JPS6356569A - Heat-resistant resin coating material - Google Patents

Abstract

PURPOSE:To obtain the titled coating material, by adding a ketone to a silicone coating material prepared by blending a polyladder organosiloxane with a polydiethoxysilane and having improved preservation stability. CONSTITUTION:A coating material obtained by adding (B) a ketone, e.g. acetone, etc., to (A) a silicone coating material prepared by blending a polyladder organosiloxane expressed by formula I (R1 is CH3/C6H5=2/1), etc., with a polydiethoxysilane expressed by formula II (R2 is C2H5/H=1/1), etc.

Description

[Detailed Description of the Invention] [Summary] As a method for improving the storage stability of silicone paints,
Polyladder A resin paint made by adding ketones to a silicone paint that is a mixture of organosiloxane and polyjetoxysilane.

[Industrial application field]

The present invention relates to a heat-resistant resin paint with improved storage stability.

In order to quickly process large amounts of information, information processing technology has made remarkable progress, and the semiconductor devices that play the leading role in this, such as ICs and LSIs, have become larger in capacity through miniaturization and integration of unit elements, and VLSI has been put into practical use. has been done.

Here, miniaturization and integration are achieved using thin film formation technology and photoetching technology (photolithography or electron beam lithography). A multilayer three-dimensional circuit is formed by repeating the process of forming a conductor pattern, insulating it, providing through holes as necessary, and then forming a conductor pattern thereon to establish conduction with the conductor pattern in the lower layer.

Here, since the conductor pattern has a thickness of several thousand layers, in multilayer wiring, a step occurs in the insulating layer on the conductor pattern, and this needs to be alleviated.

That is, silicon dioxide (SiOt) is used as the glabella insulating layer.
It is suitable as an insulating material because it has excellent electrical properties such as withstand voltage and insulation resistance, and chemical properties such as heat resistance and stability.

However, when this 5i02 layer is formed by a chemical method such as electron beam evaporation or sputtering, it is formed in a similar shape to the underlying layer, which causes disconnection of the conductor pattern formed thereon at the position of the step. However, there are problems in terms of credibility.

Therefore, chemical vapor deposition (abbreviated as CVD) is used to thermally decompose silicon compounds such as silane (SiH*) in an oxidizing atmosphere to create a SiO□ layer with reduced steps. There is.

However, the growth rate of CVD films is slow at less than 1000 Å per minute, and the processing steps are troublesome.

On the other hand, there is a method of coating silicone resin by a spin coating method using a spinner, which is simple and can be formed thickly, and also eliminates steps and surface irregularities, so it is possible to create a multilayer structure. It is used as an insulating layer.

Here, among the many insulating resins such as polyimide, silicone resin is used because it has excellent heat resistance, and it decomposes when heat treated at a temperature of 500°C or higher in an atmosphere containing oxygen (0□). This is because even if this starts, the insulation resistance does not decrease because it decomposes into SiO□, and the smoothness hardly changes.

[Conventional technology]

A silicone resin is one in which an organic group and a functional group are bonded to a tetravalent Si atom to form a chain-like organic compound.

Here, the organic groups are methyl group (CH3), ethyl group (C2
1! S) + refers to phenyl group (C6H5)...etc., and functional groups include halogen group, O11 group, methoxy group, etc.
It refers to...etc.

Based on the number of organic groups and functional groups attached to the Si atom, it is divided into four types: M units, D units, T units, and Q units.
Among them, the T unit is known to have one organic group per Si atom and to have a ladder-shaped structure, and is most suitable as a material for forming an insulating layer due to its adhesion to the substrate and flexibility.

FIG. 1 shows the structural formula of such a silicone resin used for interlayer insulation, and because it has a ladder-shaped structure, it is called polyladder organosiloxane (abbreviated as PLO3).

Here, R, refers to an organic group, and C1h group and C, R5 group exist at this position in a quantitative ratio of 11, and in reality, it does not have a complete ladder structure, and the bond is This shows that it is partially cut and is formed containing an OH functional group.

Such PLOS is generally called PLOS-G and is commercially available.

Now, PLOS-G is used by adjusting the viscosity using a solvent such as butyl cell solve acetate (abbreviated as BCA), creating an insulating layer by spin-coating it on the substrate to be processed, and forming a conductive pattern on this. However, it has been found that when formed thickly, cracks tend to occur (and there are also problems with adhesion to the substrate to be processed).

Therefore, it is currently used by mixing it with polyjethoxysilane (abbreviated as PDεS) whose structural formula is shown in FIG. 2 at a ratio of about 1:1.

Here, R2 in FIG. 2 represents each organic group of C2H5 and H,
This shows that they are present in a 1:1 ratio.

In this way, interlayer insulating layers are currently made using a mixture of PLOS-G and PDES, and problems such as cracking have been solved.

The action of PDES in this case is to form a network structure through a condensation reaction in which the OH groups present in PLOS-G and the 011 groups present in PDES bond.

Now, in the manufacturing process of LSIs and VLSIs, in order to smoothly mass-produce PLOS-G and P[lES, it is necessary to mix them in advance and use them as needed, rather than mixing them before use. For this purpose, it needs to be kept stable for about one month in the refrigerator.

However, there was a problem in that the condensation reaction gradually progressed even in the refrigerator, increasing the viscosity of the mixed liquid, and the lifespan was as short as a binary interval.Therefore, it was necessary to improve this problem.

[Problem that the invention seeks to solve]

As mentioned above, PLOS-G and PD are used as interlayer insulating layers.
Although a mixture with ES has been used and good results have been obtained, the problem is that the storage stability is poor.

[Means for solving problems]

The above problem can be solved by adding a ketone to a silicone paint containing a mixture of PLOS-G and PDES.

[Effect]

In the present invention, the viscosity increases when a mixture of PLOS-G (!: PDES) is stored because OH groups present in PLOS-G react with 0HfA in PDES and condensation progresses. , this is due to the progress of gelation.

Therefore, in order to prevent condensation, both OH groups should be prevented from coming close to each other.

Therefore, the present invention focuses on the fact that PDES and ketones easily react, and prevents the condensation reaction from proceeding by adding a ketone to a mixed solution of PLOS-G and PDES in advance.

Figure 3 shows PDES when acetone is added to PDBS.
It shows a state in which an acetone molecule is added to the 0 atom inside.

Here, even if a ketone is added, it does not necessarily react as shown in Figure 3 due to the low storage temperature, but since the ketone has a polar group, it approaches the OH group of PDES, and therefore The condensation reaction between PLOS-G and PDES is prevented.

〔Example〕

Acetone (CI,
Prepare C0CH5), first add acetone and PLOS-G to a solution of PDES dissolved in an equal amount of BCA and stir.
A resin liquid was prepared by uniformly mixing.

Here, the mixing ratio of PLOS-G and PDES is 1:1.

This resin liquid was stored in a refrigerator maintained at 3°C.
- No increase in viscosity occurred even after several months had passed, proving that the storage stability was improved.

In addition, this resin liquid was spin-coated in the conventional manner, and then
The results of condensation and curing by heating at 00° C. for 1 hour were similar to those of a conventional insulating layer to which no acetone was added, and showed excellent properties as an interlayer insulating layer.

〔Effect of the invention〕

As described above, by implementing the present invention, PLoS-G and PLoS-G
It is possible to increase the storage stability of the resin liquid consisting of DIES, thereby making it possible to improve workability.

[Brief explanation of drawings]

Figure 1 shows polyladder organosiloxane (PLOS-G).
), Figure 2 is the structural formula of polyjethoxysilane (PDBS), and Figure 3 is the structural formula of polyjethoxysilane subjected to an addition reaction with acetone.淋、Pakusu"?'Fl l) cH3161Jr=2A Tree ° Rirada 1 or 77" Noshi O Hatsun (FLOE-6r) 6')
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Claims (1)

[Claims] A heat-resistant resin paint characterized by adding ketones to a silicone paint that is a mixture of polyladder organosiloxane and polydiethoxysilane.