of pieces (chip division) by being pressed against with a pressing roller or the like, and a plurality of laminated substrates 12 having the housing space 28 are produced. In step S11, the crystal oscillators 30 are mounted on the upper surface electrodes 20 via the conductor layers 32 in the respective housing spaces 28 of the plurality of laminated substrates 12.

Then, in step S12, the upper surface of each laminate substrate 12 is hermetically sealed (lid-bonded) with the ceramic lid 14 having the sealing glass layer 34 formed thereon, thereby completing a plurality of first packages 10A in which the crystal oscillators 30 are mounted.

In the method for manufacturing the first package 10A (method for manufacturing a ceramic substrate), Al can be formed as the crystal phase as described above₂O₃And ZrO₂Containing Mn in addition to the main crystal phase₃Al₂(SiO₄)₃Or MgAl₂O₄The ceramic substrate of (1) is also suitable for a high-frequency circuit board, and has a bending strength of 650MPa or more and a Young's modulus of 300GPa or less. Further, the ceramic substrate can be manufactured at a low firing temperature, which has a low incidence of chipping when the chip is divided, can improve the yield, and can realize the miniaturization of products (such as ceramic packages and high-frequency circuit boards) using the ceramic substrate at a low cost.

Next, a ceramic package according to a second configuration example (hereinafter referred to as a second package 10B) will be described with reference to fig. 3 and 4.

The second package 10B has almost the same configuration as the first package 10A as shown in fig. 3, but differs from the first package 10A in the following point.

That is, the metal lid 40 is hermetically sealed to the frame 18 of the laminated substrate 12 using a high-temperature sealing material 42 such as silver solder.

Further, a bonding layer 44 is present between the upper surface of the frame 18 of the laminated substrate 12 and the high-temperature sealing material 42. The bonding layer 44 has a metallization layer 46 made of the same material as the upper electrode 20, for example, a nickel (Ni) electrolytic plating layer 48 formed on the metallization layer 46, and for example, a gold (Au) electroless plating layer 50 formed on the Ni electrolytic plating layer 48, on the upper surface of the frame 18.

The metal lid 40 is formed in a flat plate shape having a thickness of 0.05 to 0.20mm, and is formed of an iron-nickel alloy plate or an iron-nickel-cobalt alloy plate. On the lower surface (the entire surface or a portion corresponding to the frame 18) of the metal lid 40, a solder such as a silver-copper eutectic solder is formed as a high-temperature sealing material 42. The thickness is about 5 to 20 μm.

Specifically, the metal lid 40 is manufactured by punching a composite plate, which is formed by laminating a solder foil such as silver-copper solder on the lower surface of an iron-nickel alloy plate or an iron-nickel-cobalt alloy plate and rolling the laminated plate, into a predetermined shape by a punching die.

The high-temperature sealing material 42 may be solder 1(85 Ag-15 Cu), solder 2(72 Ag-28 Cu), solder 3(67 Ag-29 Cu-4 Sn) shown in Table 2 below, or the like.

TABLE 2

The Ni electrolytic plating layer 48 and the Au electroless plating layer 50 function as layers for improving the wettability of the high-temperature sealing material 42 to the metallized layer 46.

Next, a method for manufacturing the second package 10B will be described with reference to fig. 4. The steps overlapping with those in fig. 2 will not be described.

First, in step S101 of fig. 4, a mixed powder, an organic component, and a solvent for producing a ceramic tape are prepared. The prepared mixed powder, organic components and solvent are the same as in step S1a, step S1b and step S1c, and therefore, a repeated explanation thereof is omitted.

Then, in step S102, the organic component and the solvent are mixed and dispersed in the mixed powder, and then, in step S103, a ceramic compact (ceramic tape) as a ceramic matrix precursor is produced by a known molding method such as an extrusion method, a doctor blade method, a rolling method, or an injection method.

In step S104, the ceramic tape is cut and processed into a desired shape to produce a first large-area tape for the first substrate 16a, a second large-area tape for the second substrate 16b, and a third tape for the frame 18, and through holes for forming the first through holes 26a and the second through holes 26b are formed by micro drill processing, laser processing, or the like.

On the other hand, in step S105, a raw material powder, an organic component and a solvent for the conductor paste are preparedAnd (3) preparing. As described above, the raw material powder to be prepared includes at least 1 kind of metal powder such as W (tungsten), Mo (molybdenum), nickel (Ni) and the like, and Al is added thereto in an appropriate amount of, for example, 1 to 20 mass%, particularly 8 mass% or less₂O₃Powder, or SiO₂Powder or mixed powder of the same powder as the ceramic substrate. Examples of the organic component to be prepared include a resin (for example, ethyl cellulose) and a surfactant. Examples of the solvent to be prepared include terpineol (terpineol).

Then, in step S106, the organic component and the solvent are mixed and dispersed in the mixed powder to prepare a conductor paste.

Next, in step S107, the first to third tapes prepared as described above are printed and coated with the conductor paste by a method such as screen printing or gravure printing.

Then, in step S108, the first to third tapes on which the conductor paste is printed are aligned, laminated, and pressure-bonded to prepare a laminate.

Then, in step S109, dividing grooves for dividing the chips are formed on both surfaces of the laminated body by, for example, knife cutting.

In the next step S110, the laminate is set at H₂/N₂Firing is carried out in a molding gas atmosphere (humidifier temperature 25-47 ℃) of 30%/70% at a temperature range of 1250-1500 ℃. In this way, a laminated body and a laminated raw plate (multi-electronic component substrate) in which the conductor paste is simultaneously fired are produced. The multiple electronic component substrate has a shape in which a plurality of frames 18 are arranged integrally. By this firing, the conductor paste becomes an electrode (upper surface electrode 20, etc.) and a metallization layer 46.

In the next step S111, at least the surface of the metallized layer 46 is cleaned with alkali, acid, or the like (pretreatment). That is, after the alkali cleaning, the acid cleaning is performed. In the pretreatment, the base and the acid may be diluted to appropriate concentrations for use. The pretreatment is carried out at a temperature of about 20 to 70 ℃ for several minutes to several tens of minutes.

In step S112, Ni plating layer 48 (film thickness: 1.0 to 5.0 μm) is formed on metallization layer 46 by performing Ni electrolysis or electroless plating.

In step S113, an Au electrolytic or electroless plating layer 50 (film thickness: 0.05 to 0.3 μm) is formed on the Ni plating layer 48.

Then, in step S114, the multi-electronic component substrate is divided into a plurality of parts (chip division) by pressing with a squeegee or the like, and a plurality of laminated substrates 12 each having the housing space 28 are produced. Then, in step S115, the crystal oscillators 30 are mounted on the upper surface electrodes 20 via the conductor layers 32 in the respective housing spaces 28 of the plurality of laminated substrates 12.

Then, in step S116, the high-temperature sealing material 42 is opposed to the upper surface (bonding layer 44) side of the frame 18, and the frame 18 is covered with the metal lid 40 having the high-temperature sealing material 42 formed on the back surface. Then, the pair of roller electrodes of the seam welder are rotated while being brought into contact with the outer peripheral edges of the metal lid 40 facing each other, and a current is passed between the roller electrodes to melt a part of the high-temperature sealing material 42, thereby hermetically sealing the metal lid 40 to the frame 18. As the atmosphere in sealing, in N₂Sealing is performed in gas or vacuum. This completes the plurality of second packages 10B in which the crystal oscillators 30 are mounted.

Examples

In examples 1 to 12 and comparative examples 1 and 2, Al of the ceramic substrate was confirmed₂O₃And ZrO₂Other crystal phases, mechanical properties (flexural strength) and Young's modulus), and electrical properties (relative permittivity and dielectric loss tangent).

(example 1)

Raw material powder was prepared. The raw material powder was Al having an average particle diameter of 1.70 μm₂O₃Powder, ZrO having an average particle size of 0.50 μm₂Powder, MnO powder having an average particle diameter of 1.0 μm, SiO powder having an average particle diameter of 1.0 μm₂Powder, BaO powder having an average particle diameter of 1.0. mu.m.

The raw material powders were mixed in the proportions (Al) shown in Table 3 below₂O₃Powder: 78.60 mass% ZrO₂Powder: 21.40 mass%, MnO powder: 3.04% by mass of SiO₂Powder: 2.78 mass%, BaO powder: 0.77 mass%) was mixed to obtain a mixed powder. The obtained mixed powder is mixed with polyvinyl butyral, a tertiary amine and a phthalic acid ester (diisononyl phthalate: DINP) as organic components, IPA (isopropyl alcohol) and toluene as solvents are mixed and diffused to prepare a slurry, and then a ceramic tape having a thickness of 60 to 270 μm is produced by a doctor blade method. The obtained ceramic tape was fired at 1440 ℃ C (maximum temperature) H₂+N₂The ceramic substrate of example 1 was prepared by firing in the molding gas atmosphere of (1). The conductor is formed by simultaneous firing. As the ceramic substrates, a first ceramic substrate for confirming a crystal phase, a second ceramic substrate for confirming a bending strength, a third ceramic substrate for confirming a young's modulus, and a fourth ceramic substrate for measuring electrical characteristics (relative permittivity and dielectric loss tangent) were prepared. The same applies to examples 2 to 12 and comparative examples 1 and 2 described below.

(example 2)

In the raw material powder, MnO powder was 2.81 mass% and SiO was used₂A ceramic substrate according to example 2 was produced in the same manner as in example 1 above, except that the powder was 2.57 mass%, the BaO powder was 0.71 mass%, and the MgO powder was 0.54 mass%.

(example 3)

In the raw material powder, Al is added₂O₃The powder was 89.30 mass% to obtain ZrO₂The ceramic substrate according to example 3 was produced in the same manner as in example 2, except that the amount of the powder was 10.70 mass%.

(example 4)

MnO powder was 3.34 mass% and SiO in the raw material powder₂A ceramic substrate according to example 4 was produced in the same manner as in example 1 above, except that the powder was 2.04 mass%, the BaO powder was 0.71 mass%, and the MgO powder was 0.54 mass%.

(example 5)

In the raw material powder, MnO powder was 2.27 mass% and SiO was used₂The powder was 3.11 mass%, the BaO powder was 0.71 mass%, and the MgO powder was 0 mass%.The ceramic substrate according to example 5 was produced in the same manner as in example 1 except that the amount of the inorganic filler was 54 mass%.

(example 6)

In the raw material powder, MnO powder was 2.44 mass% and SiO was used₂A ceramic substrate according to example 6 was produced in the same manner as in example 1 above, except that the powder was 2.23 mass%, the BaO powder was 1.42 mass%, and the MgO powder was 0.54 mass%.

(example 7)

In the raw material powder, MnO powder was 2.57 mass% and SiO was used₂A ceramic substrate according to example 7 was produced in the same manner as in example 1 above, except that the powder was 2.35 mass%, the BaO powder was 0.64 mass%, the MgO powder was 1.07 mass%, and the firing temperature (maximum temperature) was 1470 ℃.

(example 8)

MnO powder was 4.36 mass% and SiO was added to the raw material powder₂A ceramic substrate according to example 8 was produced in the same manner as in example 1 above, except that the powder was 4.00 mass%, the BaO powder was 1.11 mass%, the MgO powder was 0.83 mass%, and the firing temperature (highest temperature) was 1390 ℃.

(example 9)

In the raw material powder, Al is added₂O₃70.00% by mass of powder to ZrO₂A ceramic substrate according to example 9 was produced in the same manner as in example 8 above, except that the amount of the powder was 30.00 mass%.

(example 10)

In the raw material powder, Al is added₂O₃The ceramic substrate of example 10 was produced in the same manner as in example 2 except that the average particle size of the powder was 0.50 μm and the firing temperature (maximum temperature) was 1390 ℃.

(example 11)

In the raw material powder, MnO powder was 6.04 mass% and SiO was used₂5.53 mass% of powder, 1.53 mass% of BaO powder, 1.15 mass% of MgO powder, and firingThe ceramic substrate according to example 11 was produced in the same manner as in example 10 described above, except that the forming temperature (highest temperature) was 1310 ℃.

(example 12)

In the raw material powder, Al is added₂O₃70.00% by mass of powder to ZrO₂A ceramic substrate according to example 12 was produced in the same manner as in example 10 above, except that the amount of the powder was 30.00 mass%.

Comparative example 1

In the raw material powder, Al is added₂O₃The powder was 75.80 mass% to obtain ZrO₂Powder content 24.20% by mass, MnO powder 0.00% by mass (not added), SiO₂A ceramic substrate according to comparative example 1 was produced in the same manner as in example 1, except that the powder was 0.60 mass%, the BaO powder was 0.00 mass% (not added), the MgO powder was 0.10 mass%, and the firing temperature (highest temperature) was 1500 ℃.

Comparative example 2

In the raw material powder, Al is added₂O₃Powder 80.00 mass% to ZrO₂A ceramic substrate according to comparative example 2 was produced in the same manner as in comparative example 1, except that the amount of the powder was 20.00 mass% and the firing temperature (maximum temperature) was 1580 ℃.

(evaluation)

< identification of crystalline phase >

The first ceramic substrates of examples 1 to 12 and comparative examples 1 and 2 were identified by X-ray diffraction. As a criterion for determining whether or not a crystal phase is included, the intensity of a main peak (104 crystal plane) of alumina has a main peak intensity of 3% or more. That is, the crystal phase included is confirmed based on the position (peak position) having 3% or more of the main peak intensity with respect to the intensity of the main peak of alumina, the miller index, the lattice constant, and the like.

< flexural Strength >

The second ceramic substrates of examples 1 to 12 and comparative examples 1 to 2 were each measured at room temperature based on the 4-point bending strength test of JISR 1601.

< Young's modulus >

The third ceramic substrates of examples 1 to 12 and comparative examples 1 to 2 were measured at room temperature by the JISR1602 static modulus test method.

< relative dielectric constant >

The fourth ceramic substrates of examples 1 to 12 and comparative examples 1 to 2 were measured using the capacitance method of jis c2138 at a frequency of 1MHz at room temperature.

< dielectric loss tangent >

The details of examples 1 to 12 and comparative examples 1 and 2 are shown in table 3, and the evaluation results are shown in table 4. In table 4, the relative dielectric constant of the electrical characteristics is represented by "r", and the dielectric loss tangent is represented by "tan".

TABLE 3

TABLE 4

In examples 1 to 12, the flexural strength (flexural strength) was 650MPa or more and the Young's modulus was 300GPa or less. Further, Al of the sintered body₂O₃Has a crystal grain diameter of 0.7 to 3.0 μm and ZrO₂The crystal grain diameter of (B) is 0.05 to 1.0 μm.

Also, for example 1, as the crystal phase, except for Al₂O₃And ZrO₂In addition, only Mn was observed₃Al₂(SiO₄)₃. Because of this relationship, the electrical characteristics, particularly the dielectric loss tangent, were 170, which is inferior to those of the other examples 2 to 12. As for the mechanical properties, the flexural strength was as high as 720MPa, and the Young's modulus was as low as 268GPa, which gave good results.

The bending strength in mechanical properties was 1030MPa for example 12, and the results were the best for examples 1 to 12. The Young's modulus in the mechanical properties of example 9 was 249GPa, and the results were the best in examples 1 to 12. The dielectric loss tangents in the electrical characteristics of examples 3 and 10 were 17 and 15, and the results were the best in examples 1 to 12.

In examples 2, 4 to 8, and 11, the bending strength in the mechanical properties was in the range of 700 to 910MPa, and the Young's modulus in the mechanical properties was in the range of 255 to 300GPa, which is excellent. The dielectric loss tangent in the electrical characteristics is also in the range of 20 to 40, and the results are good.

In example 6, the crystal phase was changed to Al₂O₃And ZrO₂In addition, MgAl is observed₂O₄And BaAl₂Si₂O₈。

On the other hand, in comparative examples 1 and 2, as the crystal phase, except for Al₂O₃And ZrO₂In addition, no other crystalline phases were observed. With respect to the mechanical properties, in comparative example 1, the flexural strength was 970MPa, which is higher than that of example 10, but the Young's modulus was up to 336 GPa. For comparative example 2, the Young's modulus was as high as 324GPa, although the flexural strength was 650MPa, which is lower than that of example 1.

The ceramic substrate and the method for manufacturing the same according to the present invention are not limited to the above embodiments, and it is needless to say that various configurations can be adopted without departing from the gist of the present invention.

Claims

1. A ceramic substrate characterized in that,

the crystalline phase of the ceramic matrix is Al₂O₃And ZrO₂Is a main crystal phase and contains Mn in addition to₃Al₂(SiO₄)₃Or MgAl₂O₄，

And the ceramic substrate has a bending strength of 650MPa or more as measured at room temperature by the JISR 1601-based 4-point bending strength test, and a Young's modulus of 300GPa or less as measured at room temperature by the JISR1602 static modulus of elasticity test,

the ceramic base is manufactured by a manufacturing method including the steps of:

a step of producing a molded body containing Al₂O₃70.0 to 90.0 mass% Al in terms of ZrO₂10.0 to 30.0 mass% in terms of Zr and Al₂O₃And ZrO₂When the total of (A) and (B) is 100 mass%, Mn is contained in an amount of 2.0 to 7.0 mass% in terms of MnO, and SiO is contained in an amount of₂2.0 to 7.0 mass% of Si in terms of BaO, 0.5 to 2.0 mass% of Ba in terms of BaO, and 0 to 2.0 mass% of Mg in terms of MgO;

and a firing step of firing the molded article at 1250 to 1500 ℃.

2. Ceramic substrate according to claim 1,

the bending strength of the ceramic base body is 650MPa to 1100MPa, and the Young modulus is 240GPa to 300 GPa.

3. Ceramic substrate according to claim 1,

the ceramic substrate has a dielectric loss tangent of 200 × 10 at 1MHz measured at room temperature at a frequency of 1MHz in accordance with the electrostatic capacity of JISC2138^－4The relative permittivity measured at room temperature at a frequency of 1MHz in accordance with the capacitance method of JISC2138 is 10 to 15.

4. A method for manufacturing a ceramic substrate according to claim 1, comprising:

a step of producing a molded body containing Al₂O₃70.0 to 90.0 mass% Al in terms of ZrO₂10.0 to 30.0 mass% in terms of Zr and Al₂O₃And ZrO₂When the total of (A) and (B) is 100 mass%, the composition containsMn in an amount of 2.0 to 7.0 mass% in terms of MnO, and SiO₂2.0 to 7.0 mass% of Si in terms of BaO, 0.5 to 2.0 mass% of Ba in terms of BaO, and 0 to 2.0 mass% of Mg in terms of MgO;

and a firing step of firing the molded article at 1250 to 1500 ℃.

5. A ceramic substrate manufacturing method as defined in claim 4,

a step of forming a conductor layer containing a metal on the molded body after the molding body production step,

in the firing step, the molded body on which the conductor layer is formed is fired.

6. A ceramic substrate manufacturing method as defined in claim 4,

the firing step is performed in a forming gas of hydrogen and nitrogen having a hydrogen content of 5% or more.