JPS60102629A - Formation of pattern - Google Patents

Abstract

PURPOSE:To enable formation of a resist pattern on a metallic surface with good accuracy by providing a colored film layer on the metallic surface, laminating a photosensitive resin film layer thereon and exposing a pattern to said layer then developing the photosensitive resin film layer. CONSTITUTION:A colored film layer is provided on the surface of a base plate which consists of copper, aluminum, iron or the like and on which a photosensitive resin film layer is laminated or the layer of foil, plating, vapor deposition, etc. consisting of said metals (metallic surface). The colored conversion film layer consisting of the oxide or sulfide, etc. of the metal forming the metallic surface is brought into an aq. soln. contg. an oxidizing agent or sulfide. A photosensitive resin film such as dry film, liquid resist or the like is laminated on the colored film layer by a method such as coating, laminating or the like. The photosensitive resin film layer is exposed via a pattern mask having a prescribed shape and the exposed layer is developed by a resist developing soln. to form the resist pattern having the prescribed shape on the metallic surface.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photophosphorography technology used for microfabrication, and more specifically, the present invention relates to photophosphorography technology used for microfabrication, and more specifically, the present invention relates to photolithography technology used for microfabrication. The present invention relates to a method for forming a resist pattern comprising a photosensitive resin coating layer used for forming a metal graphic workpiece (pattern) comprising a photosensitive resin coating layer.

Conventionally, in forming fine patterns for large-scale integrated circuits, etc., a resist pattern consisting of a photosensitive greasy coating layer is used, and a concavo-convex pattern of a predetermined shape made of a layer of metal etc. is based on the etching method. A method of forming the material-4- is known.

Hereinafter, as a typical example, a method of forming a pattern by an etching method will be described.

First, a predetermined metal coating layer is provided on a suitable substrate by coating, vapor deposition, adhesion, etc., and then a photosensitive resin coating such as dry film, liquid resin, etc. is laminated on this metal coating layer. do. Next, the photosensitive resin coating layer is exposed to light through a pattern mask having a predetermined shape, and the layer is developed with a resist developer to form a resist pattern having a predetermined shape on the metal coating layer. Thereafter, the portions of the metal coating layer that are not covered by the resist pattern are removed from the substrate using an etchant, and finally the resist pattern is peeled off from the substrate using a stripping solution or the like, and the metal coating layer is removed from the substrate. A pattern of a predetermined shape consisting of layers is formed.

In the method of using a resist pattern made of such a photosensitive resin coating layer, conventionally, a photosensitive resin is coated or laminated on the surface of a metal layer or a substrate (hereinafter referred to as the metal surface). As a treatment, in order to ensure adhesion between the photosensitive resin coating layer and the metal surface, the metal surface on which the photosensitive resin coating layer is laminated was roughened by surface preparation, chemical etching treatment, etc. .

However, the adhesion between the photosensitive resin coating layer and the metal surface is
Such surface roughening does not sufficiently improve the problem, and the photosensitive resin coating layer may peel off from the metal surface, for example, during development after pattern exposure, or during etching or electroforming processes. The problem remained. In particular, when forming a resist turn with a thin line pattern of 150 μm or less in line 111, the above-mentioned resistance from the metal surface of the turn was noticeable.

On the other hand, since the surface roughness of the roughened metal surface is large, the light during pattern exposure is diffusely reflected and scattered on this surface, and the shape of the area given to the photosensitive resin coating layer by the pattern mask is There was also the problem that the resolution of the pattern deteriorated and the accuracy of the formed resist I/) pattern was reduced.

The object of the present invention is to obtain sufficient adhesion between the photosensitive resin coating layer and the metal surface such that #1 does not cause peeling between the photosensitive resin coating layer and the metal surface, and to provide a pattern mask. An object of the present invention is to provide a method for forming resist no-turns that can form resist patterns with high precision on metal surfaces that faithfully correspond to the predetermined shape of <turns given to the photosensitive resin coating 11+2 layer by It is an object of the present invention to provide a method for forming a resist pattern which is particularly suitable for forming a fine pattern having a resist pattern width of 150 μm or less.

The second object is achieved by the present invention as follows.

That is, the pattern forming method of the present invention is a method for forming a resist pattern of a predetermined shape made of a photosensitive resin coating layer on a metal surface, and includes the following steps: (1) providing a colored coating layer on the metal surface;

(2) a step of laminating a photosensitive resin coating layer on the colored coating layer; (3) a step of pattern-exposing the photosensitive resin coating layer; and (4) a step of laminating the pattern-exposed photosensitive resin coating layer. The method is characterized by comprising a step of developing.

In the method of the present invention, first, a photosensitive resin coating layer or a substrate made of copper, aluminum, iron, etc. or a foil made of these metals is laminated on the surface thereof.

The surface of the plating, vapor deposition, etc. layer (metal surface) is provided with a shiko stone Buddha coating layer.

By providing this colored coating layer on the metal surface,
It is located below this colored coating layer. ] 2 metal surface;
Furthermore, the adhesion with the photosensitive resin coating layer laminated on the colored coating layer is increased through the colored coating layer, and the diffused reflection of light on the metal surface during turn exposure is suppressed. ] It is possible to increase the resolution in turn exposure.

This colored coating layer has minute irregularities on its surface suitable for providing good adhesion with the photosensitive resin coating layer after the coating layer is formed, and furthermore, the surface C of the layer has fine irregularities during no-turn exposure. It is preferable that the color be black or a color closer to black, which has the effect of suppressing diffused reflection of light.

Such colored coating layers include black nickel metal,
Examples include a black electrodeposited coating layer such as silver or black chrome plating, and a colored metamorphic coating layer made of a drunkenide or sulfide of the above-mentioned metal material.

A black electrodeposited coating layer such as blank nickel or black chrome coating can be formed by laminating black nickel, black chrome, etc. on the metal surface by an electrodeposition method or the like.

Further, the colored metamorphic film layer made of metal oxide or sulfide forming the metal surface,
It can be formed on the metal surface by a method such as contacting with an aqueous solution containing an oxidizing agent or sulfide, or contacting with a gas containing oxygen at a high temperature of 100° C. or higher.

After the colored film layer is thus provided on the metal surface, in the method of the present invention, a photosensitive resin film such as a dry film or liquid resist is coated on the colored film layer, laminated, etc. It is laminated by the following method. This laminated photosensitive resin coating layer is electrodeposited on the metal surface in sufficient detail through the colored coating layer, so that it forms a resist pattern on the metal surface during subsequent processing steps such as development, etching, and electroforming. It is possible to prevent the photosensitive resin coating layer left on the metal surface from peeling off.

Next, the photosensitive resin coating layer is exposed to light through a pattern mask having a predetermined shape, and the layer is developed with a resist developer to form a resist pattern having a predetermined shape on the metal surface.

At this time, during pattern exposure, diffuse reflection of light on the surface of the colored film layer on the metal surface is suppressed, and a resist pattern that faithfully corresponds to the pattern mask can be formed with good resolution.

Therefore, a fine resist pattern in which the pattern +lj is 150- or less can be formed with high precision.Moreover, this fine resist pattern does not require the use of metal materials in the development, etching, etc. processes like conventional ones.
There is no longer any peeling from the surface.

The resist pattern formed on the metal surface formed by the method of the present invention in this way can be formed by etching, electroforming, etc. Alternatively, it is used to form a pattern of a predetermined shape on a substrate, consisting of a plating layer or a vapor deposited layer of other metals.

According to the pattern forming method of the present invention as described below, sufficient adhesion between the metal surface and the photosensitive resin coating layer can be obtained, and the developing process when forming a resist pattern or after forming the resist pattern can be performed. In processes such as etching and electroforming, it was possible to prevent the photosensitive resin coating layer constituting the resist pattern from peeling off from the metal surface. Furthermore, it has become possible to form a resist pattern on a metal surface with high precision, which faithfully corresponds to a predetermined pattern given to a photosensitive resin coating layer by a pattern mask. In particular, it has become possible to form a fine resist pattern with good adhesion to the metal surface, in which the interval between patterns 1 and 1, which requires good adhesion to the metal surface, is 150 or less.

Hereinafter, the method of the present invention will be explained in more detail according to Examples.

Example 1 As described below, a resist pattern made of a photosensitive resin tri-film in a certain shape was formed on a coating layer made of copper by the method of the present invention, and further, using this, a copper coating 89 was formed. A printed circuit board was fabricated by etching the layers into a predetermined shape.

First, a through hole was made using an NG drill at a predetermined position in a phenolic resin laminate plate having copper foil laminated on both sides with a thickness of 35 tiles. Next, the copper foil surface of this phenolic resin laminate was coated with a liquid containing colloidal palladium (product name: H5l).
After activation treatment using 0IB (manufactured by Hitachi Chemical Co., Ltd.),
30°C electroless copper plating bath (product name: Cast 201
(manufactured by Hitachi Chemical Co., Ltd.), and electroless copper plating was performed so that the plating layer thickness was about 1 μs. Furthermore, phenolic resin laminates formed by this electroless copper plating.
- Using a copper sulfate plating solution (product name: Surcap AC90, manufactured by Uezai Kogyo Co., Ltd.) on the copper plating layer, 3A/d
Copper sulfate electrolytic plating was performed at i2 for 40 minutes, and a copper plating layer with a thickness of 25 scales was laminated.

This phenolic resin laminate whose surface is copper plated is
The surface was treated by immersion in a dihydrochloric acid aqueous solution for 30 minutes, and then 2OA/dm in a black chrome plating solution (trade name: Nero Star Process, manufactured by Ebara Nigelite).
2, electrolytic plating was performed for 5 minutes. After plating was completed, the surface of the plated phenolic resin laminate was washed with water and dried. At this point, a copper foil layer with a thickness of 35 scales, a copper plating layer with a thickness of 26 scales, and a black chrome plating layer with a thickness of about 1 scale are laminated on both sides of the phenolic resin laminate in order from the phenol resin laminated side. has been done.

Next, a photosensitive dry film with a thickness of 50 scales (product name: T
1020. (manufactured by Du pant) is laminated,
This photosensitive dry film layer has a conductor portion with a minimum line width of 15
The film was exposed to ultraviolet light through a negative mask having a fine pattern of an electric circuit with zero scale and conductor spacing of 50 μm to form a latent image faithfully corresponding to the pattern on the photosensitive dry film layer.

Development was carried out by spraying a 10% aqueous solution of sodium carbonate onto the surface of the photosensitive dry film layer.

The resist pattern formed in the following manner is a 7-chrome black plate of a phenolic resin laminate.

The minimum line III of the conductor part is 1.
The conductor spacing was 50 scales and the conductor spacing was 50 -, which was formed faithfully to the fine pattern given by the pattern mask and with good resolution.

The resist pattern or the phenolic resin laminate formed on its surface was immersed in 50 volume I, 1% hydrochloric acid aqueous solution at 50 to 70°C for 1 minute to remove the black chrome coating layer in the areas not covered by the resist pattern. Removed. Furthermore, after washing this with water, ammonia alkaline copper chloride etchant (trade name: Alphain 8106, manufactured by Lmura Kogyo Co., Ltd.) was applied.
Remove the copper film layer in the part not covered by the resist pattern using
An electrical circuit fine pattern with conductor spacing of 100 μm was formed on a phenolic resin laminate.

Finally, the resist pattern was peeled off using a 3% by volume NaOH aqueous solution, and the phenolic resin laminate on which the electric circuit fine pattern was formed was immersed for 1 minute in a 50% by volume aqueous hydrochloric acid solution at 50 to 60°C. The black chrome plating layer remaining on the copper plating layer was removed, washed with water, and dried. After it has dried sufficiently, UV solder resist ink (product name: UR-300, manufactured by Sanwa Chemical Industries) is printed on the surface on which the electric circuit fine pattern is formed, and this is cured with ultraviolet rays to form an electric circuit printed board. It was created.

In this example, although the above-mentioned resist pattern formed by the method of the present invention is a fine pattern with a minimum line width of about 150 μs, it is difficult to process the steps such as development and etching in this example. There was no peeling during this process.

Example 2 A copper foil with a thickness of 70 mm was adhered onto a polyester film with an adhesive (trade name Ninirufan, manufactured by Nippon Matai) with a thickness of 20 scales by heat pressure bonding.

This polyester film with copper foil glued is 50 to 6
30g/I of Pakuna 19 (manufactured by Nihon Kagaku Kizai Co., Ltd.) at 0℃
After degreasing by immersing in an aqueous solution for 30 seconds, it was washed with water, and then immersed in a 180 g/l aqueous solution of Ehonol C Special (manufactured by Japan Metal Finishes Co., Ltd.) at 100 to 110°C for 5 minutes to remove copper oxide. A black metamorphic layer consisting of the following was formed on the surface of the copper foil. After that, this was washed with water, dried, and a liquid resist (product name: OM
R83 (manufactured by Tokyo Ohka) was applied so that the thickness of the resist pattern layer to be formed was about 5 scales, and this was applied as a fine pattern for an electric circuit in which the minimum line Q+ of the conductor part was 130 μs and the conductor spacing was 30−. A latent image faithfully corresponding to the pattern was formed on the liquid resist layer by exposing the liquid resist layer to ultraviolet light through a negative mask. Spray development was performed using a developer for OMR83 to form a resist pattern having the above-mentioned fine pattern on the black modified film layer.

The resist pattern obtained in this example as described above is also sufficiently based on the black metamorphic film layer on the polyester film, and the minimum line width of the conductor part of this resist pattern is 130 gm, and the conductor spacing is The fine pattern given by the 30-layer pattern mask and the pattern mask was faithfully formed with good resolution.

The polyester film on which this resist pattern is formed is immersed in a 20 volume 2 hydrochloric acid solution for 20 seconds to remove the black modified film layer in the areas not covered by the resist pattern, and then washed with water and then treated with an ammonia alkaline copper chloride etchant. (Product name: Alphain 910B, manufactured by Uezai Kogyo Co., Ltd.) to remove the copper foil layer in the portions not covered by the resist pattern, and remove the minimum conductor portion of the copper foil layer in the shape given by the pattern mask. Line width is 80u
+: An electrical circuit fine pattern with a conductor spacing of 80 μm was formed on a polyester film.

Finally, methylene chloride was sprayed to peel off the resist pattern, and the polyester film on which the electric circuit fine pattern was formed was immersed for 1 minute in a 30 volume dihydrochloric acid aqueous solution to remove the resist pattern remaining on the copper foil layer. The black metamorphic film layer was removed to form an electric circuit fine pattern.

In this example, although the above-mentioned resist pattern formed by the method of the present invention is a fine pattern with a minimum line +1J or about 130 scales, the development in this example There was no peeling during processes such as machining and nitching.

Patent applicant: Canon Co., Ltd.

Claims (1)

[Claims]]) A method for forming a resist pattern of a predetermined shape made of a photosensitive resin coating layer on a metal surface, comprising: (1) providing a colored coating layer on the metal surface; ) laminating a photosensitive resin coating layer on the colored coating layer; (3) pattern-exposing the photosensitive resin coating layer; and (4) developing the pattern-exposed photosensitive resin coating layer. A pattern forming method characterized by comprising the steps of: 2) A patent claim in which the colored film layer is a black electrodeposited film layer such as black nickel plating or blank chrome plating, or a colored metamorphic wave B layer made of an oxide or sulfide of the metal forming the metal surface. The pattern forming method according to item 1.