JP3291517B2 - Dry etching mask, method for manufacturing the same, method for manufacturing decorative article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a fine pattern over a small area of a flat, inclined, or curved surface of an article.
The present invention relates to a method for forming fine pattern lines and patterns over the entire area of a surface having a diameter of less than 1 mm.

[0002]

2. Description of the Related Art Heretofore, as a method of drawing a fine pattern on the surface of a flat substrate, there is the following method.
It is well known in the field of manufacturing semiconductor devices,
Hereinafter, a method for forming a predetermined pattern on a plane having a small area such as diamond by using a conventional method will be described with reference to FIG.

First, the diamond 21 is rotated on a spinner (not shown) while a resist 22 is applied on the entire upper surface of the diamond 21. At this time, the resist flows on the surface of the diamond from inside to outside with rotation, and the film thickness tends to be uniform. However, it is difficult for the resist to flow at the edge of the surface of the diamond 21, and a so-called resist pool 22a is generated (FIG. 5A).

Next, for patterning, a mask 23 on which a chromium pattern is drawn is set, and light is irradiated from above the mask 23 by an exposure device to expose the resist film (FIG. 5B). However, at the edge of the surface of the diamond 21, the amount of exposure is insufficient due to the accumulation of the resist, so that an appropriate fine pattern cannot be obtained. In particular, this method is not suitable for forming a pattern over the entire area of the surface of the diamond 21.

As described above, unlike a semiconductor wafer having a relatively large surface with a diameter of tens of cm to tens of cm, a resist is applied to a small surface such as diamond, that is, a narrow surface of several cm or less. It is extremely difficult to apply thickly. Also, in the case of a semiconductor wafer, a certain amount of resist accumulation occurs, and a normal pattern cannot be formed at the edge of the wafer. However, in a semiconductor wafer, a chip manufactured in this portion is originally planned as a defective product.
There is no particular problem.

As described above, it is extremely difficult to form a fine pattern over the entire area of a specific surface by the conventional method of applying a resist on a minute surface such as diamond and etching it through an exposure process. It is. Next, the results of experiments actually performed by the present inventor using this conventional method will be described.

FIG. 6A shows a star plane, FIG. 6B shows a diamond table surface, FIG. 6C shows a cubic plane, and FIG.
(D) A resist was applied to articles having various surface shapes such as a cylindrical flat surface, and an attempt was made to rotate the spinner to obtain a constant film thickness. However, since a thicker resist pool (black portion in the figure) occurs at the periphery of the surface than at the center of the surface, the subsequent exposure process and etching process are hindered, and a fine pattern over the entire area is formed. It was difficult to form. The resist pool that causes the exposure trouble usually spreads along the periphery of the resist-coated substrate.
Although it is a band shape having a width of 3 to 0.7 mm, the occurrence of a resist pool whose position and shape cannot be predicted is often added to this.

Therefore, it is very difficult to easily form a fine pattern over the entire area of these surfaces,
Even if successful, it is not suitable for mass production.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the problems of the conventional method, and a fine pattern is formed over the entire area of not only a plane but also a slope or a curved surface of an object. Dry etching mask that enables simple and inexpensive mass production, a method of manufacturing the dry etching mask, and a method of improving the decorativeness of jewelry and other decorative articles using the dry etching mask The purpose is to provide.

[0010]

[Means for Solving the Problems]

(Means) As shown in FIGS. 1 to 3, the above problem is solved by applying a resist to a surface of a first substrate, exposing the resist through a mask having a pattern, developing the resist, and then removing the resist. Selectively etching and removing a pattern to form a pattern, and etching the surface of the first substrate using the resist on which the image pattern is formed as a mask to form an uneven pattern on the surface of the first substrate And after pouring a viscous material onto the surface of the first substrate on which the pattern image of the concavo-convex pattern is formed, solidifying the viscous material to form a second substrate having a concavo-convex pattern opposite to the first substrate A step of forming, a step of etching the entire surface of the second substrate to form a mask having an opening pattern, a step of preparing a third substrate, and attaching a release film to a surface thereof; Having mask Selectively forming a first film by the CVD method (DLC film or synthetic diamond film) to said third peeling film on the substrate as a mask, the first
By removing the peeling film between the film (DLC film or synthetic diamond film) and the third substrate, a master mask made of the first film (DLC film or synthetic diamond film) having an opening pattern is manufactured. And a method for manufacturing a dry etching mask having the above steps.

[0011] The above-mentioned object is to provide a step of attaching a peeling film to the surface of the first substrate, applying a resist on the peeling film of the first substrate, and applying the resist through a mask having a pattern. Exposing and developing the resist, selectively removing the resist by etching to form a pattern, removing the peeling film between the resist and the first substrate, and removing the resist from the resist having an opening pattern. And a step of manufacturing a dry etching mask.

(Operation) Next, the operation of the present invention will be described. According to the present invention, first, a fine pattern is transferred to a resist film using a reticle mask, and thereafter, a master mask of the fine pattern is manufactured by an etching technique. Then, using this master mask, the plasma C
By forming a DLC film or a synthetic diamond film using a VD apparatus, a large number of working masks having an opening pattern are manufactured at low cost.

According to the microfabrication of the new method of the present invention, dry etching is performed using these working masks. For this reason, compared to the conventional fine pattern forming method that requires a large amount of expensive reticle, complicated processing such as resist coating, temperature processing, etching, or exposure control, etc. A fine pattern can be formed at low cost.

According to the invention of the present application, since the occurrence of a resist pool which causes an exposure trouble is eliminated, a fine pattern or a character, or a groove having an interval of the order of several μm is formed on the entire area within a specific surface of a decorative article or the like. The diffraction grating can be formed very simply. Further, since the working mask having the opening pattern can be used as a master mask, it is not necessary to manufacture the master mask twice if the same pattern is used.

In particular, a mask formed of a DLC or synthetic diamond film has the following excellent characteristics and can be used as a mask for various fine processing. (1) The hardness is very high. (2) Compressive strength is very hard. (3) Very high tensile strength. (4) High etching resistance. (5) The coefficient of thermal expansion is very small. (6) It is a good electrical insulator. (7) It is chemically stable and hardly attacked by corrosive atmosphere. (8) Thermal conductivity is 2.5 times that of copper (Cu), which is very high. (9) High wear resistance. (10) Oxidation resistance temperature is up to 90 at 600 ° C or higher in air
0 ° C., 1400 ° C. at high vacuum, eg 2 × 10 ^-6 Torr
And very high.

The DLC or synthetic diamond film becomes graphite at 2000 ° C. (11) The pattern accuracy of the mask can be 1 μm or less.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION

(A) Microfabrication technology studied by the present inventor before the present invention The present inventor considered whether decoration such as lines and patterns could be applied over the entire minute surface of jewelry such as diamond, and so on. Various other methods were studied. Before describing the embodiments of the present invention, one of them will be described with reference to FIGS.

First, as shown in FIG. 7A, a diamond 26 is placed on a glass substrate 24 having a flat surface. At this time, the surface on which the pattern is drawn is brought into contact with the surface of the glass substrate 24. Next, a cylindrical metal cylinder 25 is placed so as to surround the diamond 26. Next, as shown in FIG. 7 (b), MMA (methacrylic resin) is poured into a gap surrounded by the diamond 26, the metal cylinder 25 and the glass substrate 24, and the MMA is polymerized. To be fixed.

Further, as shown in FIG. 7C, amalgam 28 is poured inside the metal cylinder 25. At this time, the surface of the amalgam 28 is flattened. Next, as shown in FIG. 7D, the glass substrate 28 is separated from the diamond 26, and a resist 29 is applied on the surface of the diamond 26 using a spinner (not shown).

Then, as shown in FIG. 8A, the entire surface is exposed through a mask 30, so that the mask pattern is transferred to a resist 29 and then developed. Further, the surface of the diamond is etched by irradiating argon ions (Ar) through the resist 29 (FIG. 8B). In this way, the pattern 31 can be drawn over the entire minute surface of the diamond 26 (FIG. 8C).

According to this method, FIG.
(B) As shown in FIG.
Even if the resist pool 29a is formed on the diamond 7, it does not reach the surface of the diamond 26, so that a fine pattern can be formed over the entire area of the fine diamond surface. However, this method has the following problems.

(1) During polymerization of MMA, since the volume shrinks by about 21%, distortion of the MMA surface is likely to occur. (2) During MMA polymerization, heat is generated by the polymerization reaction,
The MMA surface is likely to be distorted. (3) When applying the resist 29, the metal cylinder 25
Since the metal cylinder 25 is small and has a three-dimensional shape, when the metal cylinder 25 is rotated by a spinner, the metal cylinder 25 is easily vibrated, and it is difficult to apply a resist having a uniform thickness.

According to this method, if skilled, the resist 2
Although it is possible to apply 9 evenly, mass productivity is poor. (B) As a result of repeating the above experiment, the inventor of the present application has made the following invention. Hereinafter, embodiments of the present invention will be described with reference to the drawings.

FIGS. 1A to 1D are cross-sectional views illustrating a method for manufacturing a dry etching mask according to an embodiment of the present invention. First, as shown in FIG. 1 (a), a resist 2 is applied on a substrate 1 made of glass, film, or the like, and is applied to a spinner (rotator) (not shown) to uniformly form a film having a thickness of 0.5 μm. I do. After that, as shown in FIG. 1B, exposure is performed through a reticle 3 having a chrome pattern using an exposure device (not shown), and the reticle pattern is transferred to the resist 2.
Thereafter, development is performed to form a resist pattern 2a. The fine pattern at this time is almost the same as that of a general semiconductor device manufacturing technique. For example, as shown in the figure, a groove pattern having a width of 1 μm and an interval of 1 μm is formed. Of course, it can also be manufactured with a groove width and a groove interval of 1 μm or less.

Next, as shown in FIG. 1C, Ar ions are irradiated using the resist pattern 2a as a mask. As a result, the portion not covered with the resist is selectively etched by Ar ions, so that the substrate 1a having the concavo-convex pattern is formed. The depth of the groove at that time is 0.1 μm to 1 μm. Next, as shown in FIG. 2A, a viscous MMA4 (methacrylic resin) is poured into the uneven surface of the substrate 1a, and then a glass substrate 5 having a flat surface from above is placed and pressed from above. Then, it is solidified by a heat treatment to form MMA4 having irregularities.
a is created (FIG. 2 (b)).

Next, the MMA 4a is irradiated with Ar ions from above the MMA 4a to etch the entire surface of the MMA 4a.
The concave portion of A4a is first removed by etching, leaving a thick convex portion. As a result, an MMA 4b having an opening pattern is manufactured as shown in FIG. Next, a method for manufacturing a master mask will be described with reference to FIG.
First, as shown in FIG. 3 (a), another glass substrate 5 is prepared, and the surface thereof is made of water-soluble nylon to a thickness of 0.1 μm.
Is applied.

Then, using the MMA 4b having the opening pattern formed in the step of FIG. 3B as a mask, the ECR plasma CVD apparatus shown in FIG. 5 is used to form a plasma CVD (Chemical Vapor Deposition) method on the glass substrate 5. DLC (Diamond Like Carbon) is grown to form a DLC film. Here, a method of forming the DLC film 7 on the glass substrate 5 using the plasma CVD apparatus of FIG. 4 will be described.

First, the glass substrate 5 is placed on the substrate holder 16 in the reaction chamber 15, and the MMA 4b having an opening pattern is set above the glass substrate 5 as a mask. Then, after evacuation is performed to reduce the pressure, the substrate 5 is set to a predetermined temperature by the substrate temperature control circuit 11. Next, methane (CH ₄ ) is used as a reaction gas, and microwaves are applied through the waveguide 14 to the plasma generation chamber 1.
2 and generates methane in a plasma state in a high magnetic field generated by the magnet coil 13. The methane gas in the plasma state is supplied to the reaction chamber 15 by the bias circuit 10.
And grown as a DLC film on the glass substrate 5 using the MMA 4b as a mask.

Table 1 shows the conditions for forming the DLC film at this time. For example, a film is formed under the conditions shown in Sample 1 in Table 1. In addition, each condition can be changed suitably.

[0030]

[Table 1]

In the present invention, the case where the film is formed by the CVD method has been described, but the film can be formed by the PVD method. In this way, a DLC film is formed on the glass substrate 5. After that, when the glass substrate 5 is immersed in water, the peeling film 6 between the DLC film 7 and the glass substrate 5 dissolves in water. DLC with opening pattern
Only the film 7 can be taken out.

The DLC film 7 having this opening pattern is
As shown in FIG. 3D, it is used as a mask in a subsequent substrate etching step. That is, when the substrate 8 is irradiated with Ar ions and etched using the DLC film 7 as a mask,
A pattern corresponding to the opening pattern is formed on the DLC film 7 on the substrate 8.
Can be formed on the surface. Since the mask made of the DLC film 7 has very high hardness and high etching resistance, it is particularly effective when a pattern is formed on a substrate made of a material having high hardness.

The DLC film 7 having an opening pattern
Can be used as a mask instead of the MMA 4b in the plasma CVD apparatus of FIG. As mentioned above,
In the present invention, in order to form a fine pattern, a resist is applied at the first stage, a pattern is formed on the resist by exposing through a reticle, and selective etching is performed through the resist. Although a complicated process of drawing on the surface is required, a mask having an opening pattern made of a DLC material is manufactured based on the pattern of the substrate surface.
The mask having the same opening pattern can be easily reproduced by using the apparatus.

As described above, since a mask having a fine opening pattern can be easily mass-produced, the present invention is very excellent in mass productivity of forming a fine pattern. In particular, in the present invention, a fine pattern can be formed without the necessity of a resist coating step, focusing of an exposure device, and the like, so that the substrate surface does not necessarily have to be flat. Further, for the same reason, the object for forming the fine pattern may be a solid, or the surface of the solid may be small. The present invention is also applicable to a case where patterns are simultaneously formed on a plurality of surfaces of a polyhedron.

In this manner, it is possible to easily form a case where a large number of fine grooves for light interference are formed on each surface of a polyhedron such as a decorative article, and fine patterns, patterns, characters, and the like. (C) Second Embodiment A second embodiment of the present invention relates to a case where the DLC film 7 is used as a mask for selective film formation.

In the manufacturing method according to the second embodiment, the steps shown in FIGS. 1 (a) to 3 (c) in the first embodiment are common. Omitted.
The DLC film 7 having the opening pattern formed in the steps up to FIG. 3C can be used as a mask in a subsequent step of forming a film on a substrate, as shown in FIG. 3D. That is, when the DLC film 7 having an opening pattern is used as a mask and the plasma CVD apparatus shown in FIG. 4 is used as a DLC film forming apparatus, the plasma is selectively grown on the substrate surface via the opening pattern of the DLC film 7. Can be formed.

Here, the object for forming the fine pattern does not necessarily have to be a flat surface as a whole, but may be an oblique surface such as a polyhedron or a curved surface. Since the mask made of the DLC film 7 has very high hardness and high etching resistance, it is particularly effective when a fine pattern is formed on jewelry or the like made of a material having high hardness. In the embodiment, the DLC or the synthetic diamond film is described as an example of the mask material, but it is needless to say that other mask materials can be applied.

[0038]

As described above, according to the present invention, a fine pattern is formed on a substrate having a flat surface by using an exposure technique until a master mask is manufactured, and an opening pattern is formed from the master mask. Is formed, and then a working mask having an opening pattern is manufactured from the master mask by using a plasma CVD method or the like.

Therefore, at the stage of manufacturing the first master mask, an exposure technique that requires precise control and the like is used.
Subsequent fabrication of the working mask requires only film formation using the master mask, so that microfabrication is extremely simple, and a large number of working masks can be easily fabricated. Further, by forming these working masks with a DLC film or a synthetic diamond film, the working mask can be applied to various types of fine processing depending on the characteristics of the material.

In particular, the use of the mask of the present invention makes it possible to easily apply fine patterns and characters on the surface of jewelry or the like having high hardness, which is very suitable for mass production.

[Brief description of the drawings]

FIGS. 1A to 1D are diagrams illustrating a method for manufacturing a dry etching mask having a fine pattern according to a first embodiment of the present invention.

FIGS. 2A to 2C are diagrams illustrating a method for manufacturing a fine-pattern dry etching mask according to the first embodiment of the present invention.

3 (a) to 3 (c) show a method for manufacturing a dry etching mask having a fine pattern according to the first embodiment of the present invention, and FIG. 3 (d) shows a method using the mask. FIG. 4 is a diagram for explaining a method of etching by etching.

FIG. 4 is a diagram illustrating a configuration of a plasma CVD apparatus used in the method for manufacturing a dry etching mask according to the present invention.

FIGS. 5A and 5B are diagrams illustrating a conventional method for forming a fine pattern.

6 (a) to 6 (d) are diagrams for explaining a problem of a conventional fine pattern forming method.

FIGS. 7A to 7C are diagrams illustrating a method of forming a fine pattern studied by the present inventor before reaching the present invention.

FIGS. 8A and 8B are diagrams illustrating a method of forming a fine pattern studied by the present inventor before reaching the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1, 1a Substrate 2, 2a Resist 3 Reticle (exposure mask) 4, 4a, 4b MMA (methacrylic resin) 5 Glass substrate 6 Stripping film 7 DLC film 8 Substrate 10 Bias circuit 11 Substrate temperature control circuit 12 Plasma generation chamber 13 Magnet Coil 14 Waveguide 15 Reaction chamber 16 Substrate holder

Claims (9)

(57) [Claims] 1. A resist is applied to a surface of a first substrate,
Exposing the resist through a mask having a pattern,
After the development, a step of selectively removing the resist by etching to form a pattern, and etching the surface of the first substrate using the resist on which the image pattern is formed as a mask, thereby forming a pattern on the first substrate. A step of forming a concavo-convex pattern on the surface, and after pouring a viscous material onto the surface of the first substrate on which the pattern image of the concavo-convex pattern is formed, solidifying the viscous material to form a concavo-convex pattern opposite to the first substrate Forming a second substrate having: a step of forming a mask having an opening pattern by etching the entire surface of the second substrate; and preparing a third substrate, and attaching a peeling film to the surface. A step of selectively forming a first film by a CVD method or a PVD method on a peeling film on the third substrate by using a mask having the opening pattern as a mask; Board and Peeling film to remove during manufacturing method of a dry etching mask and a step of producing a master mask consisting of a first film having an opening pattern. 2. The method for manufacturing a dry etching mask according to claim 1, wherein the first film is a DLC film or a synthetic diamond film. 3. A step of forming a second film as a first master mask having an opening pattern according to claim 1 by a CVD method or a PVD method to produce a working mask made of a second film having an opening pattern. A method for producing a dry etching mask comprising: 4. The method for manufacturing a dry etching mask according to claim 3, wherein the second film is a DLC film or a synthetic diamond film. 5. A dry etching mask comprising a DLC film or a synthetic diamond film produced by the method for producing a dry etching mask according to claim 1. 6. An uneven pattern is formed on a flat, inclined, or curved surface of a decorative article by dry-etching using a dry etching mask made of a DLC film or a synthetic diamond film having an opening pattern according to claim 5. Dry etching method. 7. A step of attaching a peeling film to the surface of the first substrate, applying a resist on the peeling film of the first substrate, and exposing the resist through a mask having a pattern. Forming a pattern by selectively etching and removing the resist after development, and removing the peeling film between the resist and the first substrate to form a master mask made of a resist having an opening pattern. And a method for producing a dry etching mask. 8. A method of manufacturing a decorative article, wherein a concave-convex pattern is formed on a flat, inclined, or curved surface of the decorative article by performing dry etching using the dry etching mask according to claim 5 as a mask. . 9. A method for manufacturing a decorative article, wherein the pattern according to claim 1 is a fine pattern enabling light interference.