CN103732558B - Aluminum oxide pottery and use its ceramic wiring board and ceramic package - Google Patents

Aluminum oxide pottery and use its ceramic wiring board and ceramic package Download PDF

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CN103732558B
CN103732558B CN201280039604.6A CN201280039604A CN103732558B CN 103732558 B CN103732558 B CN 103732558B CN 201280039604 A CN201280039604 A CN 201280039604A CN 103732558 B CN103732558 B CN 103732558B
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crystalline phase
aluminum oxide
quality
pottery
oxide pottery
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CN103732558A (en
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东登志文
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Kyocera Corp
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Kyocera Corp
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
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    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
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    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
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    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
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    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/02—Containers; Seals
    • H01L23/06—Containers; Seals characterised by the material of the container or its electrical properties
    • H01L23/08—Containers; Seals characterised by the material of the container or its electrical properties the material being an electrical insulator, e.g. glass
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
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    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention provides the high aluminum oxide pottery of a kind of physical strength and apply its wiring substrate and ceramic package.Using aluminium sesquioxide as principal constituent, contain with Mn 2o 3be scaled 2.0 ~ 5.0 quality % manganese and with SiO 2be scaled the silicon of 3.0 ~ 7.5 quality %, analyzing what try to achieve by the Rietveld of X-ray diffraction take aluminium sesquioxide as the ratio of the crystalline phase of principal constituent is 99.0 ~ 99.9 quality %, and the median size of crystalline phase is 0.8 ~ 1.5 μm, and the area ratio of the hole of per unit area is less than 3.1%.

Description

Aluminum oxide pottery and use its ceramic wiring board and ceramic package
Technical field
The present invention relates to the ceramic wiring board and the ceramic package that are applicable to require the aluminum oxide of the insulated substrate of high strength pottery and apply this aluminum oxide pottery.
Background technology
In the past, as the wiring substrate that the packaged piece for receiving the electronic unit such as semiconductor element, quartz crystal unit uses, from the view point of the higher and resistance to air loss excellence of physical strength, multiplex ceramic wiring board.
In Fig. 2, show an example of the exploded perspective view of the ceramic package for carrying electronic unit.Ceramic package for carrying the electronic units such as crystal application products is formed as follows, such as, conductor 102 is formed on the surface of the ceramic substrate 101 comprising aluminum oxide sintered compact, for to the electronic unit of the surface mounting at this conductor 102 (such as, crystal application products) 109 carry out the hardware 105(of gas-tight seal at this, for lid 105) formation (for example, referring to patent documentation 1) that engages via engagement members 107 such as the silver solders being coated on metal layer 103.
The applicant, before, as the baseplate material being applicable to this ceramic package, has proposed the aluminum oxide pottery (for example, referring to patent documentation 2, patent documentation 3) of the easy fired type that simultaneously can burn till with copper system conductor.
In recent years, the mobile electronic device such as mobile phone, IC-card is popularized gradually, these electronicss require all the more miniaturization, slimming and high performance, therefore, load the electronic unit 109 in these electronicss or also require further miniaturization and slimming for the ceramic package of housing electronic parts.
When carrying out miniaturization and the slimming of ceramic package, need to make formation be positioned at the thickness t of the B.B.P 101a of the ceramic substrate 101 of ceramic package bottom surface and become the width w of substrate dyke 101b of the part engaged by lid 105 0narrow.
But, at the thickness t of B.B.P 101a and the width w of substrate dyke 101b 0such as, when becoming very thin and reach below 0.5mm, even if apply above-mentioned baseplate material, the B.B.P 101a or the substrate dyke 101b that still there is ceramic substrate 101 when engaging lid 105 are out of shape, and the problem of crackle occurs thus on ceramic substrate 101.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2001-196485 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-101238 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2006-100364 publication
Summary of the invention
Invent problem to be solved
Therefore, the wiring substrate of the object of the invention aluminum oxide pottery of being to provide physical strength high and the high strength of applying it and ceramic package.
For solving the method for problem
The feature of aluminum oxide pottery of the present invention is, take aluminium sesquioxide as principal constituent, contains with Mn 2o 3be scaled 2.0 ~ 5.0 quality % manganese and with SiO 2be scaled the silicon of 3.0 ~ 7.5 quality %, analyzing what try to achieve by the Rietveld of X-ray diffraction is 99.0 ~ 99.9 quality % with the ratio of the described aluminium sesquioxide crystalline phase that is principal constituent, and the median size of described crystalline phase is 0.8 ~ 1.5 μm, and the area ratio of the hole of per unit area is less than 3.1%.
The feature of ceramic wiring board of the present invention is, it forms by having metal layer on insulated substrate surface, and described insulated substrate is made up of above-mentioned aluminum oxide pottery.
The feature of ceramic package of the present invention is, it is by forming via engagement member jointing metal component on the surface of insulated substrate, and described insulated substrate is made up of above-mentioned aluminum oxide pottery.
Invention effect
According to the present invention, the aluminum oxide pottery that physical strength is high can be obtained.In addition, by being applied as the material of insulated substrate by such aluminum oxide pottery, ceramic wiring board and the ceramic package of high strength can be obtained.
Accompanying drawing explanation
Fig. 1 is the exploded perspective view of the embodiment representing ceramic package of the present invention.
Fig. 2 is the exploded perspective view of an embodiment of the ceramic package represented in the past.
Embodiment
Below, the mode of enforcement of the present invention is described.The aluminum oxide pottery of present embodiment is principal constituent with aluminium sesquioxide, contains with Mn 2o 3be scaled 2.0 ~ 5.0 quality % manganese and with SiO 2be scaled the silicon of 3.0 ~ 7.5 quality %.
In addition, with regard to this aluminum oxide pottery, analyzing what try to achieve by the Rietveld of X-ray diffraction take aluminium sesquioxide as the ratio of the crystalline phase of principal constituent is 99.0 ~ 99.9 quality %.
And, with regard to this aluminum oxide pottery, be that the crystalline phase of principal constituent is (hereinafter referred to as alumina crystalline phase with aluminium sesquioxide.) median size be 0.8 ~ 1.5 μm, and the area ratio of the hole of per unit area is less than 3.1%.
Aluminum oxide pottery according to the present embodiment, although except as except the aluminium sesquioxide of principal constituent also containing the manganese of a great deal of and silicon, but as the ratio of the alumina crystalline phase of principal crystalline phase up to more than 99 quality %, in addition, the median size of this crystalline phase is little and the area ratio of hole is also little, therefore become the material of mechanical characteristics excellence, the aluminum oxide pottery that 3 flexural strengths are more than 680MPa can be realized.
Usually, if make containing auxiliary components such as manganese oxide in aluminium sesquioxide, then on the crystal boundary of the alumina crystalline phase of the aluminum oxide pottery as porcelain, such as, easily formed and be derived from MnAl 2o 4deng the crystalline phase of composite oxides, but in the aluminum oxide pottery of present embodiment, make the ratio of the discernible crystalline phase that the crystal boundary of alumina crystalline phase exists at below 1 quality %, form alumina crystalline phase by being derived from the amorphous phase of manganese oxide or silicon oxide and the state that sinters, therefore other different compared to crystalline texture crystalline phases and alumina crystalline phase adjoin the situation of existence, the development of the transformation between crystalline phase is suppressed, can realize the high strength of the aluminum oxide pottery as sintered compact thus.At this, alumina crystalline phase is present in porcelain in the mode forming particulate state crystal grain.
On the other hand, when the ratio 99.0 quality % that the Rietveld by X-ray diffraction analyzes the alumina crystalline phase of trying to achieve is low, crystalline phase in aluminum oxide pottery beyond alumina crystalline phase will exist in a large number, therefore, and the physical strength step-down of aluminum oxide pottery thus.
When the ratio 99.9 quality % that the Rietveld by X-ray diffraction analyzes the alumina crystalline phase of trying to achieve is high, owing to becoming the quite few state of the sintering aid such as manganese oxide and silicon oxide amount, therefore alumina crystalline phase bonding force each other reduces, and also there is the trend that physical strength reduces in this situation.
The content of the manganese contained in aluminum oxide pottery is with Mn 2o 3the ratio meter converted is less than 2.0 quality % or SiO 2when the content of the silicon converted is less than 3.0 quality %, because the component amount becoming sintering aid tails off, therefore on the crystal boundary of alumina crystalline phase, part not throughout sintering aid becomes many, in addition, be easy to grain growing occurs because alumina crystalline phase self also becomes, therefore this situation also can cause physical strength to reduce.
The content of the manganese contained in aluminum oxide pottery is with Mn 2o 3convert more than 5.0 quality % or SiO 2when the content of the silicon converted is more than 7.5 quality %, the ratio of the alumina crystalline phase as high-strength material in aluminum oxide pottery tails off, and therefore, also there is the trend that physical strength reduces in this case.
In addition, when the median size of alumina crystalline phase is beyond 0.8 ~ 1.5 μm of scope, the physical strength of aluminum oxide pottery also reduces.At this; think that the reason that physical strength reduces when the median size of alumina crystalline phase is less than 0.8 μm is; alumina crystalline phase micronize, specific surface area becomes large, therefore for the crystal boundary of alumina crystalline phase existence not throughout the part of the auxiliary agent such as manganese oxide, silicon oxide.
Think that the reason that physical strength reduces when the median size of alumina crystalline phase is greater than 1.5 μm is, if the size that there is the source of destruction becomes large, the trend that ceramic physical strength reduces, if the median size of alumina crystalline phase becomes large, the size in the destruction source produced when being subject to load becomes greatly.
In addition, when the area ratio of the hole of the per unit area of this aluminum oxide pottery is greater than 3.1%, the size of break source also becomes large, therefore causes physical strength to reduce.
At this, the ratio of the crystalline phase contained in aluminum oxide pottery is tried to achieve as follows, that is, carry out X-ray diffraction to aluminum oxide pottery is pulverized the pulverous sample obtained, Rietveld analysis is carried out to the X-ray diffraction pattern obtained, and then tries to achieve the mass ratio of each crystalline phase.
The content of each composition contained in aluminum oxide pottery can by atomic absorption analysis and ICP(InductivelyCoupledPlasma) analyze and try to achieve.Now, the aluminum oxide pottery of gained is dissolved in acidic solution, the qualitative analysis of element contained in aluminum oxide pottery is carried out by atomic absorption analysis, then, the liquid obtained by dilution standard liquid, as standard test specimen, utilizes ICP Emission Spectrophotometer to carry out quantification to specific element.It should be noted that, the valence mumber according to each element shown in the periodic table of elements tries to achieve oxygen level.
The median size of alumina crystalline phase is tried to achieve as follows, that is, for the abrasive surface after the section grinding of the sample by aluminum oxide pottery, utilize scanning electron microscope to take the photo of 1000 ~ 5000 times, then, utilize this photo to be tried to achieve by intercept method.
The area ratio of hole is tried to achieve as follows, namely, after the surperficial mirror ultrafinish of aluminum oxide pottery, utilize image analysis apparatus to try to achieve the total area of viewed hole (perforate) in the regulation area being set to range of observation, and then try to achieve the ratio of this total area relative to range of observation and regulation area.
Physical strength is tried to achieve by the method based on JIS-R1601.
As mentioned above, with regard to the aluminum oxide pottery of present embodiment, even if added ingredientss such as the manganese containing a great deal of and silicon, the crystalline phase still formed beyond alumina crystalline phase generates the crystal structure be suppressed, therefore the material of mechanical characteristics excellence is become, in this aluminum oxide pottery, be respectively Mn making the composition formula of manganese and silicon 2o 3and SiO 2time, make Mn 2o 3/ (Mn 2o 3+ SiO 2) represented by mass ratio be 30 ~ 50%, and, making above-mentioned aluminum oxide pottery containing magnesium and molybdenum, make the content of magnesium be scaled 0.3 ~ 0.7 quality % with MgO, when making the content of molybdenum be scaled 0.3 ~ 0.7 quality % with MoO and make porosity be less than 3.0%, the physical strength of aluminum oxide pottery (3 flexural strengths) can be made to be more than 700MPa.
In addition, the aluminum oxide that should form pottery, except manganese and silicon, also even adjusts the composition of magnesium and molybdenum, therefore can make the beautiful pottery without irregular colour (comprising porcelain bleeding (chinaware シ ミ)), outward appearance with intention.
In addition, using the aluminum oxide of this formation pottery as aftermentioned such insulated substrate, its surface formed metal layer time, can Metallization strength be improved.
And then, in this aluminum oxide pottery, at Mn 2o 3/ (Mn 2o 3+ SiO 2) represented by mass ratio when being 30 ~ 40%, 3 flexural strengths can be brought up to more than 710MPa.Now, what it is desirable to contain in aluminum oxide pottery take aluminium sesquioxide as the ratio of the crystalline phase of principal constituent is 99.2 ~ 99.9 quality %.
As mentioned above, the aluminum oxide pottery of present embodiment is excellent in mechanical characteristics, therefore the suitable insulated substrate as various ceramic wiring board, ceramic package etc.
Now, if form metal layer on the surface of the insulated substrate comprising aluminum oxide pottery, then Metallization strength can be made to reach 43N(kgm/s 2) more than, particularly reach 51N(kgm/s 2) more than.Its reason is, surrounds the amorphous phase containing the oxide compound of manganese and silicon around alumina crystalline phase, soaks into well to the metal layer formed on the surface of aluminum oxide pottery (sintered compact of metal-powder) side wettability.
Fig. 1 is the exploded perspective view of the embodiment representing ceramic package of the present invention.
The ceramic package of present embodiment by the surface of the insulated substrate 1 at pottery have in around shape the metal layer 3 that configures form, at this in above the metal layer 3 around shape configuration, be provided with the engagement member 7 for being engaged with metal layer 3 by the hardware such as lid, metal frame 5.
The substrate dyke 1b that the B.B.P 1a of insulated substrate 1 by tabular and the edge part at this B.B.P 1a are arranged is formed, and is formed with the conductor 11 for mounting electronic parts 9 on the surface of B.B.P 1a.
This ceramic package using the aluminum oxide ceramic applications of the high strength of present embodiment in as the B.B.P 1a of insulated substrate and substrate dyke 1b, and reduce the size of ceramic package, therefore, even if make the thickness t of B.B.P 1a and the width w of substrate dyke 1b 0thinning, also can suppress using produce when the hardware 5 of lid engages B.B.P 1a, substrate dyke 1b distortion, the generation of crackle can be prevented.In addition, according to such ceramic package, even if carry out the reliability tests such as temperature cycling test, the deformation that the interface that also can reduce insulated substrate 1 and metal layer 3 produces, can obtain the ceramic package of high reliability.Now, the mean thickness being suitable for B.B.P 1a is 0.05 ~ 0.3mm, particularly 0.05 ~ 0.2mm, and in addition, the mean thickness of substrate dyke 1b is below 0.15mm thin ceramic packaged piece like this.
As long as the metallic substance that the material melting point that the material forming metal layer 3 uses than engagement member 7 is high, from the viewpoint of can burn till with ceramic substrate 1 simultaneously, the material that to be suitably with molybdenum, tungsten or their alloy be principal constituent.Now, also can the composition of coordinated insulation substrate 1 and sintering temperature and make complex copper, silver etc. in molybdenum, tungsten.
In addition, as the ceramics component contained in metal layer 3, even if desirably carry out also not melting in the temperature province sintered at the metallic substance of metal layer 3, still residue in the high stupalith of the inner such fusing point of metal layer 3 after sintering.Now, such as, the oxide compound etc. of aluminum oxide, zirconium white, magnesium oxide and rare earth element is suitable, and from the viewpoint of the intensity of the metal layer 3 that raising is principal constituent with molybdenum, tungsten etc., preferred aluminium sesquioxide (aluminum oxide) is as the principal constituent of insulated substrate 1.It should be noted that, wish that conductor 11 is also identical composition.
As engagement member 7, during preferred heating in lower temperature (at this, be less than 900 DEG C) under melting, the easily diffusion in low viscosity, in metal layer 3 material, such as, the material containing low melting point metals such as silver solder (Ag-Cu), Wood's metals is suitable.
As hardware 5, kovar alloy (コ バ ー Le can be applied), Composite has material or the stupalith of pottery in the metallic substance such as 4-2 alloy, aluminium silicon carbide (ALSiC) and metallic substance.
Then, the aluminum oxide pottery manufacturing present embodiment, the method for ceramic wiring board and ceramic package that applies this aluminum oxide pottery are described.
First, to by aluminium sesquioxide powder (hereinafter referred to as alumina powder.), manganese oxide powder (Mn 2o 3powder) and silicon oxide powder (SiO 2powder) by after adding organic binder bond in the mixed ceramic powder of specified amount, by it by pressing, scrape the unprocessed molding that the known manufacturing process such as the skill in using a kitchen knife in cookery, rolling process, injection form such as tabular.Now, if make Mn 2o 3powder and SiO 2the ratio of powder is with Mn 2o 3/ (Mn 2o 3+ SiO 2) count 30 ~ 50% than (mass ratio), then can reduce the crystalline phase ratio beyond the alumina crystalline phase contained in the aluminum oxide pottery of gained further.
Alumina powder, Mn as used herein can be made 2o 3powder and SiO 2the median size of powder is all in the scope of 0.3 ~ 1.0 μm, the median size that can make the alumina crystalline phase in the aluminum oxide pottery after burning till thus is 0.8 ~ 1.5 μm, and can crystalline phase beyond inhibited oxidation aluminium crystalline phase in the precipitation of the crystal boundary of alumina crystalline phase.
Then, after the surface of this unprocessed molding forms conductive pattern as required, such as, in reducing atmosphere, burn till at the temperature of 1300 ~ 1600 DEG C.
When the ceramic package of the formation shown in shop drawings 1, first, make green sheet as the unprocessed molding being used as B.B.P 1a, then, form conductive pattern on its surface.
Unprocessed molding as substrate dyke 1b makes as follows, that is, carry out hole machined to green sheet, then, the surface around the hole of this green sheet partly forms conductive pattern.Now, also can prepare in advance as required and only carried out the sheet material of hole machined.
Then, in the side defining conductive pattern of the green sheet as B.B.P 1a, be layered on the surface around hole and define conductive pattern green sheet, make it closely sealed, form the ceramic package molding of shape shown in Fig. 1.
As the paste of conductive pattern, the sintering temperature of ceramic powder can be coordinated and use the metallic substance of various composition, when unprocessed molding such as uses the ceramic powder of the alumina powder containing more than 80 quality %, dystectic metallic substance of molybdenum, tungsten etc. can be used.
In addition, form the plated film of nickel on metal layer 3 surface of the ceramic package of gained, on the surface of metal layer 3 of plated film defining nickel, via engagement member 7, the hardware such as lid, metal frame 5 is engaged.
The ceramic package with hardware 5 like this made, the physical strength of insulated substrate 1 is high, in addition, metal layer 3 is high with the bond strength via the hardware 5 of engagement member 7, without bad order, and, can high-air-tightness be realized when insulated substrate 1 engages lid.
Embodiment
Then, to for confirming that the experimental example that effect of the present invention is carried out is described.
First, as the raw material powder for making aluminum oxide pottery, alumina powder, Mn that median size is 0.5 μm have been prepared 2o 3powder, SiO 2powder, MgO powder and MoO 3powder.
Then, by these raw material powders with after the ratio mixing shown in table 1, adopt acrylic adhesives as shaping with organic resin (tackiness agent), carry out using toluene as solvent being mixed with slurry, then, employing scraper legal system makes the green sheet of specific thickness.
The green sheet of gained is stacked to specific thickness, and the conductive pattern that to print with the metal shown in table 1 be as required principal constituent, burns till at the temperature shown in table 1.Firing atmosphere employing dew point is the nitrogen-hydrogen mixed atmosphere of+25 DEG C.
Then, the aluminum oxide pottery about gained has carried out following evaluation.
The ratio of each crystalline phase is tried to achieve as follows, that is, pulverize the aluminum oxide pottery of gained, by X-ray diffraction identification principal crystalline phase, is analyzed try to achieve by Rietveld.
The median size of alumina crystalline phase is tried to achieve as follows, that is, carry out section grinding to the section of the sample of aluminum oxide pottery, utilizes scanning electron microscope to take the photo of about 3000 times, then, utilize this photo to be tried to achieve by intercept method to the abrasive surface of gained.
The area ratio of hole is tried to achieve as follows, namely, by the surface of aluminum oxide pottery by after abrasive mirror ultrafinish, utilize image analysis apparatus (Nireco LUZEX-FS) to try to achieve the total area of the hole (open pore) observed in the area of regulation, try to achieve the ratio of this total area relative to the area of regulation.Now microscope multiplying power is about 100 times, makes mensuration area be 9.0 × 10 4μm 2and measure 10 places, calculate thus.
Physical strength is tried to achieve as follows, that is, make the beam-like sample of thickness 3mm, width 4mm, length 40mm, at room temperature measure 3 flexural strengths, tried to achieve by the mean value of 35 based on JISR1601.
With regard to Metallization strength, in green sheet, conductive pattern is formed in the mode becoming the size of 2mm × 20mm after burning till, after burning till by method same as described above, carry out plating Ni, adopt eutectic Ag-Cu braze material it to be engaged to the pin of Fe-Ni-Co, load when peeling off pulling vertically upward using the speed of 20mm/min is evaluated as Metallization strength.
In addition, the metal layer on surface being formed at aluminum oxide pottery is formed without after the nickel (Ni) of electrolysis and the plated film of gold (Au), adopt stereoscopic microscope to observe its outward appearance with about 40 times, the presence or absence of the irregular colour (bleeding caused by the colour developing of added ingredients) of aluminum oxide ceramic surface is evaluated.In addition, the presence or absence of plating attachment is also evaluated, the sample observing irregular colour or plating attachment is judged to be bad (×).It should be noted that, in Table 1, the judgement of zero is the sample not having bad order.
In addition, the composition of the sample produced is tried to achieve by atomic absorption analysis and icp analysis.Now, the aluminum oxide pottery of gained is dissolved in acidic solution, is carried out the qualitative analysis of contained element in aluminum oxide pottery by atomic absorption analysis, then, using dilution standard liquid liquid as standard test specimen, utilize ICP Emission Spectrophotometer to carry out quantification to specific each element.Valence mumber according to each element shown in the periodic table of elements tries to achieve oxygen level.The composition of sample all forms consistent with the modulation shown in table 1.
As shown in Table 1 sample No.1 ~ 4,6 ~ 8,10 ~ 17,3 flexural strengths of 18 and 19 are more than 680MPa, wherein, said sample take aluminium sesquioxide as principal constituent, containing with Mn 2o 3be scaled 2.0 ~ 5.0 quality % manganese and with SiO 2be scaled the silicon of 3.0 ~ 7.5 quality %, analyzing what try to achieve by the Rietveld of X-ray diffraction take aluminium sesquioxide as the ratio of the crystalline phase of principal constituent is 99.0 ~ 99.9 quality %, and the median size of alumina crystalline phase is 0.8 ~ 1.5 μm, and the area ratio of the hole of per unit area is less than 3.1%.
In addition, sample No.1,3,4,7,8,11,12,15,16,3 flexural strengths of 19 and 20 are more than 705MPa, wherein, said sample is respectively Mn making the composition formula of manganese and silicon 2o 3and SiO 2time, Mn 2o 3/ (Mn 2o 3+ SiO 2) represented by mass ratio be 30 ~ 50%, said sample is also containing magnesium and molybdenum, and magnesium is scaled 0.3 ~ 0.7 quality % with MgO, and molybdenum is scaled 0.3 ~ 0.7 quality % with MoO, and porosity is less than 3.0%.In addition, the Metallization strength of these samples is more than 51N, and the surface of sample, without irregular colour, plating attachment, keeps good outward appearance.
Wherein, particularly, the ratio with regard to alumina crystalline phase is 99.2 ~ 99.9 quality %, and Mn 2o 3/ (Mn 2o 3+ SiO 2) represented by mass ratio be 30 ~ 40% sample No.1,3,4,7,11,12,15,16,19 and 20, its 3 flexural strengths are more than 710MPa.
On the other hand, with regard to sample No.5,9,18,21 ~ 24, its 3 flexural strengths are all lower than 680MPa.
Accompanying drawing explanation
1,101 ... insulated substrate
1a, 101a ... B.B.P
1b, 101b ... substrate dyke
3,103 ... metal layer
5,105 ... hardware (lid)
7,107 ... engagement member
9,109 ... electronic unit
11,102 ... conductor

Claims (4)

1. an aluminum oxide pottery, is characterized in that, take aluminium sesquioxide as principal constituent, contains with Mn 2o 3be scaled 2.0 ~ 5.0 quality % manganese and with SiO 2be scaled the silicon of 3.0 ~ 7.5 quality %,
Mn is respectively making the composition formula of described manganese and described silicon 2o 3and SiO 2time, Mn 2o 3/ (Mn 2o 3+ SiO 2) represented by mass ratio be 30 ~ 50%,
Described aluminum oxide pottery also contains magnesium and molybdenum,
Described magnesium is scaled 0.3 ~ 0.7 quality % with MgO,
Described molybdenum is scaled 0.3 ~ 0.7 quality % with MoO,
It is crystalline phase, the MnAl of principal constituent that described aluminum oxide pottery has with aluminium sesquioxide 2o 4crystalline phase and Mo crystalline phase are that the ratio of the crystalline phase of principal constituent is 99.0 ~ 99.9 quality % with aluminium sesquioxide described in being tried to achieve by the Rietveld analysis of X-ray diffraction, and
Merge described MnAl 2o 4crystalline phase and described Mo crystalline phase and the ratio of the crystalline phase obtained is below 1 quality %,
In addition, described take aluminium sesquioxide as the median size of the crystalline phase of principal constituent is 0.8 ~ 1.5 μm,
And the area ratio of the hole of per unit area is less than 3.0%.
2. aluminum oxide according to claim 1 pottery, is characterized in that, described take aluminium sesquioxide as the ratio of the crystalline phase of principal constituent is 99.2 ~ 99.9 quality %, and Mn 2o 3/ (Mn 2o 3+ SiO 2) represented by described mass ratio be 30 ~ 40%.
3. a ceramic wiring board, is characterized in that, it forms by arranging metal layer on insulated substrate surface, and described insulated substrate is made up of the aluminum oxide pottery described in claim 1 or 2.
4. a ceramic package, is characterized in that, it is by forming via engagement member jointing metal component on the surface of insulated substrate, and described insulated substrate is made up of the aluminum oxide pottery described in claim 1 or 2.
CN201280039604.6A 2012-06-25 2012-11-28 Aluminum oxide pottery and use its ceramic wiring board and ceramic package Active CN103732558B (en)

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