JPS63129086A - Ceramic structure - 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] ■ Behind the invention E Technical field The present invention relates to ceramic structures.

Prior Art and its Problems In recent years, with the miniaturization of electrical T-equipment and the increase in the output of T-conductor parts, various insulating materials used as substrates and the like are required to have high thermal conductivity and high density. For these reasons, aluminum nitride sintered bodies have been attracting attention.

Aluminum nitride sintered bodies have good thermal conductivity because the thermal conductivity of aluminum nitride is five times higher than that of alumina.
Moreover, it has the advantage of having a small coefficient of thermal expansion.

By the way, the density of circuits that can be mounted on a single board is limited, and it is considered effective to use a multilayer board in order to further improve the mounting density.

Among them, MOLW on a ceramic green sheet
Multilayer ceramic substrates, which can be obtained by printing wiring with a paste such as silica, aligning the positions, stacking the required number of layers, and firing, are expected to be put into practical use due to their excellent heat dissipation properties.

In fact, high purity AI! AlN multilayer wiring board obtained by forming through holes in a green sheet made by adding a binder to a mixed powder of N powder and CaC2 powder, printing a conductor with a paste of W added with AuN, planting a layer, and firing it. It has been reported (Ceramic Industry Association Magazine 1986, 305-306)
Page 2HO2).

However, this material does not have sufficient properties such as electrical resistance, thermal conductivity, and adhesive strength, and it is desired to improve the conductive material when AIN is used as a sheet.

■ Purpose of the Invention The purpose of the present invention is that when using an AlN green sheet, the adhesive strength between the substrate and the metal is high, it is dense and has good heat dissipation, the metal has good conductivity, and the heat of the substrate itself is high. The object of the present invention is to provide a ceramic structure that has high conductivity and electrical resistance and has suitable performance as a metallized substrate, and also has extremely good characteristics as a multilayer wiring board.

■Disclosure of invention These objects are achieved by the invention described below.

That is, the first aspect of the present invention is that at least one of W, Mo, and Ta is 80 to 99.5% by weight, and the balance is at least one of Ca, a Ca compound, Y, and a Y compound. This is a ceramic structure in which a composition containing the above is metallized onto an AuN base material and is co-fired.

Further, the second invention provides a mixture containing 80 to 99.5ffi% of at least one of W, Mo, and Ta, and the balance containing at least one of Ca, a Ca compound, Y, and a Y compound. For 100 parts by weight, A
N□03° This is a ceramic structure in which an Al2N base material is metallized with a composition containing 30% by weight or less of at least one of Al1N, A14 C3, Mn, and Ni and then co-fired.

■Specific structure of the invention Hereinafter, the specific configuration of the present invention will be explained in detail.

The ceramic structure of the present invention uses W, M as the conductor material.
80-99 at least one of o and Ta
．． 5% by weight, preferably 80 to 90% by weight, and the remainder contains at least one of Ca, Ca compounds, Y, and Y compounds, and the insulating material is AIL.
Metalized AlN is obtained by simultaneous sintering using N green sheets.

Then, as a conductor material, Al2 o3, AlN
.

It is more desirable to use a material containing at least one of Al4C3, Mn and Ni in an amount of 30% by weight or less, preferably 5 to 10% by weight.

The reason why the metal component of the conductor material is at least one of W, Mo, and Ta is because the firing temperature in the simultaneous firing described later is about 1800°C, so it is necessary to mainly use a metal with a melting point of 1800°C or higher. This is because there is.

In addition, the metal component is 80 to 99.5% by weight.
If it is less than 0% by weight, it will cause an increase in the resistance of the conductor part formed from the conductive material, and if it exceeds 99.5% by weight, the adhesive strength between the substrate and the four-part part will decrease.

The reason why at least one of Ca, a Ca compound, Y, and a Y compound is added is to facilitate metallization of Al1N. That is, the sintering of AIN is
Since this is a liquid phase sintering process in which the oxide layer Al1203 on the N surface is formed with Ca, Ca compounds, Y, and Y compounds listed in -F, these compounds, which are liquid phase forming components, are added to the metal component to increase the density of the metal. This is to improve the bond between the Al2N surface blood and the metal.

The reason why the remaining amount of metal is 20 to 0.05% by weight is as follows.
This is because, outside this range, the four-body resistance increases, resulting in defects as a conductor, and the adhesive force to the substrate becomes weak.

In this case, the Ca compound is ■ (physically CaO1C
aB6, CaF2, CaH2, Ca3N2, C
aCl2, Ca(CN)2, CaC2, CaSiF
6, CaS, (a3P2, CaS i, CaS i
2. Calcium formate, calcium acetate,
Calcium oxalate, calcium acetyl salicylate, calcium ascorbate, calcium bromolactobiolate, calcium N-carbamoyl asparadate, calcium citrate, calcium 2-ethyl butanoate, calcium gluconate, calcium lactate, calcium levulinate, calcium Mesooxalate, calcium palmitate, calcium pantothinate, calcium phenoxyto, calcium propionate, calcium methoxide, calcium ethoxide, calcium propoxide, calcium isopropoxide, calcium bisacetylacetonate complex, etc., and Y compounds As Y2 o3. YF3, YB6,
Y2 N3, YCffi3, YBr3, YI3.
Y) 12-3. YN% Y(CN), YC2, Y2 N
3, YP, YSi, YAj22, YSb, YAs, Y
Bi, Y2Se3, Y2Te3. Examples thereof include yttrium acetate, yttrium oxalate, yttrium methoxide, yttrium ethoxide, yttrium propoxide, yttrium isopropoxide, yttrium phthalocyanine complex, and yttrium porphyrin complex, among which CaO1Y203 is preferred.

These additives are also normally used as sintering aids when producing Al2N sintered bodies.

In the present invention, as mentioned above, roughly Al2O3, Al1N, Al4
At least one of C3, Mn and Ni may be added.

It is preferable to supply AJ2203 when there is little Affi203 layer on the AIN surface or when there are few oxides in the metal. This is because the adhesive strength between AlN and metal increases.

AIN is preferably added when there is a difference in the coefficient of thermal expansion between the metal and Al2N (however, the coefficients of thermal expansion of Mo and Al1N are approximately equal). This is to perform f+ control of the coefficient of thermal expansion.

Al4C3 is preferable because it easily reacts with the oxide component at 1800° C. to generate active Al2N. Also Af
fi203 is also converted to AfLN.

The active Al2N generated in this way is
Integrates with N to improve adhesive strength! j, because it does. When r- is schematically shown to generate AR,N,
It will look like this:

Al24 c3 +Aj22 o3 +3N2-+6A
It N+3CO Mn, Ni is preferable in order to improve the adhesion between the Al2O3 layer on the AQN surface and the metal.

Also, when adding these compounds, the time of addition is 30 H.
The reason why fHQ% is set below is that if it exceeds 30% by weight, the conductor resistance increases.

Conductor materials containing such components are usually used in the form of a paste, but the binder used in this case may be any salt binder that can be used later, such as ethyl cellulose. ,for example,
Examples include α-terpineol.

In addition, when making a paste, the average particle size of each additive is W
, o, i~54 for Mo, Ta, 0.1~10- for Ca, Y compounds, etc., 0. for AJ2 compounds, Mn, Ni, etc.
It should be about 1 to 10-.

The ceramic structure in the present invention uses A as an insulating material.
Use RN green sheets.

The AlN green sheet is obtained by adding and mixing powder to be used as a sintering aid when creating an AlN sintered body to ARN, and press-molding the mixture at room temperature.

Such powders include calcium, barium, strontium, or rare earth metal hydrides, oxides,
Fluorides, chlorides, cyanides, thiocyanides, carbides, silicofluorides, sulfides, gayrides or intermetallic compounds; calcium boride, strontium boride, barium boride, rare metal borides, magnesium boride , aluminum boride; rare earth elements, calcium, barium, strontium; aluminum oxide, calcium oxide, magnesium oxide, beryllium oxide, boron oxide; boron nitride; silicon carbide; organic compounds or 4r organ complexes of calcium or yttrium; etc. .

Among them, it is preferable to use calcium, yttrium, or a compound thereof.

Specifically, regarding the method of creating an AIN green sheet, see Japanese Patent Application Nos. 59-215971 and 59-2658.
No. 52, No. 59-265853, No. 59-26585
No. 4, No. 59-265855, No. 59-265856
No. 60-55094, No. 60-55095, No. 60-55096, No. 60-57164, No. 61-
No. 19870, No. 61-125362, No. 61-14
The method up to the step of obtaining a molded body in the method for manufacturing an AlN sintered body described in No. 4183 and the like can be referred to.

Next, a method for manufacturing the ceramic structure of the present invention will be described.

The conductor material is at least one of W, Mo, and Ta.
species, at least one or more of Ca, Ca compounds, Y and Y compounds, and optionally AJ22 o3. A
At least one of l2N%Aj24C3, Mn, and Ni is mixed in a predetermined ratio, and a binder that can be debound later and a solvent that dissolves this binder to form a slurry are added to the mixture, and the mixture is thoroughly mixed. Obtained by kneading to make a paste.

This paste is printed on the ARN green sheet obtained as described above, and if necessary, a predetermined number of 41 sheets are bonded by thermocompression.

Thereafter, the binder is removed from this product by gradually raising the temperature in a mixed gas of N2 and N2 at a temperature in the range of room temperature to 700°C. The reason for setting the atmosphere during binder removal as above is to reduce decarburization, and the reason for setting the above temperature range is to ensure that the binder does not decompose at temperatures below room temperature. This is because removal of the binder results in non-resistance, and if the temperature exceeds 700°C, the decomposition temperature of the binder is far exceeded, so the binder becomes non-resident.

Thereafter, further 175
It is baked at a temperature of 0 to 1850°C for about 0.5 to 3 hours.

Specifically, the firing may be performed by normal pressure firing.

Note that Al1N usually has a thickness of about 5 to 50 mm, and metal has a thickness of about 2 to 20 mm.

Further, multi-layering is possible up to about 10 layers.

The ceramic structure of the present invention created in this way is
The adhesive strength between A42N and metal is 2 Kg/- or more, and the thermal conductivity of metallized AuN is 180 at room temperature.
W/mK or more -L.

Further, the electrical resistance of Al2N is 1014 Ωcm or more, and the electrical resistance of metal is 20 mΩ/mouth or less.

Moreover, by increasing the number of layers, the number of IC and LSI chips mounted can be increased, and a multilayer wiring board that is extremely advantageous for IC packages and the like can be realized.

■Specific effects of the invention According to the invention, at least one of W, Mo, and Ta is added to a nailing percentage of 80 to 99.5%, and the balance is Ca.
, a Ca compound, Y, and at least one of a Y compound
containing seed crystals, or preferably a mixture thereof1
For 00 Shigekawabe, AIL2 o3, Al2
Al1N contains at least 30j71]% or more of at least one of N, Al14C3, Mn and Ni.
Because it is metallized, the adhesive strength between the substrate, plate and metal is high, it is dense and has good heat dissipation, and the metal has good conductivity.
In addition, the substrate itself has high thermal conductivity and electrical resistance.
A ceramic structure with suitable performance as a metallized plate is used.

For this reason, a multilayer wiring board with extremely good characteristics can be
can be done.

(2) Exemplary Embodiments of the Invention The present invention will be explained in more detail by showing exemplary embodiments of the present invention.

Example 1 (1) Creation of AI2N green sheet - AlN powder with uniform particle size of 3-
0-YC2 powder was added in an amount of 2 times 1'' and mixed.

Next, a pressure of about 1,000 g/C was applied to this mixture at room temperature to form a molded product with a thickness of 100-100 g/C.

In this way, the AlNff-n sheet (length 2cm, width 2cm)
cffI, length 1m+n) was created.

(2) Creation of conductor material (paste) As shown in Table 1, ethyl cellulose is used as a binder in a mixture of metal, Additive T, and Additive II, and the binder is further dissolved to form a slurry. Using α-terpineol as a solvent, a mixture of α-terpineol and ethyl cellulose in a weight ratio of 88:12 was added, and this mixture was kneaded to [- minutes] to prepare a base.

Note that the ratio of the metal component to the binder component is weight - [ratio of 8
The ratio was set to 0:20.

(3) Printing The L paste was printed to a thickness of 10P on the AILN green sheet prepared as described in 1 and bonded under heat.

(4) Burning: Debinding in a 5:1 mixed gas of nitrogen and hydrogen at a temperature in the range of room temperature to 700°C, and further at 1800°C for 2
Baked for an hour.

In this way, samples 101 to 136 (invention) in Table 1,
and Samples 201 to 205 (comparison) were created.

The properties of these samples are shown in Table 1.

The characteristics were measured as described in F.

(1) Thermal conductivity Measurements were made on the metallized substrate at room temperature.

(2) Electrical resistivity Regarding the AIN substrate, the Ag paste electrode setting was measured on both sides.

Further, for metal, a pattern of 10 crn was used for measurement.

(3) Form 3 to 5 tin plating +V of 211I11 x 2 cm size on the tensile strength test sample at equal intervals, glue the lead wire to the plated part, and run the lead wire in the IC direction perpendicular to the tin plating. The tensile strength was measured by pulling with a force of 2 g.

From Table 1, the effects of the present invention are clear.

Example 2 Example! A multilayer ceramic substrate was created using the composition of each sample of the present invention created in . That is, 5 x 5
Print the conductor on the ctnA It N green sheet and
After laminating the layers, firing was performed in the same manner as in Example 1.

As a result, an extremely good multilayer wiring board that can mount up to eight LSIs has been realized.

Claims (6)

[Claims] (1) A composition containing 80 to 99.5% by weight of at least one of W, Mo, and Ta, and the balance containing at least one of Ca, Ca compound, Y, and Y compound, A ceramic structure characterized by metalized material. (2) The ceramic structure according to claim 1, wherein a metalized AlN base material is laminated. (3) The ceramic structure according to claim 1 or 2, wherein AlN and the composition are co-fired during metallization. (4) Based on 100 parts by weight of a mixture containing 80 to 99.5% by weight of at least one of W, Mo, and Ta, and the balance containing at least one of Ca, Ca compound, Y, and Y compound. , Al_2O_3, Al
A ceramic structure comprising an AlN-based base material metallized with a composition containing 30% by weight or less of at least one of N, Al_4C_3, Mn, and Ni. (5) The ceramic structure according to claim 4, wherein a metallized AlN base material is laminated. (6) The ceramic structure according to claim 3 or 4, wherein AlN and the composition are co-fired during metallization.