JPS60165719A - Mask substrate for manufacturing semiconductor integrated circuit, surface protecting solution of wafer and method of use thereof - Google Patents

Abstract

PURPOSE:To protect the surfaces of a mask, a wafer and the like by dissolving resin having a plenty of film formability and separability in a solvent, and coating the solution on the mask, wafer and the like. CONSTITUTION:Vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, cellulose derivatives, epoxy resin, polychloroprene and their mixtures are used. A polymer of a composition of 85-93wt% of vinyl chloride and 7-15wt% of vinyl acetate is particularly preferable. A solvent is selected from fatty or romatic hydrocarbon, ketone, alcohols, esters, chlorinated or fluorided hydrocarbon in response to the type or resin, and the amounts of metal impurities are suppressed to prevent the diffusion and contamination of the impurities. A colrant is added to readily discriminate the irregular film. A protective film is sufficient with 0.02-0.3g/cm<3>, but preferably 0.1-0.2g/cm<3> to prevent the disconnection at the separating time. With this configuration, effective surface protective film can be formed on a mask or a wafer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surface protection liquid for mask substrates, wafers, etc. for manufacturing semiconductor integrated circuits, and a method for using the same.

Mask substrates, wafers, etc. that are used in the process of manufacturing semiconductor integrated circuits are required to be of high quality with no damage or dirt. There has been a problem in that dust, oil, etc. may adhere to the photomask chips for various reasons, and pattern defects may occur due to burns or stains caused by oxidation to unnecessary portions, increasing the defective rate of photomask chips. For example, even if the product has been carefully cleaned and finished in a clean room, the cleanliness may be insufficient during transportation in a carrier box or rack or during automatic transportation, or there may be problems with cleaning due to damage during transfer of mask substrates, wafers, etc. Once the plants grow, the washing process will have to be repeated many times.

In order to eliminate such defects on mask substrates, wafers, etc., it has been proposed to provide a protective film on the surfaces of these. In Japanese Patent Publication No. 52-12057@, a protective film of sodium oxide/chloride is applied to the surface of a semiconductor wafer, and in Japanese Patent Publication No. 50-5021, a protective film of silica is applied to the surface of a semiconductor that has been cleaned with a cleaning stone. Furthermore, in Japanese Patent Application Laid-Open No. 14857-179850,
It has been disclosed to provide a protective coating consisting of a polyvinyl alcohol-based resin on the surface of a photomask or reticle. However, these prior art methods require a sodium carboy to remove the protective film.
Sodium oxychloride mixed aqueous solution (Tokuko Sho 5
2-12057), hydrofluoric acid (Special Publication No. 50-5
This method requires an etching solution such as water (Japanese Patent Laid-Open No. 179850/1983), and the process becomes complicated.

The purpose of the present invention was to eliminate the drawbacks of the above-mentioned Jubei Keijutsu.
It is used as a surface protection liquid for semiconductor manufacturing masks, wafers, etc.

j- be.

The above six objects of the present invention have been achieved by using, as a surface hardening liquid, a resin having film-forming properties and peelability properties, which is generally understood as a solvent.

Specifically, the present invention resides in a surface protection liquid for semiconductor integrated circuit mask substrates, wafers, etc., which is characterized by comprising a film-forming and removable material, and a solvent that dissolves the material. .

The present invention also provides a protective film by coating the surface of a mask substrate, wafer, etc. for manufacturing semiconductor integrated circuits with a protective film consisting of a resin that has film-forming and peeling properties and a solvent that dissolves the resin, and leaving it to dry. There is also a method for protecting the surface of a mask substrate, wafer, etc. for manufacturing semiconductor integrated circuits, which is characterized by forming the same.

The non-invention will be explained in detail below.

As described above, the mask substrate for semiconductor integrated circuit manufacturing of the present invention,
The surface preservation material for wafers and the like is composed of a film-forming and peelable material, and a solvent that dissolves the material.

Examples of 1-temperature vinyl-vinyl acetate copolymer, polyvinyl butyral, cellulose fat conductor,
Examples include, but are not limited to, epoxy resin and polychloroprene. These resins can be used alone or in combination of two or more. Particularly preferred resins contain 85 to 93% vinyl chloride, preferably 85% to 93% vinyl chloride.
9-91%, vinyl acetate 7-15%, preferably 9-91%
It was found to be a vinyl chloride-vinyl acetate copolymer with a concentration of 11%.

The solvent for dissolving the resin is appropriately selected depending on the type of resin. It is preferable to use a volatile solvent in order to speed up drying after applying the decanting liquid to the surface of a mask substrate, wafer, etc. Examples of such solvents include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, alcohols, esters, chlorinated hydrocarbons, and fluorinated hydrocarbons.

Since the resin and solvent are used as a surface protection liquid for mask substrates, wafers, etc., they need to be of high purity. Table 11 of mask substrate, Weber, etc. for 1%! ′
] In order to completely prevent impurities from spreading and staining, impurities from impurities (such as 'g z AlXAu) are added.

13a, Bi, BXCa, Cd, Cs, Cu
, Fe, Ga.

K1 Ll, Mg, Mn, Na, Ni, Pb,
, Si, 8n.

Sb, Ti, Zn, etc.) It is a sub-optimal to suppress the influence of t.

Furthermore, in order to make it easier to distinguish coating unevenness after the surface of a mask substrate, wafer, etc. is coated, a usable coloring agent such as a dye or a pigment may be added.

The method of protecting the surface of a mask substrate, wafer, etc. for manufacturing semiconductor integrated circuits according to the present invention includes applying the above-mentioned protective liquid to the surface of the mask substrate, wafer, etc. and drying it to form a protective layer. Consists of things.

Any conventionally known method can be used to apply the protective liquid, examples of which include a spray method, a roll method, a spinner method, a dip method, and a blade method.

Since the protective film formed on the surface of the mask chain plate, wafer, etc. by the method of the present invention is made of a resin that has membrane rupture-forming and peeling properties, the mask substrate, wafer, etc. It is distributed as a film of uniform thickness on the surface, and when it is desired to remove it after use, it can be easily peeled off from the surface of the mask substrate, wafer, etc. by attaching cellophane tape or the like to the edge and pulling it up. This protective film can be put to practical use in the range of 0.02 to 311/d, but when the protective film is peeled off when using a mask substrate, wafer, etc., the protective film may be cut during peeling. 0.1-0.
A range of 29/d is preferable.

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Vinyl chloride-vinegar vinyl copolymer (UCC VXHD,!: 86% vinyl chloride and 14% vinyl acetate)
j, te city tlJj) 20 g k dollar all4.
5.59 mm and acetone 45.5 g as a mixed heating medium to prepare a protective solution having a weight of 18.018%.

In a clean room, the mask substrate, the upper surface of the mask substrate, and the wafer were immersed in this coating, and a protective solution was applied to both surfaces and dried to form a protective coating with an O concentration of 1.5 g/m2.

After storing it in a plate carrier for 7 days, cellophane tape was attached to the edge of the first plate and when it was lifted up, the mask substrate and the other 11 wafers were removed. The protective film was peeled off until the ii1 part was removed without being cut, and a completely clean surface of 7a could be reproduced without any traces on the surfaces of the mask substrate and wafer.

Example 2 17 g of a vinyl chloride-vinyl acetate copolymer containing 89% vinyl chloride and 11% vinyl acetate, 3 g of polyvinyl butyral resin (trade name t3M-1), V, and 0.0 g of an oil bath dye as a coloring agent. 019 is dissolved in a mixed hot medium of Dorol 51.9 and tomethyl ethyl ketone 119#,
It was made of 1M protective alloyed metal with a solid weight of 10.54% by weight.

The above-mentioned protective GT (Ti film,
Protection of 0.1g/- per dry! The situation was formed.

After 200 days of collective care on the plate carrier, adhesive tape was applied to the edge of the protective film and pulled up, and the same results as in Example 1 were obtained.

Example 3 A vinyl chloride-vinyl acetate copolymer containing 91% vinyl chloride and 9% vinyl acetate was mixed with 52 g of doluol, 780.2 g of methyl imbutyl ketone, and 0.0 g of phthalate.
8I power, the mixed heating medium has a similar content of 1.
3.07-4-layer protective solution was prepared.

The above protective liquid was applied onto both surfaces of the mask substrate and the wafer by a plate method in a clean room, and after drying, a protective layer of 0.2 g/ml was formed.

It was stored on a plate carrier for one year. When EZ cellophane tape was applied to the edge of the protective film and pulled up, the same results as in Test 111 were obtained.

As is clear from the above examples, the following effects were obtained by the present invention.

tat Mask substrates, wafers, etc. that have been coated with a protective film by the method of the present invention can be protected from contamination on their surfaces by the use of a protective tank, and can also be protected by the resin cushioning machine that makes up the entire structure. This reduces damage during transportation and reduces the need for tedious loading docks.

(b) In the conventional method of forming a protective film on the surface of a mask substrate, wafer, etc., an etching process was necessary to remove the protective film, which was rare, but in the invention, 4-, such an etching process is not required. By pasting cellophane tape on the edge of the protective film and pulling it up, the protective film can be easily peeled off.

Even if there is a layer of dust such as rattan dust on the surface of the mask substrate, Ueno, etc., there is also the advantage that the dust can be removed when the protective film is peeled off.

Mask substrates, wafers, etc. from which the fcl protective film has been peeled off can be subjected to the next process without having to clean the entire surface of the mask again, thus making it possible to save labor in cleaning operations.

Agent Masubuji Kantani - 11 - Procedural amendment (spontaneous) ■, Indication of the case Patent application No. 1983-21.480 2, Name of the invention Surface protection liquid for mask substrates, wafers, etc. for semiconductor integrated circuit manufacturing and its usage 36 Relationship with the person making the amendment Patent applicant Kimoto Co., Ltd. 4, Agent 3-9-5 Nihonbashi Honmachi, Chuo-ku, Tokyo 103 5. Subject of amendment 6. Contents of amendment (1) Patent The scope of claims is amended as shown in the attached sheet.

(2) Specification page 8, line 7, page 9, line 11, page 9, line 2
Insert rloOJ before rrJJ on the 20th line of the same page and the 12th line of the 10th page of the same page.

"C5" in the third line of page 7 is corrected to "CO".

Claims (1) A surface protection liquid for mask substrates, wafers, etc. for manufacturing semiconductor integrated circuits, comprising a resin having film-forming and peeling properties and a solvent that dissolves the resin.

(2) The resin having film-forming and peeling properties is selected from the group consisting of vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, cellulose derivatives, epoxy resins, polychloroprene, and mixtures thereof. Surface protection liquid as described in section.

(3) Vinyl chloride-vinyl acetate copolymer is vinyl chloride 8
The surface protection liquid according to claim 2, which has a composition of 5 to 93% by weight and 15% by weight of vinyl acetate.

(4) Applying a protective liquid consisting of 4tJ resin, which has film-forming and removable properties, and a solvent that dissolves the resin, to the surface of a mask substrate, wafer, etc. for manufacturing semiconductor integrated circuits, and drying it to form a protective film. A method for protecting the surface of mask substrates, wafers, etc. for semiconductor integrated circuit manufacturing, characterized by:

(5) The resin that has film-forming and peeling properties is Salt C Hivinyl-i! 5. The surface protection method according to claim 4, wherein It is selected from the group consisting of acid vinyl copolymers, polyvinyl butyral, cellulose derivatives, epoxy resins, polychloroprenes, and mixtures thereof.

(6) Vinyl chloride-vinyl acetate copolymer is vinyl chloride 8
The surface protection method according to claim 5, which has a composition of 5 to 93% by weight and 7 to 15% of vinyl acetate.

(7) The surface protection method according to claim 4, wherein the protective liquid contains a dye and/or a pigment.

(8) The amount of the protective film formed on the surface of the mask substrate, wafer, etc. is 0.02-0.3 g/ ]OOcn? The surface protection method according to claim 4.

(9) The amount of the protective film formed on the surface of the mask blade plate, wafer, etc. is 0.1 to O-2g/1. The surface protection method according to claim 8, which is OOc+a.

Claims (1)

[Scope of Claims] (11) A surface protection liquid for mask substrates, wafers, etc. for manufacturing semiconductor integrated circuits, comprising a resin having film-forming and peeling properties and a hot medium that dissolves the resin. (2) The m-shield that has film-forming and peeling properties is vinyl chloride-1!!vinyl chloride copolymer, polyvinyl butyral,
The surface protection liquid according to claim 1, which is selected from the group consisting of cellulose derivatives, epoxy resins, polychloroprene, and mixtures thereof. (3) Vinyl chloride-vinyl acetate copolymer is added to vinyl 8
The surface protection liquid according to claim 2, which has a composition of 5% to 93% vinyl acetate and 7% to 15% vinyl acetate. (4) Mask substrate for semiconductor integrated circuit manufacturing, wafer-1-
ru-, etc., is coated with a protective layer consisting of a resin that has film-forming and peeling properties and a hot medium that dissolves one portion of the resin, and is dried to form the entire protective film. A method for protecting the surface of removable circuit mask substrates, wafers, etc. (5) A resin having film-forming and peeling properties is selected from the group consisting of vinyl-vinyl acetate copolymer, polyvinyl butyral, cellulose derivatives, epoxy resins, polychloroprene, and mixtures thereof. Surface protection method described in section. (6) Vinyl chloride-vinyl acetate copolymer is vinyl chloride 8
The surface protection method according to claim 5, wherein the surface protection method is made of a material having a composition of 5 to 93% by weight and 7 to 15% by weight of vinyl acetate. (7) The surface protection method according to claim 4, wherein the protective liquid is rich in dye and/or pigment. (8) The surface protection method according to claim 4, 6C, wherein the thickness of the protective film formed on the surface of the mask substrate, wafer, etc. is 0.02 to 31//crd. 2-(9) The method for maintaining clothing space according to claim 8, wherein the front side of the protective film formed on the surface of the mask substrate, wafer, etc. is 0.1 to 0.2.17/ffl.