JPS60262425A - Working method of substrate - Google Patents

Abstract

PURPOSE:To provide a homogenous fine pattern on a substrate, by using as a treating mask a phase-separated film consisting of organic macromolecules and silicone resin or polysilane resin. CONSTITUTION:Organic macromolecules of acrylate resin or the like are added to silicone resin of polydimethyl siloxane or the like or to polysilane resin of polymethyl phenylsilane or the like so as to produce a phase-separated macromolecule film 1 on a substrate 2. The film is treated with O2 gas plasma so that the organic macromolecule regions 3 are removed while the silicone resin regions 4 are oxidized to leave SiO2 5 on the substrate. The substrate 2 is etched with the use of the film 5 as a mask, which is then removed. When the phase separation is of the order 1mum, it is advantageous that the film has a thickness equivalent to or smaller than the subject thickness. According to this constitution, a homogeneous fine pattern having a large area and a high shape ratio can be provided easily and economically if no regularity is required for the pattern.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for easily forming a large area, high shape ratio, or homogeneous fine pattern on a substrate.

[Prior art]

A photolithography method is usually used to form a fine structure of several tens to several pyn or one pyn or less on an arbitrary substrate. In this method, a photosensitive resist is applied onto a substrate, exposed to light through a mask, and then the resist is developed to transfer the pattern of the mask.

Subsequently, the substrate is etched using the resist pattern as a mask, or lift-off processing is performed.

[@Problems that Ming tries to solve]

Although the above method is an optimal method for forming a regular fine structure pattern on a substrate, it is not effective and efficient for forming a fine pattern on a substrate surface. If regularity is not required for the fine pattern formed on the substrate, the above-mentioned photolithography method involves many unnecessary steps such as a mask creation step and an exposure step (and cannot be called an economical method).

In order to process a substrate over a large area, a large-area mask is required, which is difficult to manufacture, or a small-area mask must be repeatedly exposed for a long time. Additionally, a special jig is required for substrates with unique shapes.

An object of the present invention is to solve the above-mentioned problems and provide a method for manufacturing a substrate that can easily and economically obtain a large area, high shape ratio, and homogeneous fine pattern on one substrate surface. There is a particular thing. ) [Means for solving the problem] The present invention forms a phase-separated film of silicone resin or polysilane resin and organic polymer on a substrate to be processed, and uses this as a processing mask to prevent phase separation. The feature is that the pattern is transferred onto the substrate to be processed.

In the present invention, a phase-separated polymer film is formed, which is composed of one or more selected from the group of silicone resins or polysilane resins (hereinafter referred to as Sj resin) and one or more organic polymers. A phase-separated polymer film can be formed by dissolving a Si resin and an organic polymer in a common solvent and using a normal polymer film production method such as casting or spin coating. Examples of the above-mentioned S+ resin include silicone resins such as polydimethylsiloxane, polymethylphenylsiloxane, and polysilsesquioxane, polymethylphenylsilane, polydiphenylsilane, and copolymers of boridimethylcipne and polymethylphenylsilane. One or more types of polysilane resins such as the following can be used. Basically, any organic polymer may be used as long as it is decomposed and vaporized by oxygen gas plasma, has poor compatibility with Si resin, and uses the same solvent as Si resin. Generally, Si resin has poor compatibility with organic striped molecules, so one or more of, for example, acrylate resins and methacrylate resins can be effectively used. The thickness of the phase-separated polymer membrane may be set to any desired thickness if necessary, but it is usually determined based on the phase-separated state. In other words, when the phase separation is, for example, on the order of 1, the film thickness is preferably equal to or less than that.

The subsequent D-loe of the substrate, that is, the formation of a fine pattern on the substrate, is performed by treating the phase-separated polymer film with, for example, oxygen gas plasma, and then using the silicon oxide portion remaining after that. Therefore, the mask preparation, exposure process, and resist development process that are required in the photolithography method are completely unnecessary. This is a substrate processing process that does not require wet processing. Examples of main nO process steps will be explained with reference to FIGS. 1 to 3, but the present invention is not limited thereto in any way.

In FIG. 1, a phase-separated polymer film 1 is formed on a substrate 2 (FIG. 1(a)). Next, the organic polymer portion 3 in the phase-separated polymer film is removed by oxygen gas plasma treatment, and the Si resin portion 42 is oxidized to leave silicon oxide 5 on the substrate (FIG. 1(b)).

Next, the silicon oxide on the substrate is used as a mask material to etch the substrate (FIG. 1(C)). Next, the silicon oxide is removed (FIG. 1(d)).

In FIG. 2, an organic polymer film 6 is formed on a substrate 2 to be processed, and a phase-separated polymer film 1 is further formed thereon (FIG. 2(a)). Next, while removing the organic polymer portion 3 in the polymer film phase-separated by oxygen gas plasma treatment,
The Si# bright portion 4 is oxidized to silicon oxide 5. At the same time, the portions of the organic polymer film not covered with the silicon oxide are removed (FIG. 2(b)). Next, the substrate is etched using the pattern of the organic polymer film 6 as a mask material (FIG. 2(C)). Next, the remaining organic polymer film is removed (FIG. 2(d)).

In FIG. 3, an organic polymer film 6 is formed on a substrate 2 to be processed, and a phase-separated polymer film 1 is further formed thereon (FIG. 3(a)). Next, the organic polymer portion 3 in the fc bilayer film is phase-separated by a concessional gas plasma treatment, and the organic polymer portion 3 is removed, and the Sj resin portion 4 is oxidized to silicon oxide 5.

At the same time, the portions of the organic polymer film not covered by the silicon oxide are removed. At this time, the pattern of the organic polymer film 6 is deposited by an oxygen gas plasma stage so as to be thinner than the conditioned silicon (FIG. 3(C)). Next, the pattern of one organic polymer 6 is removed together with the silicon oxide on it and the deposited material (FIG. 3(d)).

As described above, according to the method of the present invention, a fine pattern can be provided on a substrate without an exposure process. In addition, the state of phase separation, the ratio of the area occupied by the Si resin to the area occupied by the organic polymer in the phase-separated polymer membrane, and the size of the phase-separated Si resin part in the membrane are Mixing ratio of resin and organic polymer and Si to be mixed
It can be selected depending on the type of resin and organic polymer.

Examples will be described below.

[Example 1] A substrate was prepared by depositing aluminum to a stem thickness on a silicon substrate. Next, polysilsesquioxane 0
3 g and poly n-butyl methacrylate Q kg were dissolved in xylene 2θd, and 20
Coating was carried out under the conditions of θθrp'n and 60 seconds. The coating film thickness is Q
/j#m. After heat treatment for 11 hours, oxygen gas plasma treatment was performed for 10 minutes at an oxygen gas pressure of OmTorr and an RF power of 2θθW using a parallel plate plasma etching device (manufactured by Nichisha Almoto Co., Ltd., model DEM-451). Poly n-butyl methacrylate was removed and polysilsesquioxane was made into silicon oxide.The silicon oxide part became a nearly circular island shape with a diameter of 03~a.
It was a 2μ wing. Next, the aluminum was etched to a thickness of 2 μm using the etching apparatus. CC for etching
7. I used gas. After etching, the silicon oxide portion was removed by plasma etching using CF4 gas. When the pattern was observed using a scanning electron microscope, it was found that the silicon oxide pattern had been transferred.

[Example 2] A silicon substrate with a silicon oxide film (film thickness aS μm) was prepared, and AZ1350 photoresist (trade name: Shinprey Co., Ltd.) was applied thereon to a thickness of aS μm, and heat treated at 20θ° C. for 1 hour. Next, 05 g of polysilsesquioxane aSg and poly n-butyl methacrylate were added to xylene 2θIL.
IK melted, 2000r concave by spin coating method on the substrate,
It was applied for 60 seconds. After heat treatment for 100″CS/hour, oxygen gas plasma treatment was performed using a parallel plate plasma etching device (manufactured by Nichisha Anelva Co., Ltd., I)F) M-451.
Type) Oxygen gas pressure used 3θmTorrs RF power i
s.

It was etched with W for 9 minutes. When observed with a 1m scanning magneton microscope, AZ1350 photoresist was crystallized on the substrate aSμ.
It was formed into a cylindrical shape with m1 diameter of a3 to a2 μm. Next, the silicon oxide film was etched using this AZ photoresist pattern as a mask. ncftfi! ! Etching device (manufactured by Nichisha Anelva Co., Ltd.) used CF, gas pressure/X
/ 0" TOrr % Etching was performed for S minutes with RF power isow. After etching, the AZ photoresist was removed with oxygen plasma and observed with a scanning electron microscope.
A cylindrical silicon oxide with a height of aS μm1 and a diameter of a5 to a2 μm was formed on the silicon substrate.

[Example 3] Polydimethylsiloxane aS as a phase-separated polymer membrane
A solution of g and poly (/, l-dimethyltetrafluoropropyl methacrylate) (1), and l dissolved in xylene 10d was spin-coated (θθ0rpn).

Processing was carried out in the same manner as in Example 2, except that the same process was used as in Example 2. When observed using a scanning microscope, it was found that there was a flatness Q on the silicon substrate! ; Arn, cylindrical silicon oxide with a diameter of 1 to 25 μm was formed.

[Example 4] A silicon substrate is prepared, and AZ is deposited on it in the same manner as in Example 3.
A photoresist film and a phase-separated polymer film were formed. However, the AZ photoresist film was not heat-treated. Next, oxygen gas plasma treatment was performed for 11 minutes under the same conditions as in Example 3. Next, silicon oxide was deposited on this to a thickness of 2 μm. The AZ photoresist was then removed in isoamyl acetate.

When observed with a scanning electron microscope, a silicon oxide film having fine holes with a diameter of a cor Okpm was formed.

〔Effect of the invention〕

As explained above, the substrate 27 of the present invention [J method is
The mask manufacturing process and exposure process required in photo-etching are time consuming and unnecessary, and they are also considered difficult in photo-etching.
Microfabrication of micrometers or less is also possible, and processing from several micrometers to less than 1 micrometer is possible, and it is possible to easily and economically obtain a large area, high shape ratio, and homogeneous #fine pattern on a substrate. Therefore, it has the advantage that it can be used for fabricating a heat sink mounted on a conductor element such as LSI5IC, fabricating a lubricating protective film for a magnetic disk, fabricating a substrate for B loe and Raman absorption source measurement 1 analysis on the sensor surface, and fabricating a filter. There is.

[Brief explanation of drawings]

Figure 1 (a) to (d), Figure 2 (a) to fd), Figure 3
m(a)) to (d)u are all diagrams showing examples of the present invention, and are Mizuko process diagrams illustrating a method of processing a substrate. 1...8i resin and organic polymer phase separation membrane, 2.
... Substrate, 3 ... Organic polymer part in the phase separation membrane, 4 ... Si resin part in the phase separation membrane,
5... Si resin part (silicon oxide) after oxygen gas plasma treatment, 6... Organic polymer film, 7
...Deposited material.

Claims (4)

[Claims] (1) A phase-separated film of silicone resin or polysilane resin and organic polymer is formed on the substrate to be processed, and this is used as a processing mask to transfer the phase-separated pattern onto the substrate to be processed. D Loe method of substrate. (2) forming a phase-separated film of silicone resin or polysilane resin and organic polymer on the substrate to be processed;
Next, the second step is to perform oxygen gas plasma treatment to remove the organic polymer and oxidize the silicone resin or polysilane resin to form a fine pattern of silicon oxide on the substrate.Next, the substrate is etched using this as a mask.
2. The method of processing a substrate according to claim 1, further comprising the step of rolling. (3) Covering ■ A step of forming a film on the substrate to serve as a mask material during etching of the substrate, then a step of forming a phase-separated broken film of silicone resin or polysilane resin and Mg molecules on the mask material; Next, this is treated with oxygen gas plasma to remove organic polymers, and the silicone resin or polysilane resin is oxidized to form fine patterns of conditioned silicon on the substrate.Then, the oxidized silicon is used as a mask to form fine patterns on the substrate. A special feature of Wfi11 characterized in that it includes a step of etching a mask material on a substrate to transfer a fine pattern of saponified silicon onto the mask material, and then a step of etching the substrate using the patterned mask material as a mask. A method for processing a substrate according to item 1. (4) a step of forming an organic polymer film on the substrate to be processed, then a step of forming a phase-separated film of silicone resin or polysilane resin and organic knitted molecules on the S-containing polymer layer;
Next, this is subjected to oxygen gas plasma treatment to acclimatize the silicone resin or polysilane resin to silicon oxide, remove the organic polymer in the phase separation film, and at the same time remove the parts of the substrate that are not covered by the acclimatized silicon. The organic polymer film is selectively removed to form an organic polymer pattern on the substrate, and the organic polymer pattern is used to form a pattern on the substrate by lift-off processing. A method for processing a substrate according to claim 1.