JPS60243902A - High dielectric constant porcelain composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to high-permittivity porcelain I] compositions, and in particular to low-temperature sintered type high-permittivity phase layers synthesized by solid-phase reaction of complex oxides. It is suitable for Hiramik] Ndenza.

[Problems with conventional related technology] Conventionally, high dielectric constant porcelain compositions have barium ditanate (B a T + 03 > as a main component), and calcium zirconate (CaZr03) and calcium ditanate (CaTi□ Composite dielectric porcelain materials are widely used.These porcelain materials usually have a
Since sintering must be carried out at a high temperature of ~1400°C, gold and platinum, whose main component is metallurgical, are used as internal electrodes suitable for this sintering temperature, especially for the platform of multilayer ceramic capacitors.

It has the disadvantage that palladium or an alloy thereof must be used. Because it is sintered at a relatively high temperature, it requires a lot of thermal energy such as electric power and gas, which causes significant thermal deterioration of the firing furnace and firing pods, which also has the disadvantage of contributing to increased costs.

For this reason, since we use inexpensive internal electrodes mainly composed of silver, etc., we can sinter at a low temperature of 1000°C or less, and the dielectric constant is large and the dielectric loss is small. There was a desire to develop a porcelain composition.

In response to these demands, Pb(Fe2/3W1/3)X-
(F01/2Nb1/2) 1-×03 (x is 02≦0
5) Materials are known. Also, JP-A-53-155
In Publication No. 91, an attempt was made to add SiO to this material system. However, in this material system, the temperature characteristics of dielectric loss (t: a nδ) are poor and the insulation resistance is also low. Small. Roughly weak mechanical strength, 2 cracks, 1 chip
This has been a major practical problem when manufacturing multilayer ceramic capacitors because of the tendency for this to occur.

[Objective of the invention 1] The above-mentioned drawbacks have been improved, the dielectric constant and insulation resistance are large, the dependence on firing temperature is small, the temperature characteristics of 1 an δ are excellent, the mechanical strength is excellent, and the high temperature load and moisture resistance are improved. 9 low humidity sintered type high permittivity porcelain composition
The purpose is to provide.

[Summary of the invention 1 The present invention provides barium oxide (BaO), calcium chloride (
At least one type of lead oxide (PbO), oxide ore (F e 203 ), 1M diAb (Nb205),
Tungsten oxide (WO3).

From copper oxide (Cub) to 4r, xPb (toe1/2”b)
) O-yM (CU 1/2 W1/2) 03
(Iko1/23 Dashi M is at least one of Ba and Ca), X=90 to 99.5. Ti% of the basic composition 100 with y = 0.5 to 10 is added to Ti%, and -C magnesium oxide (MgO) and nickel fluoride (N10) are each added in an amount of 0.01 to 1.0% by weight as additives. The high dielectric constant ceramic composition and the high dielectric constant ceramic composition further contain 0.01 to 1.0% by weight of manganese oxide (MnO) as an additive.

Next, the reasons for limiting the composition of the present invention will be described. Okay.

xPb (Fe1/2 Nb1/2)-yM (CL
J y2 W172 ) 03 TV'i:5
X of RelFA book 1 inch product is 90-99.5. V is 0.
The reason for limiting the composition range to 5 to 10 is that when X = less than 90, the dielectric constant at room temperature is low and it is not suitable for condensate + lJ monthly yield, and when V = less than 0.5 (31 M (C
This is because the effect of u1/2W1/2)03(M:Ba, Ca) is hardly affected, and when y=10 or more, C decreases the dielectric constant and increases tan δ. Also, the reason why the MgO content was limited to 0.01 to 1.0% by volume is 0.0%.
If it is less than 1% by weight, no improvement in mechanical strength or insulation resistance can be expected, and if it exceeds 1.0% by weight, dielectric and insulation resistance will decrease.

This is also because sufficient sintering is not achieved, the specific gravity is low, and the sintering temperature becomes substantially high. NiO content 0.01
The reason why it was limited to ~1.0% by weight.

If it is less than 0.01 wt %, the effect of NiO, which can improve the dependence of insulation resistance on firing humidity, will hardly appear, and if it exceeds 1.0 wt %, sufficient sintering will not occur and the dielectric constant will decrease. and pick up the decrease in insulation resistance, and further l: a
n 6 increases and UL, J: can be used. Furthermore, the reason for limiting the MnO content to 0.01 to 1.0% by weight is that if it is less than 0.01% by weight, the thermal properties of tan δ + The effect of MnO on improving the high humidity fJ'l+F characteristics a3 and the moisture resistance characteristics was hardly exhibited.

This is because when the content exceeds 1.0% by weight, [, U t: an δ] increases.

[Embodiments of the Invention] A high dielectric constant ceramic composition according to the present invention is manufactured, for example, as follows. Mazu′, as Idemitsu Gensaku.

PI) (,), Fe OWO, Nb2O5,.

23′.

CaC0Ba, C03, Cub, MgCO3゜3゜M n CO3, N i O, etc. were weighed and weighed so as to have the compounding ratios shown in Table 1. After wet-mixing these raw materials in a ball mill, roasting is performed at 700-800℃ (
, P and VL are ground again in a ball mill to form a dry powder.
Add binder such as A, approximately 0゜3 ton/c
A disk-shaped sample with a straight W' of 17 mm and a thickness of 1.2 mm was prepared at a pressure of i. These molded bodies were placed in a 4J47 made of magnesia and fired for 2 hours at 850 to 950°C in 131 air containing an acidic atmosphere, and then silver paste was applied to the sintered body and baked at 600 to 700°C. This was used as a measurement sample.

Here, the dielectric constant and jan δ were measured at 9 frequencies and 1 KllZ, and are shown in Table 1.

(Leaving space below) In Table 1, two reference examples are outside the scope of the present invention, and are shown for comparison.As is clear from Table 1, the examples within the scope of the present invention have a large dielectric constant. It shows a high temperature of about 21.000-30°000, and the dielectric loss (1, an δ) is 0.3-0.8
It is possible to perform firing at a temperature of 900° C. or higher while exhibiting an extremely small polishing value of about 100%.

Furthermore, FIG. 1 shows Example 17. Figure 2 shows Example 44, 3
The figure shows Example 71. FIG. 4 shows the temperature characteristics of the dielectric constant and j a rTδ of Example 98. In addition, as reference examples, reference example 2 A5 J: and 44 are shown in FIG. 5, reference example 26 is shown in FIG. 6, and reference example 68 is shown in FIG. 7. J, which is clear from Table 1 and Figures 1 to 7, shows the temperature characteristics of 9
The ceramic composition of the present invention is Pb(Fe1/2Nb1/2
) 03 to M (CLJ 172 W1/2) 03
Due to the solid solution size of (M: Ba, Ca), the dielectric constant of (Pb(FeNb)0 at room temperature is 101/2
It can be seen that 1 is dramatically improved by 3.5 to 5 times compared to the case of 1/2 3 Q mo 1%, and that lan δ is significantly reduced by about 1/10. Addition of a small amount of M20°NiO to the sea urchin not only significantly increases the corrosion resistance but also
．． As shown in 5, 6J5 and 46.47.48, the specific resistance increases by 4:
It can be seen that the dependence can be greatly improved by dramatically reducing the amount of stress.1 This means that r? i, Ei',: lL'
(15) -20°C of electric furnace and lli of culm HQ
This means that even if there is a general setting I-ra (X), it is possible to manufacture IC products with stable insulation resistance.

Furthermore, the addition of MnO at a low temperature (-F) 5
'(: ) to J-3() 1-a nδ from 1/2 to 1
/ 5 and significantly flf F salmon.

i! 'N product (125°C) also has 1. ' E) r
It can be seen that lδ remains constant from 2/3 to 1/2.

MQO, N iO, Mr) 0 so 4'L 't, l' Addition 1' (is 0°01 to 1.0% by weight of 1 to 1)
t below 1 cq, ↓.

Each works on the 11 prizes and improves their characteristics.

Take advantage of each other's strengths! It can be seen that this is due to the characteristic of a crowd that there is absolutely no effect.

Next, bending strength was used for the total mechanical strength 1+Ili.

To measure bending, the resulting dielectric ceramic disc was ground on both sides to a thickness of 1 mm to give it a mirror surface. Ge.

After that, a sample plate with a width of 3 mm was cut from the center of each round of the diamond cutter C, and the cut surface was sequentially polished with SiC sandpaper from 800# to 1500# to 2000# to remove Li2 damage caused by scratches on the cut surface. After that, the edges were finished by rounding, and the bending strength was 1 bending [(transverse rupture strength) G is according to the following formula.

Pml Transverse rupture force −−□−−−−−−−− d2W where )) m: Maximum breaking load 1n (Ky) 1: Pressure between fulcrums 1IIIt (cm) d: First test thickness (cm) W : Width of the sample (cm).

Data of Example 1 of the present invention are shown in Table 2 together with reference examples.

Second. 1. As is clear from the results in Table 2, a small amount of MgO,N
It is clear that the mechanical strength can also be significantly improved by adding iO. This fact is very advantageous for chip components that are directly soldered onto a circuit board.

15.1.0% by weight or more (7) MrlO, Mg'O
.

Adding NiO does not improve mechanical strength.

Next, a high temperature negative 611 test d3 and a splash resistance fL test were conducted.

Product K・7 used for this high temperature load test d3 and moisture resistance test
The condensate is mixed with a powder after roasting, for example, with a binder such as privinyl butyral, polyethylene glycol, or octyl phthalate.
■Use an appropriate amount of solvent such as tylarniol.

4. Create a normal slurry ~, create a 50 μm J9 sheet 1~ using a Dr. Plaid device, print electrodes, laminate, cut [Di, then bake, and remove the external electrodes.
A laminated cubic capacitor of 5×3.2 mm and 1 μF was fabricated. This laminated condenser is tested for 100 pieces according to the 1 old single load test J specified in the Japan Electronics Machinery Association Standard RC-3698B Laminated Funnel for Electronic Equipment (chip type).
3 and moisture resistance tests were conducted, and the failure rate and change in capacity after test 8 are shown in Tables 3 and 4, respectively.

In addition, each test is based on the above standards, and the high temperature load test is 50
The characteristics after vDC application fL 125℃
The characteristics were evaluated after 111500 hours under C application condition at 40° C. and 95% R111.

Table 3 (white space below) Table 4 (white space below) As is clear from Tables 3 and 4, adding a small amount of MnO improves the failure rate by one person (6).
The rate of change in is also smaller, which improves the high temperature load characteristics.

1 was confirmed to have excellent moisture resistance. In the above examples, oxides were used as starting materials.

Although carbonates were used, it goes without saying that similar effects can be obtained by using other organometallic compounds such as oxal oxides in place of oxides at high temperatures.

[Effect of the invention] As described above, in the present invention, the dielectric constant is large.

Temperature characteristics of tan δ 2 Excellent mechanical strength, especially when a small amount of M
By containing qO and NiO, it is possible to significantly improve the specific resistance and also to significantly improve the dependence of the specific resistance on the firing temperature.

Furthermore, by avoiding the inclusion of a small amount of MnO, a low-temperature sintering type high-permittivity ceramic composition with improved high-temperature load characteristics and moisture resistance was obtained, which can be said to be extremely excellent in the industry.

[Brief explanation of drawings]

Figures 1 to 4 are curve diagrams showing characteristic examples of high dielectric constant ceramic compositions according to the present invention, and Figures 5 to 7 are curve diagrams of 8 dielectric constant porcelain compositions as reference examples. It is a curve diagram showing an example of characteristics. Representative patent attorney Norichika Kensuke (Hagai name) Onsen (OO) Temperature (0りん) 艷 (0(, Noritake (0c)

Claims (1)

[Claims] (1) At least one of barium oxide, calcium oxide, lead sulfide, iron oxide, and at least one of calcium oxide. Consists of tungsten oxide and copper oxide. XPb(F81/2Nb1/2)03-yM (Cu
172 W1/2 ) 03 (However, M is [3a, C
at least one type of a), x = 90 to 99
．． 5. Based on 100% by weight of the basic composition with y=0.5-10. A high dielectric constant ceramic composition containing magnesium oxide and nickel oxide as additives in an amount of 0.01 to 1.0% in heavy phase, respectively. (2. In the high dielectric constant ceramic composition described in claim (1), 0,
Contains 01-1.0% by weight! 1=A high dielectric constant ceramic composition characterized by the following.