CN1978386A - Sintering aid composition, ceramic composition, ceramic, ceramic electronic component and manufacture of ceramic electronic component - Google Patents
Sintering aid composition, ceramic composition, ceramic, ceramic electronic component and manufacture of ceramic electronic component Download PDFInfo
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- CN1978386A CN1978386A CN 200610171943 CN200610171943A CN1978386A CN 1978386 A CN1978386 A CN 1978386A CN 200610171943 CN200610171943 CN 200610171943 CN 200610171943 A CN200610171943 A CN 200610171943A CN 1978386 A CN1978386 A CN 1978386A
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Abstract
A sintering aid composition for adding in ceramic base material and sintering with said ceramic base material to produce sintering ceramic material is provided. A sintering aid composition for a ceramic comprises at least copper oxide, titanium oxide and niobium oxide. When the ternary composition is expressed as xCuO-yTiO2-zNbO2.5 (wherein x, y and z are molar ratios satisfying the relation: x+y+z=1.0), x, y and z lie inside a rectangular area enclosed by apexes A, B, C and D having coordinates A: (x, y, z)=(0.500, 0.250, 0.250), B: (x, y, z)=(0.300, 0.250, 0.450), C: (x, y, z)=(0.640, 0.040, 0.320) and D: (x, y, z)=(0.384, 0.040, 0.576), respectively, in a ternary composition diagram. This sintering aid composition suppresses deterioration in characteristics of a base material and lower the sintering temperature.
Description
Technical field
The present invention relates to sintering aid, ceramic composition, pottery and the ceramic electronic components by these preparations.
Background technology
Now, the stupalith that adopts in the ceramic electronic components as multilayer capacitor or high frequency strainer, multilager base plate etc., the known high temperature that at high temperature burns till burn till (High Temperature Co-firedCeramics:HTCC) material and can low temperature under easy fired (the Low TemperatureCo-fired Ceramics:LTCC) material that burns till.Contain Al as the HTCC material as base material
2O
3Or TiO
2Deng having stable on heating inorganic powder.This stupalith is after above-mentioned inorganic powder is shaped as principal constituent, and sintering prepares by burning till under the high temperature more than 150 ℃.As at the inner wiring conductor material that forms of the multilayer ceramic substrate that adopts the HTCC material, adopt high molybdenum or the tungsten of melting point thus.But molybdenum or tungsten have electric conductivity to hang down such shortcoming as conductor.Electric conductivity height, cheap silver or copper melting point are low, can fusion when burning till the multilayer ceramic substrate that utilizes the HTCC material, and therefore can not be used as the wiring conductor in the multilayer ceramic substrate.In addition, because the sintering temperature height of HTCC material, so the installation cost height of essential high temperature firing furnace or ultrahigh-temperature firing furnace, and owing to energy cost must uprise, so the price height of ceramic substrate.
The resistance of the conductor in the multilayer ceramic substrate is low, and the firing temperature step-down for ceramic substrate by add sintering aid in the ceramic raw material of aluminum oxide, forsterite etc., obtains the LTCC material that can burn till at low temperatures.The LTCC material can be at Ag, Cu or Ag-Pd alloy, Ag-Pt alloy sintering in the temperature of fused below 110 ℃ not.
No. 2624149 communique of patent discloses at aluminum oxide (Al
2O
3) added the existing sintering aid of the glass of low melting point in the class ceramic base material.Te Kaiping 5-24913 communique discloses the existing sintering aid that adds glass and CuO in the ceramic base material that is formed by Ca, Nb and Ti oxide compound.
Glass as existing these sintering aid principal constituents with the insufficient reduction of the corresponding firing temperature of the addition of every ceramic base material unit weight, in addition, has the situation of ceramic base material hard-to-sinter.If in order to reduce firing temperature that the interpolation quantitative change of sintering aid is many, then this characteristic of ceramic base material will be by deterioration.
Because the viscosity ratio of these existing sintering aids is higher, so be difficult to mix with ceramic base material.In addition, since the melting point of these existing sintering aids than higher, so can not significantly reduce the agglomerating firing temperature.
Summary of the invention
The invention discloses and sintering aid is added in the ceramic base material, burns till simultaneously with ceramic base material and prepare sintered ceramic material.This sintering aid contains cupric oxide and titanium oxide and niobium oxides.At this composition xCuO-yTiO
2-zNbO
2.5(x, y, z are mol ratios, and in the three composition composition diagrams when x+y+z=1.0) representing, x, y and z are in an A, B, C, D are the tetragonal ABCD zone on summit:
A：(x，y，z)＝(0.500，0.250，0.250)
B：(x，y，z)＝(0.300，0.250，0.450)
C：(x，y，z)＝(0.640，0.040，0.320)
D：(x，y，z)＝(0.384，0.040，0.576)。
By this sintering aid, can suppress the deterioration of ceramic base material characteristic and obtain the low stupalith of firing temperature.
Description of drawings
Fig. 1 shows the composition by the ceramic post sintering auxiliary agent of the embodiment of the invention 1.
Fig. 2 is the ternary composition diagram by the ceramic post sintering assistant composition of embodiment 1.
Fig. 3 shows the result of the X ray parsing of comparative example composition.
Fig. 4 shows the result of the X ray parsing of embodiment 1 composition.
Fig. 5 shows the result of the X ray parsing of comparative example composition.
Fig. 6 shows the result that the X ray of other composition of embodiment 1 is resolved.
Fig. 7 shows the result of the X ray parsing of comparative example composition.
Fig. 8 shows the result of the X ray parsing of comparative example composition.
Fig. 9 shows the ceramic composition that adopts sintering aid among the embodiment.
Figure 10 shows the evaluation result of the ceramic composition shown in Fig. 9.
Figure 11 shows the ceramic composition of the sintering aid that adopts comparative example.
Figure 12 A～Figure 12 C is the sectional view that is illustrated in the preparation method of ceramic electronic components in the embodiment of the invention 2.
Figure 13 is the sectional view of the ceramic electronic components of embodiment 2.
Figure 14 is the sectional view of the ceramic electronic components of the embodiment of the invention 3.
Embodiment
(embodiment 1)
The composition of the ceramic post sintering auxiliary agent of embodiments of the invention 1 is described.
Prepare purity 99.99%, the cupric oxide (CuO) of median size 0.1～5 μ m, titanium oxide (TiO at first, respectively
2), niobium oxides (Nb
2O
5) powder.The oxide compound of above-mentioned 3 kinds cooperates with ratio of components shown in Figure 1, obtains the test portion of test portion number No.1～42.In Fig. 1, the mol ratio of CuO is x, TiO
2Mol ratio be y.Nb
2O
5Mol ratio pass through NbO
2.5Conversion is z, wherein x+y+z=1.
In said composition 100 weight %, add entry 200 weight %, with having used the zirconic ball mill mixing of 5mm φ 24hr.After this, the blended composition obtains the powder of the composition of sintering aid 150 ℃ of following thorough dryings.
With in the composition powder that obtains in air, kept 2 hours with in 960 ℃ of heat-up rate, the top temperatures of 300 ℃/hr, apply thermal treatment and prepare adjuvant for combustion.In order to identify the generation compound after the thermal treatment, using the CuK alpha-ray to apply voltage 40keV, apply and carry out X ray under the condition of electric current 40mA and resolve the powder after the thermal treatment.This X ray is resolved the X ray intensity of having measured under the various angles of radiating in diffraction.Composite oxides mutually promptly the peak value of 33.9 ± 0.1 ° of following intensity be in the maximum test portion, this peak value is judged to be the main peak value with " Y " expression among Fig. 1.In the test portion of other compound phase that the peak value of the intensity under generation is compared 33.9 ± 0.1 ° is bigger, 33.9 ± 0.1 ° peak value is not judged to be the main peak value, illustrates with " N " in Fig. 1.
Then, judgement is as the ability of the adjuvant for combustion of the composition of test portion number No.1～42.As ceramic base material, purity 99.99%, the median size of 0.3 μ m, aluminum oxide (Al have been prepared with corundum phase
2O
3).
The test portion 10 weight % that mix this ceramic base material 90 weight %, composition, the powder of the ceramic composition of identical making 42 kinds with aforesaid method.The polyvinyl alcohol as tackiness agent (PVA) resin and the water that add specified amount in each powder make the particle of composition, after the drying, by single shaft pressurization (Yi Shaft pressurization) make columned molding.After being carried out to the unsticking mixture of body, keeping 2 hours and burn till molding with 960 ℃ of 300 ℃/hr of heat-up rate, top temperature.The density of the molding that burns till is measured by Archimedes's method, be judged to be sintering relative density 95%, density 3.80g/cm
3Above molding.In the test portion of test portion number No.1～42, Fig. 1 shows the result of determination that whether sinters molding into.
Fig. 2 is CuO, the TiO that shows the test portion of test portion number No.1～42 simultaneously
2, NbO
2.5Three composition ratio of componentss and the composition diagram of test portion number.The composition xCuO-yTiO of the sintering aid in Fig. 2
2-zNbO
2.5(x, y, z are mol ratios, x+y+z=1.0) expression.In Fig. 2, the ratio of components that some A, B, C, D represent is respectively test portion number No.30,33,9,12 test portion.The test portion of the embodiment of the sintering aid of embodiment 1 is 16 kinds the test portion altogether of test portion number No.9～12,16～19,23～26,30～No.33, and other test portion is the test portion of comparative example.The point that expression embodiment test portion is formed is located in following some A, B among Fig. 2, the tetragonal ABCD that C, D are the summit.
A：(x，y，z)＝(0.500，0.250，0.250)
B：(x，y，z)＝(0.300，0.250，0.450)
C：(x，y，z)＝(0.640，0.040，0.320)
D：(x，y，z)＝(0.384，0.040，0.576)
The point of the composition of the test portion of expression comparative example is positioned at outside the tetragonal ABCD.
As shown in Figure 1, in the test portion of the comparative example of the composition outside having tetragonal ABCD, 33.9 ± 0.1 ° peak value is not the main peak value, is the density less than 3.80 behind the ceramic post sintering of ceramic base material with the aluminum oxide.
In the ceramic test portion of the embodiment of the ratio of components that the point in having the tetragonal ABCD that surrounds with some A, a B, C, D is represented, 33.9 ± 0.1 ° peak value is the main peak value, is that the density behind the ceramic post sintering of ceramic base material is more than 3.80 with the aluminum oxide, fully sintering.Below, use figure explains this result.
Fig. 3～Fig. 8 shows the result of the X ray parsing of test portion, shows the relation of angle of diffraction 2 θ and diffracted intensity.Mark among the figure " P1 " shows Cu
4TiNb
4O
16Peak value, mark " P2 " shows CuTi
2Nb
2O
10Peak value.33.9 ± 0.1 ° peak strength is subjected to TiO
2Amount and CuO and NbO
2.5Ratio (CuO/NbO
2.5) very big influence.
At first, ratio (CuO/NbO is described
2.5) be TiO under 1 the situation
2Amount is to the influence of peak strength.
Fig. 3 shows TiO
2Amount be zero to be the result that the X ray of test portion number No.4 test portion is resolved.33.9 ± 0.1 ° peak strength is zero in this test portion, only generates CuO and NbO
2.5Compound.Be that density behind the ceramic post sintering of ceramic base material is 3.66 with the aluminum oxide that adds the said composition test portion, this pottery is not by abundant sintering.
Fig. 4 shows TiO
2Amount be that 0.040mol is the result that the X ray of test portion number No.10 test portion is resolved.In this test portion, with CuO and NbO
2.5The corresponding peak strength of compound diminish, it is big that 33.9 ± 0.1 ° peak strength becomes, and can determine that it is the main peak value.Be that density behind the ceramic post sintering of ceramic base material is 3.88 with the aluminum oxide that adds the said composition test portion, this pottery is by abundant sintering.
Fig. 5 shows TiO
2Amount be that 0.111mol is the result that the X ray of test portion number No.18 test portion is resolved.The peak value of 33.9 ± 0.1 ° (angle A 3) further becomes big in this test portion, roughly is Cu
4TiNb
4O
16Single-phase.Intensity peak under 23.7 ± 0.1 ° (angle A 1), 29.1 ± 0.1 ° (angle A 2), 37.9 ± 0.1 ° (angle A 4), 45.2 ± 0.1 ° (angle A 5), 48.6 ± 0.1 ° (angle A 6), 51.9 ± 0.1 ° (angle A 7), 54.8 ± 0.1 ° (angle A 8), 60.5 ± 0.1 ° (angle A 9), 71.1 ± 0.1 °, 81.1 ± 0.1 ° the angle appears in this test portion.Be that density behind the ceramic post sintering of ceramic base material is 3.92 with the aluminum oxide that adds the said composition test portion, show maximum density in all test portions, this pottery is by abundant sintering.
Fig. 6 shows TiO
2Amount be that 0.250mol is the result that the X ray of test portion number No.32 test portion is resolved.Even 33.9 ± 0.1 ° intensity peak little than Fig. 5 test portion also is the main peak value in this test portion.In this test portion, also generate CuTi
2Nb
2O
10Compound.Be that density behind the ceramic post sintering of ceramic base material is 3.85 with the aluminum oxide that adds the said composition test portion, this pottery is by abundant sintering.
Fig. 7 shows TiO
2Amount be that 0.400mol is the result that the X ray of test portion number No.39 test portion is resolved.Most CuTi that generate in this test portion
2Nb
2O
10Compound, 33.9 ± 0.1 ° intensity peak diminishes, and is not the main peak value.Be that density behind the ceramic post sintering of ceramic base material is 3.66 with the aluminum oxide that adds the said composition test portion, this pottery is not by abundant sintering.
Fig. 8 illustrates the result of the X ray parsing of test portion number No.41 test portion.Intensity peak only appears at and CuTi in this test portion
2Nb
2O
10The corresponding angle of compound, be the single-phase of this compound.
Then, TiO is described
2Amount CuO and NbO when being 0.111mol
2.5Than (CuO/NbO
2.5) to the influence of density behind the sintering.
At ratio (CuO/NbO
2.5) the CuO surplus in the test portion of bigger test portion number No.15 than 2.00, NbO in the No.20 that odds ratio 0.67 is littler, 21 the test portion
2.5Superfluous.In these test portions owing to generated CuTi
2Nb
2O
10Compound, 33.9 ± 0.1 ° intensity peak is less, is not judged to be the main peak value.With the aluminum oxide that adds these test portions is that the pottery of ceramic base material is not by abundant sintering.
At ratio (CuO/NbO
2.5) be that 33.9 ± 0.1 ° intensity peak is bigger, is judged to be the main peak value in the test portion number No.16 below 2.00 more than 0.67,17,18,19 the test portion.With the aluminum oxide that has added this test portion is the abundant sintering of pottery quilt of ceramic base material.
As mentioned above, the composition with ratio of components that the point in the tetragonal ABCD that Fig. 2 mid point A, B, C, D surround represents becomes and contains Cu by thermal treatment
4TiNb
4O
16Sintering aid, make the ceramic base material that added this sintering aid by abundant sintering.
Then, the effect that embodiment 1 reduces the firing temperature of sintering aid is described.For the test portion of the composition that makes the abundant agglomerating test portion of ceramic base material number No.18, the effect that 6 kinds of ceramic base materials is reduced firing temperature has been described.
At first, in air,, kept 2 hours down for 900 ℃, heat-treat and make adjuvant for combustion with 300 ℃/hr of heat-up rate, top temperature with the sintering aid composition of test portion number No.18.
Then, preparation is as the test portion of 6 kinds of ceramic base materials of test portion number No.43～48 shown in Fig. 9 of embodiment.The test portion of the ceramic base material of test portion number No.43 is by Al
2O
3Form, have the median size of the crystallizing layer and the 0.3 μ m of corundum phase.The test portion of the ceramic base material of test portion number No.44 is by Ga
2O
3Form, have the median size of the crystallizing layer and the 1.0 μ m of corundum phase.The test portion of the ceramic base material of test portion number No.45 is by TiO
2Form, have the median size of the crystallizing layer and the 1.3 μ m of rutile phase.The test portion of the ceramic base material of test portion number No.46 is by BaTiO
3Form, have the median size of the crystallizing layer and the 0.2 μ m of uhligite phase.The test portion of the ceramic base material of test portion number No.47 is by AgNbO
3Form, have the median size of the crystallizing layer and the 1.4 μ m of uhligite phase.The test portion of the ceramic base material of test portion number No.48 is by Ag (Nb
0.35, Ta
0.65) O
3Form, have the median size of uhligite phase crystallizing layer and 1.4 μ m.
The sintering aid 5 weight % that these test portions 95 weight % of ceramic base material and thermal treatment test portion number No.18 test portion composition are obtained cooperate, and make the powder of 6 kinds of ceramic compositions.
The tackiness agent that adds specified amount in above-mentioned powder is that PVA resin and water are configured as particle, after the drying, is made into columned molding by the single shaft pressurization.After this molding implemented unsticking mixture, molding at 300 ℃/hr of heat-up rate, kept 2 hours under firing temperature, is burnt till, make the test portion of 6 kinds of ceramic post sintering things of test portion number No.43～48.
The density of these test portions of ceramic post sintering thing is measured by Archimedes's method, and relative density is the sintering temperature that the temperature more than 95% has determined this test portion.In Fig. 9, show the monomeric sintering temperature of test portion of ceramic base material and the sintering temperature of having added the ceramic base material of sintering aid.
In addition, in these test portions, the insulation resistance IR when measuring specific inductivity and the dielectric loss angle tangent tan δ of 1MHz and having applied the volts DS of 500V.These test portions are high frequency characteristics of mega hertz band in addition, method (B.W.Hakki by Hakki etc., P.DColeman, " A dielectricresonator method of measuring inductive capacities in the millimeter range ", IEEE Trans.on Microwave Theory Tech., MTT-8 (1960) pp.402-410 ") measure resonant frequency f and loss factor Q long-pending (fQ is long-pending).Loss factor Q is the inverse of dielectric loss angle tangent tan δ.These measurement result has been shown among Figure 10.
In the test portion of test portion number No.43, the sintering temperature of having added the ceramic base material of sintering aid is 950 ℃, has only reduced by 500 ℃ for 1450 ℃ than the monomeric firing temperature of ceramic base material that adopts aluminum oxide.The specific inductivity of this test portion, dielectric loss angle tangent, insulation resistance are the value of aluminum oxide near ceramic base material.In addition, it is long-pending that this test portion has the good fQ of 18000GHz.
In the test portion of test portion number No.44, the sintering temperature of having added the ceramic base material of sintering aid is 1100 ℃, has only reduced by 400 ℃ for 1500 ℃ than the monomeric firing temperature of ceramic base material that adopts gallium oxide.
In the test portion of test portion number No.45, specific inductivity (104) is reduced, can access than the monomeric sintering temperature of ceramic base material that adopts titanium oxide only low 350 ℃ sintering temperature.The good fQ that this test portion has 5100GHz amasss.
In the test portion of test portion number No.46, the burden-fluxing sinter temperature that can access than the ceramic base material that adopts barium titanate only reduces by 350 ℃ sintering temperature.
In the test portion of test portion number No.47, specific inductivity (325) is reduced, obtain 850 ℃ of low sintering temperatures, it is than only low 200 ℃ of the monomeric sintering temperatures of ceramic base material that adopts niobic acid silver.
In the test portion of test portion number No.48, specific inductivity (404) is reduced, can access than the monomeric sintering temperature of ceramic base material that adopts niobium tantalic acid silver low 300 ℃ sintering temperature only.In addition, it is long-pending that test portion has the good fQ of 320GHz.
Then, as a comparative example, Figure 11 illustrates the test portion of 6 kind ceramic base materials of test portion number No.49～54.Test portion number No.49～ceramic base material of 54 and embodiment shown in Figure 9 are that the ceramic base material of test portion number No.43～48 is identical respectively.
Comparative example is will add in the ceramic base material as the glass of sintering aid or the mixture of glass and cupric oxide (CuO) in the test portion of test portion number No.49～54.Test portion number No.49,50 test portion are added the glass as sintering aid.This glass contains the SiO of 15 weight %
2, 15 weight % B
2O
3, the ZnO of 35 weight %, the Al of 20 weight %
2O
3, the CaO of 14.5 weight %, the CuO of 0.5 weight %.The ceramic composition that has added up to ceramic base material is added the glass of 5 weight %.In the test portion of test portion number No.51～54, glass and CuO mixture as sintering aid are added in the ceramic base material.This glass contains the glassy phase composition together with test portion No.49,50 test portions.The ceramic composition that has added up to ceramic base material is added the glass of 4 weight %, the ceramic composition that has added up to ceramic base material is added the CuO of 1 weight %.That is, the ceramic composition that has added up to ceramic base material is added this glass of 5 weight % and the mixture of CuO.
With test portion number No.43～48 shown in Fig. 9 similarly, Figure 11 shows the sintering temperature of the test portion of test portion number No.49～54.For any test portion shown in Figure 11, only reduced by 100 ℃ owing to added the sintering temperature of the ceramic base material of sintering aid than the monomeric sintering temperature maximum of ceramic base material, so the sintering aid of these test portions does not have a significant effect.
In addition, in the sintering aid of the test portion of test portion number No.49～54, for the sintering temperature and low that obtains equating with the sintering aid of test portion number No.43～48, ceramic composition must contain the above sintering aid of at least 30 weight %.If do not contain many like this sintering aids, special the specific inductivity of ceramic composition sharply reduces under the high situation of the specific inductivity of base material, and other characteristic also worsens, and can not give full play to the characteristic of ceramic base material.
As mentioned above,, only in ceramic base material, carry out a spot of interpolation, impel firing temperature to reduce greatly according to composition and the sintering aid of embodiment 1.And, because addition is a small amount of, so do not make the deterioration in characteristics of ceramic base material.
Owing to according to embodiment 1 sintering aid firing temperature is reduced, so can realize saving energy during the Low fire ceramic material, the conductor that can burn till the low melting point of Ag etc. simultaneously is the electrode and the stupalith of principal constituent.
In addition, embodiment is the sintering aid of the test portion of test portion number No.43～48, though make composition with thermal treatment, even not thermal treatment, in ceramic base material, add composition itself, also obtain same effect.
Composition according to the sintering aid of embodiment 1 has low melting point, in addition, has the high intermiscibility with ceramic base material.Thereby, can make ceramic composition at few addition at low sintering temperature.
(embodiment 2)
Figure 12 A～Figure 12 C shows preparation method's the sectional view of the ceramic electronic components 1001 of the embodiment of the invention 2.Figure 13 is the sectional view with the ceramic electronic components 1001 of the preparation of preparation method shown in Figure 12 A～Figure 12 C.
At first, in the ceramic base material of forming by the aluminum oxide of 100 weight % of median size with 0.05～5 μ m, add the test portion number No.18 sintering aid composition of the 2.5 weight %～20 weight % with 0.05～10 μ m median size, make ceramic composition.In addition, as the replacement of the composition of this sintering aid, also thermal treatment under the temperature more than 900 ℃ can be obtained, Cu
4TiNb
4O
16The mutually equally distributed sintering aid of composite oxides be added in the ceramic base material.
And, to 100 weight % of this ceramic composition, mix the water of 50～300 weight %, utilize ball mill to mix 12～72 hours with the dispersion media that adopts 1～5mm φ high-purity alpha-alumina, make the slurry that comprises ceramic composition.With this slurry from ball mill, take out, drying.
Then, in slurry 100 weight %, resin glue 5～15 weight % of cooperation PVB resin etc., dispersion medium 40～120 weight % of N-BUTYL ACETATE, ethanol etc., plasticizer 2～12 weight % of dibutyl phthalate (DBP), butylbenzene methyl phthalate (BBP) etc., further cooperate defoamer, dispersion agent as required on a small quantity, utilize ball mill to adopt 10mm φ high-purity alpha-alumina to disperse 12～72 hours, make ceramic size.
Then, the thickness of ceramic size with regulation is coated on the carrier thin film, uses kiln dried, the ceramic composition layer shown in the construction drawing 12A is a ceramic green sheet 801.Carrier thin film uses the PET film that is coated with panel forming machine demoulding processing such as (ダ イ コ one テ ィ Application グ) device by mould.
Then, on the position of regulation, forming through hole by punching processing or laser processing as required on the ceramic green sheet 801.Is that the conductive paste of principal constituent is filled in and forms pore electrod 802 in the through hole by silk screen printing etc. with silver.
After this, using silver on ceramic green sheet 801 is cloth line electrode 803 as the conductive paste of principal constituent by methods such as silk screen printing formation circuit pattern.
Then, will have the ceramic green sheet 801 of the cloth line electrode 803 of printing formation respectively, shown in Figure 12 A, one side stacked, the pressurization in coincidence one side, position, ceramic green sheet and the electrode layer mutual stacked duplexer 804 of formation shown in Figure 12 B.The size of duplexer 804 is 50～200mm normally, can be made a plurality of ceramic multi-layer baseplates 901 of rectangular configuration by duplexer 804.
In addition, by ceramic green sheet 801,, can in duplexer 804, form electrical condenser 805 by in the internal layer portion of duplexer 804, disposing cloth line electrode 803 relatively with regulation area.And, by stacked cloth line electrode 803, also can form more jumbo electrical condenser 805.In addition, by the punching electrode 802 that on ceramic green sheet 801, forms, also can be in duplexer 804 coil 807 of form layers stack structure.Thus, obtain the possible ceramic multi-layer baseplate 901 of high-density actual installation that inside has electrical condenser 805 and coil 807.
Then, silver coating is the conductive paste of principal constituent on duplexer 804, forms top layer electrode 806.After this, duplexer 804 according to the exert pressure of using regulation on the stacked direction of duplexer 804, is pressed each layer of sticking (pressure) duplexer 804.In addition, the temperature in this stacked and when pressurization is normal temperature～100 ℃ preferably, at pressure 20～1000kgf/cm
2Under carry out.
After this, cut off and press sticking duplexer 804 with individual sheetization, the duplexer 804 of this sheetization carries out the unsticking mixture under 400～600 ℃ temperature handles.
Then, duplexer 804 was kept 0.5～30 hour down for 820～960 ℃ in top temperature, in atmospheric environment, burn till, make each layer sintering.
The relative density of ceramic multi-layer baseplate 901 is more than 90%.Such ceramic multi-layer baseplate 901 can utilize the Ag of electrode materials good conductivity owing to can quantize so realize economizing at the low sintering temperature that burns till.In addition, sintering aid is not owing to contain the glass ingredient of low thermal conduction, so can realize having the ceramic multi-layer baseplate 901 of the high thermal conductivity shown in Figure 12 C, obtain ceramic multi-layer baseplate 901, its in actual installation the most suitable in the mini power amplifier module etc. of the high semiconductor device of heat generation.
Then, as shown in figure 13, on the top layer of ceramic multi-layer baseplate 901, form high capacity capacitors 903 semiconductor device 902 difficulties or that in multilager base plate 901, form difficulty such as power amplifier by actual installation, can make small-sized ceramic electronic components 1001.
By ceramic multi-layer baseplate 901, with existing power amplifier module relatively, reduced the quantity of hot hole or do not adopt hot hole and increase the degree of freedom of circuit layout, relaxed the restriction of wiring space simultaneously.Therefore, can realize the miniaturization of various modules, usually the miniaturization multifunction of machine.
(embodiment 3)
Figure 14 is the sectional view of the ceramic electronic components 1002 in the present embodiment 3.Ceramic electronic components 1002 is different with the ceramic electronic components 1001 of embodiment 2 shown in Figure 13, is provided with than other ceramic composition 1001B to have the more ceramic layer 1001A of high-k in multilager base plate 901.By configured electrodes layer 803A relatively mutually on the two sides of ceramic layer 1001A, in multilager base plate 901, form the electrical condenser 1002A of heavy body.Therefore, do not want heavy body capacitive element 903 shown in Figure 13, can reach miniaturization, the cost degradation of ceramic electronic components 1002.
Aluminum oxide is that the composition of the test portion number No.43 shown in Fig. 9 of ceramic green sheet 801 usefulness embodiment 1 of base material forms, and high-dielectric-constant ceramics layer 1001A forms with the composition of test portion number No.48.
High-dielectric-constant ceramics composition layer 1001A, be among the ceramic base material 100 weight % of titanium oxide, niobic acid silver or the formation of niobium tantalic acid silver in median size with 0.05～5 μ m, cooperate sintering aid composition 2.5～20 weight % of median size, make ceramic green sheet in the same manner with aforesaid method with 0.05～10 μ m.After this, can be enough the method making ceramic electronic components 1002 identical with embodiment 2.
The ceramic base material of this ceramic green sheet is titanium oxide, niobic acid silver, tantalic acid silver or the niobium tantalic acid silver of high-k.Can replace with high-dielectric-constant ceramics layer 1001A is the ceramic green sheet 801 of ceramic base material with the low-k aluminum oxide in the capacitor part 1002A of heavy body.
Because the composition of test portion number No.43 and the sintering aid of test portion number No.48 is identical with the composition of test portion number No.18, so can the inhibitory phase mutual diffusion.Therefore, can be arranged in the multilager base plate 901, can in multilager base plate 901, form heavy body capacitance part 1002 having the high-dielectric-constant ceramics composition layer 1001A of specific inductivity more than 400.
Claims (17)
1. be used for being added on ceramic base material, burn till jointly with above-mentioned ceramic base material and prepare the sintering aid of sintered ceramic material, it contains cupric oxide, titanium oxide and niobium oxides, is using xCuO-yTiO
2-zNbO
2.5(x, y, z are mol ratios, and in the three composition composition diagrams when x+y+z=1.0) representing, x, y and z are in an A, B, C, D are the tetragonal ABCD zone on summit:
A：(x，y，z)＝(0.500，0.250，0.250)
B：(x，y，z)＝(0.300，0.250，0.450)
C：(x，y，z)＝(0.640，0.040，0.320)
D：(x，y，z)＝(0.384，0.040，0.576)。
2. sintering aid according to claim 1, it contains useful Cu
4TiNb
4O
16The composite oxides of expression, the main peak value of using the crystallization phases that the Alpha-ray X-ray diffraction assay method of CuK measures are 2 θ=33.9 ± 0.1 °.
3. sintering aid according to claim 2, above-mentioned sintering aid is by thermal treatment.
4. ceramic composition, it contains:
Have corundum phase, rutile phase, uhligite mutually in a kind of ceramic base material; And
Be used for being added on above-mentioned ceramic base material, burn till jointly with above-mentioned ceramic base material and prepare the sintering aid of sintered ceramic material, described sintering aid contains cupric oxide, titanium oxide and niobium oxides, is using xCuO-yTiO
2-zNbO
2.5(x, y, z are mol ratios, and in the three composition composition diagrams when x+y+z=1.0) representing, x, y and z are in an A, B, C, D are the tetragonal ABCD zone on summit:
A：(x，y，z)＝(0.500，0.250，0.250)
B：(x，y，z)＝(0.300，0.250，0.450)
C：(x，y，z)＝(0.640，0.040，0.320)
D：(x，y，z)＝(0.384，0.040，0.576)。
5. according to the ceramic composition described in the claim 4, wherein above-mentioned sintering aid contains useful Cu
4TiNb
4O
16The composite oxides of expression, the main peak value of using the crystallization phases that the Alpha-ray X-ray diffraction assay method of CuK measures are 2 θ=33.9 ± 0.1 °.
6. according to the ceramic composition described in the claim 4, wherein above-mentioned ceramic base material is the titanium oxide (TiO with rutile phase
2).
7. according to the ceramic composition described in the claim 4, wherein above-mentioned ceramic base material is the niobic acid silver (AgNbO with uhligite phase
3) or niobium tantalic acid silver (Ag (Nb, Ta) O
3).
8. Low fire ceramic composition and the pottery that obtains, it contains crystallization phases, and this crystallization phases has the main peak value of using peak value that the Alpha-ray X-ray diffraction assay method of CuK measures and 2 θ=33.9 ± 0.1 °, and wherein said ceramic composition contains:
Have corundum phase, rutile phase, uhligite mutually in a kind of ceramic base material; And
Be used for being added on above-mentioned ceramic base material, burn till jointly with above-mentioned ceramic base material and prepare the sintering aid of sintered ceramic material, described sintering aid contains cupric oxide, titanium oxide and niobium oxides, is using xCuO-yTiO
2-zNbO
2.5(x, y, z are mol ratios, and in the three composition composition diagrams when x+y+z=1.0) representing, x, y and z are in an A, B, C, D are the tetragonal ABCD zone on summit:
A：(x，y，z)＝(0.500，0.250，0.250)
B：(x，y，z)＝(0.300，0.250，0.450)
C：(x，y，z)＝(0.640，0.040，0.320)
D：(x，y，z)＝(0.384，0.040，0.576)。
9. pottery according to claim 8, wherein above-mentioned ceramic base material are the titanium oxide (TiO with rutile phase
2).
10. pottery according to claim 8, wherein above-mentioned ceramic base material are the niobic acid silver (AgNbO with uhligite phase
3) or niobium tantalic acid silver (Ag (Nb, Ta) O
3).
11. pottery according to claim 8, the firing temperature that wherein burns till above-mentioned ceramic composition is below 960 ℃.
12. ceramic electronic components, it comprises:
First ceramic layer;
Stacked second ceramic layer on above-mentioned first ceramic layer; And
The Ag that is provided with between above-mentioned first ceramic layer and above-mentioned second ceramic layer is first conductor layer of principal constituent,
Wherein, above-mentioned first ceramic layer and above-mentioned second ceramic layer are Low fire ceramic compositions and obtaining, it contains crystallization phases, and this crystallization phases has the main peak value of using peak value that the Alpha-ray X-ray diffraction assay method of CuK measures and 2 θ=33.9 ± 0.1 °, and wherein said ceramic composition contains:
Have corundum phase, rutile phase, uhligite mutually in a kind of ceramic base material; And
Be used for being added on above-mentioned ceramic base material, burn till jointly with above-mentioned ceramic base material and prepare the sintering aid of sintered ceramic material, described sintering aid contains cupric oxide, titanium oxide and niobium oxides, is using xCuO-yTiO
2-zNbO
2.5(x, y, z are mol ratios, and in the three composition composition diagrams when x+y+z=1.0) representing, x, y and z are in an A, B, C, D are the tetragonal ABCD zone on summit:
A：(x，y，z)＝(0.500，0.250，0.250)
B：(x，y，z)＝(0.300，0.250，0.450)
C：(x，y，z)＝(0.640，0.040，0.320)
D：(x，y，z)＝(0.384，0.040，0.576)。
13. ceramic electronic components according to claim 12, wherein above-mentioned first ceramic layer, above-mentioned second ceramic layer and above-mentioned conductor layer are integrally to burn till in the temperature below 960 ℃.
14. ceramic electronic components according to claim 12, the above-mentioned ceramic base material of wherein above-mentioned first ceramic layer is aluminum oxide (Al
2O
3).
15. the preparation method of ceramic electronic components, it comprises following steps:
The step of preparation ceramic composition,
Prepare the step of first ceramic plate and second ceramic plate with above-mentioned ceramic composition,
The step of preparation duplexer, described duplexer have above-mentioned first ceramic layer, at second stacked on above-mentioned first ceramic layer ceramic layer and what be provided with between above-mentioned first ceramic layer and above-mentioned second ceramic layer is first conductor layer of principal constituent with Ag, and
Burn till the step of above-mentioned duplexer;
Wherein in the step of preparation ceramic composition, described ceramic composition contains:
Have corundum phase, rutile phase, uhligite mutually in a kind of ceramic base material; And
Be used for being added on above-mentioned ceramic base material, burn till jointly with above-mentioned ceramic base material and prepare the sintering aid of sintered ceramic material, it contains cupric oxide, titanium oxide and niobium oxides, is using xCuO-yTiO
2-zNbO
2.5(x, y, z are mol ratios, and in the three composition composition diagrams when x+y+z=1.0) representing, x, y and z are in an A, B, C, D are the tetragonal ABCD zone on summit:
A：(x，y，z)＝(0.500，0.250，0.250)
B：(x，y，z)＝(0.300，0.250，0.450)
C：(x，y，z)＝(0.640，0.040，0.320)
D：(x，y，z)＝(0.384，0.040，0.576)。
16. according to the preparation method of ceramic electronic components described in the claim 15, the step of wherein burning till above-mentioned duplexer contains the step of burning till above-mentioned duplexer under the temperature below 960 ℃.
17. according to the preparation method of ceramic electronic components described in the claim 15, wherein above-mentioned sintering aid contains crystallization phases, described crystallization phases has the main peak value of using peak value that the Alpha-ray X-ray diffraction assay method of CuK measures and 2 θ=33.9 ± 0.1 °.
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| JP2005271624A JP2007084353A (en) | 2005-09-20 | 2005-09-20 | Sintering aid composition for ceramic, sintering aid for ceramic, low-temperature firing ceramic composition, low-temperature fired ceramic and ceramic electronic component |
| JP271624/05 | 2005-09-20 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110272263A (en) * | 2018-03-13 | 2019-09-24 | 中国科学院上海硅酸盐研究所 | A kind of low-temperature co-fired ceramic medium material and preparation method thereof |
| CN110483034A (en) * | 2019-09-18 | 2019-11-22 | 如东宝联电子科技有限公司 | A kind of high dielectric constant NP0 type media ceramic |
| CN113666722A (en) * | 2021-09-06 | 2021-11-19 | 中国科学院上海硅酸盐研究所 | Low-temperature sintered microwave dielectric material and preparation method thereof |
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| US8198204B2 (en) | 2008-06-30 | 2012-06-12 | Nippon Carbide Kogyo Kabushiki Kaisha | Alumina ceramic |
| KR101723270B1 (en) * | 2014-11-10 | 2017-04-06 | 한국세라믹기술원 | Manufacturing method of ceramics sintered body |
| CN109206132A (en) * | 2017-07-06 | 2019-01-15 | 中国科学院上海硅酸盐研究所 | A kind of high-dielectric constant microwave-medium ceramics material and its preparation method and application |
-
2005
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110272263A (en) * | 2018-03-13 | 2019-09-24 | 中国科学院上海硅酸盐研究所 | A kind of low-temperature co-fired ceramic medium material and preparation method thereof |
| CN110483034A (en) * | 2019-09-18 | 2019-11-22 | 如东宝联电子科技有限公司 | A kind of high dielectric constant NP0 type media ceramic |
| CN110483034B (en) * | 2019-09-18 | 2022-02-25 | 李吉晓 | High-dielectric-constant NP0 type dielectric ceramic |
| CN113666722A (en) * | 2021-09-06 | 2021-11-19 | 中国科学院上海硅酸盐研究所 | Low-temperature sintered microwave dielectric material and preparation method thereof |
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