CN1053519C - High frequency high stablility sheet multilayer ceramic capacitor porcelain - Google Patents

Abstract

The present invention relates to a ceramic material for a sheet type multilayer ceramic dielectric capacitor with high frequency and high stability. The ceramic material is baked by the following three materials: 77.0 to 90.5 wt% of main crystal phase, 4 to 13.5 wt% of modifier and 4 to 9.7 wt% of ceramic preparing auxiliary solvent. The finished product has the advantages of stable electric properties and good technological properties, and can be produced in bulk.

Description

High frequency, high stable chip multilayer ceramic capacitor porcelain

The present invention relates to the porcelain of high frequency, high stable chip multilayer ceramic capacitor.

At present, how intermediate sintering temperature high frequency, high stable dielectric ceramic composition are with BaNd ₂Ti ₅O ₁₄Be base, employing BaO-Nd is arranged ₂O ₃-TiO ₂The ternary system material, BaO-Nd ₂O ₃-TiO ₂-Bi ₂O ₃System and BaO-Nd ₂O ₃-TiO ₂-PbO based material, but above-mentioned porcelain all must just can sinter porcelain at the high temperature about 1250 degree, so can only use as monolithic medium and microwave dielectric material, development along with hybrid microelectronics, the introduction of intermediate sintering temperature chip multilayer ceramic capacitor automatic assembly line, existing a plurality of units carry out the development to porcelain, but do not see generally promoting the use of of this class porcelain yet.

The porcelain that the purpose of this invention is to provide a kind of high frequency high stable chip multilayer ceramic capacitor, for product lot quantity production, its manufactured goods electric property is stable, and processing performance is good.

Component of the present invention is formed by the mixture of the following three kinds of materials of roasting,

1) about 77.0%～90.5% (Wt) pottery preparation principal crystalline phase,

The ratio of calculating with oxide is:

Brium carbonate (BaCO ₃) 11.0%～26.5% (Wt)

Titanium dioxide (TiO ₂) 29.0%～44.3% (Wt)

Neodymia (Nd ₂O ₃) 20.5%～35.5% (Wt)

Bismuth oxide (Bi ₂O ₃) 5.2%～13.0% (Wt)

Tin ash (SnO ₂) 0.2%～0.1% (Wt)

Calcium carbonate (CaCO ₃) 0.01%～0.1% (Wt)

2) about 4%～13.5% (Wt) pottery preparation modifier,

The ratio of calculating with oxide is:

Red lead (Pb ₃O ₄) 37.5%～52% (Wt)

Calcium carbonate (CaCO ₃) 8.5%～28.5% (Wt)

Titanium dioxide (TiO ₂) 23.5%～39.5% (Wt) 3) the ceramic cosolvent of about 4.0%～9.7% (Wt),

The ratio of calculating with oxide is:

Yellow alumina (PbO) 38.0%～52% (Wt)

Zinc oxide (ZnO) 26.0%～34.5% (Wt)

Silicon dioxide (SiO ₂) 4.0%～10.0% (Wt)

Boric acid (H ₃BO ₃) 10.0%～19.5% (Wt) be of the present invention as follows than the optimum formula scope: 1) principal crystalline phase: 79.0%～89.0% (Wt)

In oxide calculating ratio be: BaCO ₃13.5%～23.5% (Wt)

(Wt) TiO ₂ 34.0％～42.5％(Wt)

Nd ₂O ₃ 23.5％～33.0％(Wt)

Bi ₂O ₃ 6.3％～11.5％(Wt)

SnO ₂ 0.2％～0.5％(Wt)

CaCO ₃0.01%～0.1% (Wt) 2) modifier: 5.0%～13.5% (Wt)

In oxide calculating ratio be: Pb ₃O ₄41.0%～49.5% (Wt)

(Wt) CaCO ₃ 15.5％～25.0％(Wt)

TiO ₂27.5%～36.0% (Wt) 3) cosolvent: 5.0%～8.0% (Wt)

In oxide calculating ratio be: PbO 41.0%～50.0% (Wt)

(Wt) ZnO 28.0％～32.5％(Wt)

SiO ₂ 5.0％～10.0％(Wt)

H ₃BO ₃12.0%～17.5% (Wt) optimum formula scope of the present invention is as follows, and 1) principal crystalline phase: 83% (Wt)

In oxide calculating ratio be: BaCO ₃20.0%～22.4% (Wt)

(Wt) TiO ₂ 36.6％～40.5％(Wt)

Nd ₂O ₃ 28％～32.3％(Wt)

Bi ₂O ₃ 6.3％～10.4％(Wt)

SnO ₂ 0.23％～0.30％(Wt)

CaCO ₃0.01%～0.015% (Wt) 2) modifier: 10.3% (Wt)

In oxide calculating ratio be: Pb ₃O ₄40%～50% (Wt)

(Wt) CaCO ₃ 16％～23％(Wt)

TiO ₂28%～37% (Wt) 3) cosolvent: 6.7% (Wt)

In oxide calculating ratio be: PbO 38%～52% (Wt)

(Wt) ZnO 25％～26％(Wt)

SiO ₂ 6％～8％(Wt)

H ₃BO ₃13%～18% (Wt) is existing to be further described the present invention in conjunction with the embodiments: table 1 is in conjunction with the formula table 1 of 4 samples of the present invention

Group group preface composition number	Principal crystalline phase	The modifier proportion		The flux ratio
					CaTiO 3	PbTiO 3
		1	83.0				5.15	5.15	6.70
2	83.0			5	5.15	6.85
		3	83.0				5.15	5	6.85
4	84.5			4.4	4.4	6.70

In the described prescription of table 1, require to use chemical pure or analyze pure-oxide, wherein principal crystalline phase becomes homogeneous mixture with the deionized water wet mixed by formula rate in container, is placed in the stainless steel disc after mixing and with homogeneous mixture and dries, be ground into fine powder then, and fine powder is placed on Al ₂O ₃In the crucible, put into the calcining of tunnel kiln,, be ground into fine powder again 1140～1180 degree roastings 2～3.5 hours.

Modifier burning piece is with chemical pure or analyze pure P _B3O ₄, C _aCO ₃, TiO ₂Press formula rate and mix oven dry, be ground into fine powder, be placed on AL then with said method ₂O ₃In the crucible,, pulverize standby then 1140～1220 degree roastings 1.5～2.5 hours.

Flux is with chemical pure or analyze pure P _bO, Z _nO, S ₁O ₂, H ₃BO ₃, use and produce method that principal crystalline phase burns piece and mix and dryout by formula rate, be ground into fine powder, be placed on Al then ₂O ₃In the crucible,, pulverize standby then 350～550 degree roastings 1～1.5 hour.

Burning pieces such as above-mentioned principal crystalline phase, modifier, cosolvent are put into the M45L ultra-fine grinding mill in proportion, and extra-fine grinding 25～45 hours becomes about particle diameter 1.0 μ m, and specific area is 3.2 ± 0.2m ²The fine powder of/g.

Fine powder is added organic bond and solvent, make film and make the multilayer ceramic capacitor that the high frequency high stable uses with banded casting molding processes, the multilayer ceramic capacitor of preparation has dielectric constant greater than 90, at 1MHz, Q value under the 1Vrms is 4000, Tcc is at 0 ± 30ppm/ ℃ in-55～+ 125 degree scopes, and the preferred temperature that capacitor is made in roasting is between 1100～1140 degree, is the best with 1120 degree.

The performance of above-mentioned each sample is shown in the table 2.

The electric preface of number is according to the property energy	K 25℃	Ri 25℃100V Ω	Q value 1MHz, 1V	Tcc(PPm/℃)		Withstand voltage V/mil	The firing temperature temperature retention time
								-55～+25℃	+25～+125℃
				1#	89					＞10 11	3500	-18.9	+23.41	1150	1120℃/2h
2#	88	＞10 11	2500			-21.2	+20.6	1130	1120℃/2h
				3#	90					＞10 11	2000	-19.8	+25.6	1110	1120℃/2h
4#	89.5	＞10 11	1800			-17.6	+19.8	1125	1130℃/2h

The described number of degrees of this specification are centigrade.

The present invention our experiments show that:

1) this porcelain has system's maturity, and the domestic raw material of used multiple different purity is had compatible preferably, raw material wide material sources, characteristics such as abundance.

2) porcelain technology, multilayer chip capacitor technology had good repeatability, stability, consistency.

3) it is little that this porcelain has loss, and insulation resistance is good, withstand voltage height, and have excellent Jie's temperature characteristics, aging characteristics, characteristics such as product qualified rate height.

4) this porcelain porcelain of substituting import one fully is that country saves foreign exchange, and improves the competitiveness of homemade sheets type ceramic dielectric capacitor.

Claims (3)

1, a kind of high frequency, high stable chip multilayer ceramic capacitor porcelain is characterized in that the dielectric ceramic component is formed by the mixture of three kinds of materials below the roasting,

1) 77.0%～90.5% (Wt) pottery preparation principal crystalline phase,

The ratio of calculating with oxide is:

Brium carbonate (BaCO ₃) 11.0%～26.5% (Wt)

Titanium dioxide (TiO ₂) 29.0%～44.3% (Wt)

Neodymia (Nd ₂O ₃) 20.5%～35.5% (Wt)

Bismuth oxide (Bi ₂O ₃) 5.2%～13.0% (Wt)

Tin ash (SnO ₂) 0.2%～0.1% (Wt)

Calcium carbonate (CaCO ₃) 0.01%～0.1% (Wt)

2) 4%～13.5% (Wt) pottery preparation modifier,

The ratio of calculating with oxide is:

Red lead (Pb ₃O ₄) 37.5%～52% (Wt)

Calcium carbonate (CaCO ₃) 8.5%～28.5% (Wt)

Titanium dioxide (TiO ₂) 23.5%～39.5% (Wt)

3) the ceramic cosolvent of 4.0%～9.7% (Wt),

The ratio of calculating with oxide is:

Yellow alumina (PbO) 38.0%～52% (Wt)

Zinc oxide (ZnO) 26.0%～34.5% (Wt)

Silicon dioxide (SiO ₂) 4.0%～10.0% (Wt)

Boric acid (H ₂BO ₃) 10.0%～19.5% (Wt)

2, a kind of high frequency according to claim 1, high stable chip multilayer ceramic capacitor porcelain is characterized in that its prescription can be made up of following,

1) principal crystalline phase: 79.0%～89.0% (Wt)

In oxide calculating ratio be: BaCO ₃13.5%～23.5% (Wt)

(Wt) TiO ₂ 34.0％～42.5％(Wt)

Nd ₂O ₃ 23.5％～33.0％(Wt)

Bi ₂O ₃ 6.3％～11.5％(Wt)

SnO ₂ 0.2％～0.5％(Wt)

CaCO ₃ 0.01％～0.1％(Wt)

2) modifier: 5.0%～13.5% (Wt)

In oxide calculating ratio be: Pb ₃O ₄41.0%～49.5% (Wt)

(Wt) CaCO ₃ 15.5％～25.0％(Wt)

TiO ₂ 27.5％～36.0％(Wt)

3) cosolvent: 5.0%～8.0% (Wt)

In oxide calculating ratio be: PbO 41.0%～50.0% (Wt)

(Wt) ZnO 28.0％～32.5％(Wt)

SiO ₂ 5.0％～10.0％(Wt)

H ₃BO ₃ 12.0％～17.5％(Wt)

3, a kind of high frequency according to claim 1, high stable chip multilayer ceramic capacitor porcelain is characterized in that its optimum formula ratio is,

1) principal crystalline phase: 83% (Wt)

In oxide calculating ratio be: BaCO ₃20.0%～22.4% (Wt)

(Wt) TiO ₂ 36.6％～40.5％(Wt)

Nd ₂O ₃ 28％～32.3％(Wt)

Bi ₂O ₃ 6.3％～10.4％(Wt)

SnO ₂ 0.23％～0.30％(Wt)

CaCO ₃0.01%～0.015% (Wt) 2) modifier: 10.3% (Wt)

In oxide calculating ratio be: Pb ₃O ₄40%～50% (Wt)

(Wt) CaCO ₃ 16％～23％(Wt)

TiO ₂28%～37% (Wt) 3) cosolvent: 6.7% (Wt)

In oxide calculating ratio be: PbO 38%～52% (Wt)

(Wt) ZnO 25％～26％(Wt)

SiO ₂ 6％～8％(Wt)

H ₃BO ₃ 13％～18％(Wt)