JP2001052979A - Formation method for resist, working method for substrate, and filter structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a resist for satisfactory adhesion, a working method for a substrate, and a filter structure. SOLUTION: An aluminum film 72 is inserted between a glass substrate 71 and a resist 73, so that adhesion between them is enhanced because of the high adhesion of the aluminum film 72. Thus peeling of the resist 73 is prevented, while a base body is etched satisfactory with the resist 73 as a mask. This method can also be applied to a color filter structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to, for example, a method for forming a resist on a substrate and a method for processing a substrate, and a filter structure in the manufacture of a semiconductor device.

[0002]

2. Description of the Related Art Conventionally, a glass substrate or the outermost surface is made of SiO _2.
As a means for improving the adhesion of the resist to the Si substrate of the film, a method of coating the surface of the substrate with a silane coupling agent before applying the resist has been widely used. For example, as shown in U.S. Pat. No. 3,549,368, it is known that a hexaalkyldisilazane such as hexamethyldisilazane (HMDS) is spin-coated and pretreated before applying a photoresist.

[0003] Further, with respect to the treatment method of the silane coupling agent, various kinds of improved methods have been proposed. (For example, see Japanese Patent Publication No. 6-30338)

Further, as disclosed in, for example, JP-A-7-245252, a method has been proposed in which a wafer is subjected to a radiation treatment before the application of the resist and then the resist is applied.

[0005]

However, the technique of simply coating a silane coupling agent (for example, HMDS (hexamethyldisilazane)) is a MEMS technique.
(Micro Electro Mechanical Systems) In long-time wet etching of a glass substrate, which is frequently used in the field, the resist is likely to peel off from the glass substrate.

A method of applying a resist after performing a radiation treatment is effective for improving the adhesion, but since the surface after the discharge treatment is very activated, the surface is instantly exposed when exposed to the atmosphere. As a result, a reaction such as water adsorption occurs and the surface properties change, and the effect of the discharge treatment is lost.

Accordingly, an object of the present invention is to provide a method of forming a resist, a method of processing a substrate, and a filter structure which can form a resist with good adhesion.

[0008]

That is, the present invention provides a method for forming a resist, which comprises providing a specific metal layer on the surface of a substrate on which a resist is to be formed, and forming a resist thereon. This is referred to as a first forming method.)

According to the first forming method of the present invention, since the resist is formed on the specific metal layer provided on the surface of the base, the metal layer interposed between the base and the resist is formed by the base and the resist. There is adhesiveness to each of the resists, and the adhesiveness between the substrate and the resist is enhanced through the metal layer, so that peeling of the resist from the substrate during processing can be prevented.

The present invention also provides a specific metal layer on the surface of a substrate on which a resist is to be formed, a resist is formed thereon, the resist is patterned, and the resist is used as a mask to form the metal layer and the substrate. After processing into a predetermined pattern, the resist is removed, and further, the metal layer is heated in an oxygen atmosphere to modify the metal layer into an oxide and deactivate the metal layer (hereinafter referred to as the first method of the present invention). ).

According to the first processing method of the present invention, after performing a predetermined processing based on the resist formed by the above-mentioned first forming method, the metal layer is modified into an oxide and deactivated. The substrate can be processed well without removing the resist, and the inactivated metal layer can remain on the surface of the substrate to insulate the surface of the substrate.

Further, the present invention provides a method for forming a resist, in which a silicon layer or a carbon layer is provided on the surface of a substrate on which a resist is formed, and a resist is formed thereon. ).

According to the second forming method of the present invention, since the resist is formed on the silicon layer or the carbon layer provided on the surface of the base, the silicon layer or the carbon layer interposed between the base and the resist is formed. Thereby, the adhesion between the substrate and the resist can be improved.

Further, according to the present invention, a silicon layer or a carbon layer is provided on the surface of a substrate on which a resist is formed, and the resist is formed thereon, and the resist and the silicon layer or the carbon layer are patterned to form a mask. After the substrate is processed into a predetermined pattern using this, the resist is removed, and the silicon layer is oxidized and reformed by heating in an oxygen atmosphere, or the carbon layer is gasified and removed. (Hereinafter, referred to as a second processing method of the present invention).

According to the second processing method of the present invention, after the above-mentioned predetermined processing using the resist formed by the above-mentioned second forming method, the silicon layer is oxidized and reformed, or the carbon layer is formed by gas. Since the resist is stripped and removed, the substrate can be favorably processed without stripping the resist. For example, when an amorphous silicon layer is provided on a glass substrate, the amorphous silicon is integrated with the glass by modification. If a silicon layer is provided on a silicon substrate, it can be easily integrated with the substrate as silicon oxide. When a carbon layer is provided, the carbon layer can be gasified and removed by heating.

Further, the present invention relates to a filter structure in which a silicon layer or a carbon layer is formed under a resist as a filter material (hereinafter, referred to as a filter structure of the present invention).

According to the filter structure of the present invention, since the silicon layer or the carbon layer is provided as a base of the resist, the effect of the above-described second forming method can be obtained, and the resist having good adhesion to the substrate can be obtained. Can be provided.

Further, according to the present invention, after the substrate is irradiated with high-energy particles (including, for example, radiation), a resist is applied to the substrate in a vacuum or an inert gas atmosphere, or the resist adhesion is promoted. The present invention relates to a method for forming a resist (hereinafter, referred to as a third forming method of the present invention) in which treatment with an agent or application of a solvent for the resist is performed, and then the resist is applied.

According to the third forming method of the present invention, since the resist is applied to the substrate irradiated with the high energy particles in a vacuum or an inert gas atmosphere, the surface of the substrate is modified by the irradiation of the high energy particles. Thus, the resist can be applied while maintaining the modified state, whereby the adhesion of the resist can be improved because there is no adsorption of moisture or the like in the atmosphere. Further, the surface of the substrate is treated with a resist adhesion promoter in a vacuum or an inert gas atmosphere, or a solvent for the resist is applied, and then the resist is applied (this may be in the air or in a vacuum). For the same reason as described above, it is possible to maintain the modified state of the substrate surface and enhance the treatment effect of the resist adhesion promoter, thereby improving the adhesion of the resist. Also, if a resist is applied to a substrate coated with a resist solvent on the surface modified in the same manner as described above, and further baked,
As the resist cures, the solvent below it evaporates, and a resist film with improved adhesion to the substrate can be formed.

Further, according to the present invention, after irradiating a substrate with high energy particles,
Applying a resist on the substrate, or after treatment with a resist adhesion promoter or applying a solvent for the resist, and then applying a resist, patterning the resist, processing the substrate using this as a mask, The present invention relates to a method of processing a substrate for removing the resist (hereinafter, referred to as a third processing method of the present invention).

According to the third processing method of the present invention, the base is processed based on the above-described third forming method.
The substrate can be processed by obtaining the same effect as that of the method for forming the substrate.

[0022]

Preferred embodiments of the present invention will be described below with reference to the accompanying drawings.

<Embodiment 1> In the first forming method and the first processing method described above, the metal layer has an absolute value of oxide formation energy larger than that of molybdenum (for example, it can be used as a semiconductor device). Desirably, the metal is a highly oxidizable metal.

Such a metal layer is desirably made of a material selected from aluminum, titanium, chromium, tungsten and tantalum.

Then, for example, as shown in FIG.
After the resist is exposed and developed to form the resist in a predetermined pattern, it is desirable to etch the metal layer and the base as shown in FIG.

<Embodiment 2> In the above-described second forming method and second processing method of the present invention, for example, FIG.
As shown in FIG. 2D, after the resist is exposed and developed to form the resist and the silicon layer (for example, amorphous silicon layer) or the carbon layer (for example, amorphous carbon layer) in a predetermined pattern, FIG. )
It is desirable to etch the substrate as shown in FIG. Note that silicon hydride such as SiH ₄ is used as a raw material of silicon, and this is decomposed to deposit amorphous silicon. A hydrocarbon such as methane is used as a raw material of carbon, and this is decomposed to deposit amorphous carbon.

Further, in this embodiment, the silicon layer is used as a filter material as a base of the resist, and for example, the adhesion of the filter layer in a liquid crystal display device as shown in FIG. 4 can be improved.

In this case, it is desirable that the resist and the amorphous silicon layer or the carbon layer are laminated in the same pattern, so that it can be used for a light transmission type or light reflection type optical device.

<Embodiment 3> In the above-described third forming method and third working method of the present invention, for example, FIG.
As shown in (b), the irradiation of the high-energy particles is performed in plasma discharge or corona discharge, and the substrate is washed with hydrogen gas plasma to remove organic substances on the surface of the substrate and to modify the surface. Quality is desirable.

Then, as shown in FIG. 3 (c), after the treatment with the resist adhesion promoter or the application of the resist solvent, as shown in FIG. Is desirably formed.

After the application of the resist, the solvent may be removed by evaporating the solvent by heating.

Then, as shown in FIG. 3E, the resist is exposed and developed to form the resist in a predetermined pattern, and then the substrate is etched as shown in FIG. 3F. Is desirable.

In this case, it is desirable to remove the resist adhesion promoter simultaneously with dissolving and removing the resist, or to evaporate and remove the solvent by a heat treatment after the application of the resist.

Hereinafter, each embodiment of the present invention will be described in more detail.

In the case of the first embodiment, first, a glass substrate 71 as shown in FIG. 1A which has been subjected to general ultrasonic cleaning in acetone is put into a vacuum evaporator (not shown). As shown in FIG. 1 (b), an ultra-thin Al
An (aluminum) film 72 is formed. Thereby, the interface with the substrate is easily oxidized during the vapor deposition, so that the adhesion of the Al film 72 is improved.

Next, using a spin coater (not shown), for example, as shown in FIG.
Is applied. Subsequently, by using a mask and a contact aligner (not shown) to irradiate and develop ultraviolet rays, a desired resist pattern can be obtained as shown in FIG. At this time, the Al film 72 in the resist pattern 74 remains.

Next, by dipping the glass substrate 71 in a hydrofluoric acid solution for a long time, the Al film 72 is easily dissolved, and as shown in FIG. A pattern 75 is formed on the surface by etching. Subsequently, as shown in FIG. 1F, the resist is removed by processing with a high-temperature resist stripper, but at this stage, the aluminum film 72 on the glass substrate 71 remains as a resist pattern mark.

However, since such an aluminum film causes an electric leak, the glass substrate 7 is exposed in air.
1 is heated, the ultra-thin Al film 72 remaining on the substrate is changed to an Al ₂ O ₃ film 7 as shown in FIG.
Instead of 2A, the surface of the glass substrate 71 is insulated.

As described above, the surface of the glass substrate 71
By applying the resist 73 after the formation of the l film 72, the resist can be patterned in a state of extremely good adhesion, and the resist 73 which is difficult to peel off even after a long-time glass etching process can be obtained. .

In the conventional method, the glass substrate 7 is usually used unless a silane coupling agent such as HMDS is used.
1 and the resist 73 have poor adhesion, but the glass substrate 71 and the Al
This is because the adhesion between the film 72 and the Al film 72 and the resist 73 is extremely good, and the adhesion between the resist 73 and the glass substrate 71 is sufficient.

Further, by dissolving the Al film 72 with hydrofluoric acid by forming the Al film 72 extremely thin,
Further, it is possible to easily oxidize the Al film 72 after removing the resist 73. In this case, the Al film 72 does not necessarily have to be a film, and the Al
May be attached in an island shape.

As described above, in Embodiment 1, the glass substrate 71 is immersed in a hydrofluoric acid solution for etching. For example, ICP (inductively coupled plasma etching) and RIE (reactive ion etching) are used. Dry etching can also be performed. In the case of wet etching, isotropic etching is also possible,
In some cases, the required time can be reduced.

In the first embodiment, for example, FIG.
8 can be applied to the production of the micromirror shown in FIG. 8 (however, this is the same in other embodiments).
6 is a sectional view of a micro mirror (for example, for an optical pickup), FIG. 7 is a plan view, and FIG. 8 is a schematic perspective view. This micromirror is one in which the wafer 100 shown in FIG. 5 is diced into individual chips 128 along a grid line 129. Before dicing, a common glass substrate 118 is processed by the present invention. Thereafter, the substrate is bonded to the upper silicon substrate 117, and is further diced into each micromirror.

This micromirror is used for the silicon substrate 11
7 is removed in a substantially square ring shape by etching using photolithography technology, and the inside of this region is left as the mirror main body 121. Mirror body 121
Are coupled to the substrate 117 via two beams 119 at diagonal corners. This substrate 117 is a silicon or silicon oxide substrate 118 whose center is processed into a concave shape by etching using photolithography technology.
Is anodically bonded to the substrate 118.
Embodiment 2 can be effectively applied to the concave etching at the central portion of. In the drawing, reference numeral 120 denotes a reflecting surface, 1
22 is an upper electrode, 123 is a lower electrode, 124 is a wiring, 1
Numeral 25 indicates a gap, and 126a and 126b indicate contact holes.

Next, in the case of the second embodiment, the glass substrate 71 shown in FIG. 2A, which has been subjected to general ultrasonic cleaning in acetone, is used for plasma CVD (chemical vapor deposition) not shown. The device was put into the apparatus, and an extremely thin a-Si: H (hydrogenated amorphous silicon) film 77 was formed on the surface as shown in FIG.

Next, using a spin coater (not shown), for example, as shown in FIG.
Is applied. Subsequently, a desired resist pattern can be obtained by irradiating and developing ultraviolet rays using a mask and a contact aligner (not shown).

At this time, the a-Si: H film 77 on the surface is easily dissolved by a strong alkaline developing solution, and as shown in FIG.
Is removed, and the surface of the glass substrate 71 is exposed. next,
This glass substrate 71 is immersed in a hydrofluoric acid solution for a long time, and a pattern 80 can be formed on the surface of the glass substrate 71 by etching, as shown in FIG.

Next, the resist is removed by processing with a high-temperature resist stripping solution. As shown in FIG.
At this stage, the a-Si: H film 77 is formed on the glass substrate 71.
Remains. Next, by heating the glass substrate 71 in air, the a-S
i: H film 77 is oxidized to SiO ₂ , and FIG.
Can be integrated with the glass surface as shown in FIG.

As described above, a-S on the glass substrate 71
i: By applying the resist after forming the H film 77, the resist can be patterned in a state of extremely good adhesion, and the resist 78 which is difficult to peel even during a long-time glass etching process can be used. Obtainable.

This is because, in the conventional method, the glass substrate 7 is usually used unless a silane coupling agent such as HMDS is used.
1 and the resist 78, the glass substrate 71 and the a-
This is because the adhesion between the Si: H film 77 and the a-Si: H film 77 and the resist 78 is extremely good, and the adhesion between the resist 78 and the glass substrate 71 is sufficient.

Further, by forming the a-Si: H film 77 extremely thin, the dissolution of the a-Si: H film 77 by the developing solution is facilitated, and the aS
i: facilitate oxidation of the H film 77; Also in the case of the present embodiment, a-Si: H does not necessarily have to be a film, and a-Si: H may be attached to the surface of the glass substrate 71 in an island shape.

As described above, Embodiment 2 and Embodiment 1
The difference is that you do not need to use metal. Although the second embodiment is a glass substrate, the surface of a Si (silicon) substrate on which a semiconductor element is fabricated is
This is also effective when a resist is patterned by providing an O ₂ film. In this case, the present embodiment is suitable in that there is no fear of metal contamination. Further, a-Si on the surface:
If the H film 77 is left without being oxidized, it can be anodically bonded to another glass substrate, which is a useful technique in the MEMS field.

The second embodiment can also be applied to improve the adhesion between the color filter layer of the liquid crystal display device and the insulating film as shown in FIG. 4, for example.

In FIG. 4A, reference numeral 1 denotes a glass substrate;
Is a step, 7 is a single crystal silicon layer, 11 is a gate electrode, 1
2 is a gate oxide film, 15 is an LDD part, 18 and 19 are N
⁺ Type source or drain regions, 25 and 36 are insulating films,
26 and 41 are electrodes, 52 is a SiN film, 53 is SiO ₂
A-Si: H on the insulating film 36 as shown in FIG.
The film 20 (corresponding to the a-Si: H film 77 described above) is provided.
As shown in FIG. 4 (b), a color filter layer 51 (G) (green filter) laminated thereon in a conventional manner.
And 51 (R) (red filter layer) (corresponding to the above-described resist 78) and the insulating film 36 can be improved in adhesion.

In this case, as shown in FIG. 4C, a contact window is opened in the drain portion 19 in the filter layer, and a light shielding layer 43 serving as a black mask layer is formed here.
Next, as shown in FIG.
8B, and an ITO transparent electrode 41 is formed in a through hole provided in the flattening film so as to be connected to the light shielding layer 43.

Next, in the case of Embodiment 3, the glass substrate 71 shown in FIG.
As shown in FIG. 3B, the substrate is put into a vacuum chamber 82, and plasma 83 is generated in a hydrogen gas to perform plasma cleaning to remove organic substances on the surface of the glass substrate 71 and modify the surface of the glass substrate 71. I do. In this case, the plasma contains hydrogen ions and ultraviolet rays, but only ultraviolet rays can be used. Alternatively, hydrogen ions and / or ultraviolet rays may be irradiated during corona discharge instead of the plasma discharge.

Here, “modification” means removal of water adsorbed on the surface of the glass substrate and removal of hydroxyl groups generated by dissociation of the water adsorbed.
And generation of Si—H bonds by bonding of H to Si dangling bonds generated by cutting Si—O bonds on the surface of the glass substrate by bombardment of hydrogen ions (without bombardment of hydrogen ions. To
Only the dangling bond may be left on the surface). The presence of water adsorbed in any number of layers on the surface of the glass substrate significantly impairs the effect of HMDS to be treated next.

Next, the glass substrate 71 in this state is transferred to another vacuum chamber 89 through a gate valve without breaking the vacuum, as shown in FIG. 3C, where the gaseous HMDS ( Hexamethyldisilazane) 84 is introduced, and the HMDS film 85 is adsorbed on the surface of the glass substrate 71.

Next, in this state, the glass substrate 71 is taken out of the vacuum chamber 89 into the atmosphere, and for example, a positive resist 86 is applied by a spin coater (not shown) as shown in FIG. Next, a desired resist pattern 87 is formed by irradiating and developing an ultraviolet ray using a mask and a contact aligner (not shown), and the HMDS film 85 is also removed in the same pattern.

Next, the glass substrate 71 is immersed in a hydrofluoric acid solution for a long time, and a pattern 88 is obtained by etching on the surface of the glass substrate 71. Subsequently, the glass substrate 71 is treated with a high-temperature resist stripper to obtain a resist 85 With HMD
The S film 85 is removed. As a result, a desired pattern 88 can be obtained on the glass substrate 71 by etching.

In the case of this embodiment, despite the use of the same HMDS as in the ordinary method, the glass substrate 71 before the application of HMDS is clean, and excess adsorbed water and hydroxyl groups are present on the surface. Since the amount is small, HMDS adsorption is promoted in a favorable and uniform state, in a form in which the alkoxyl group of HMDS removes H of the Si—H bond on the glass substrate 71 side. Further, since the surface of the glass substrate 71 where the Si-H bond is directly exposed on the surface of the glass substrate 71 is hydrophobic, when the resist is directly applied in a vacuum without using HMDS, The adhesion with the resist 86 is improved.

As a result, it is possible to apply a resist having better adhesiveness than a normal HMDS process. But,
When the substrate is exposed to the atmosphere after the plasma cleaning, the moisture in the air immediately re-adsorbs to many layers, and the Si-H bond is oxidized and the Si-O bond is restored, so that the effect of the plasma cleaning is lost. I will be.

[0063]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but it goes without saying that the present invention is not limited to the following embodiments.

According to each of the above embodiments, formation of a resist and processing of a substrate were performed.

Example 1 According to the first embodiment, as shown in FIG.
The adhesion of the resist 73 was improved by forming the Al film 72 on No. 1. First, a 5-inch glass substrate 71 shown in FIG. 1A was used, and 10 min. Dipped and washed. Next, this glass substrate 71 was put into a vacuum evaporation machine (not shown),
An Al film 72 having a thickness of 2 nm was formed at a degree of vacuum of ^-7 Torr as shown in FIG.

Next, as shown in FIG. 1 (c), a positive resist 3 having a thickness of 5.0 μm was applied to the glass substrate 71 taken out of the vacuum evaporation machine into the atmosphere by a spin coater (not shown).
m at 110 ° C. for 10 min. Pre-baked. Subsequently, lithography was performed with a contact aligner using a G line and development was performed, and a desired resist pattern 74 was obtained as shown in FIG. Generally, the developing solution is a strong alkali, but at this stage, the Al film 72 in the portion without the resist still remains. Next, this glass substrate 7
1 at 130 ° C., 10 min. Post-bake treatment was performed under the following conditions.

Subsequently, the glass substrate 71 was heated at 23 ° C.
100 min. In a mixture of H ₄ F (buffer agent) and HF (etchant). Dipped. At this time, NH ₄ F and HF
Is 10 μm / 100 min. It was adjusted to be. After a long immersion, Al on the surface without resist on the surface
Easily dissolved, and a pattern 5 etched to a depth of 10 μm was formed on the underlying glass as shown in FIG.

Next, the resist 73 was removed as shown in FIG. 1F by treating the glass substrate 71 in a resist stripping solution heated to 80 ° C. At this stage, the Al under the resist 73 was removed. The film 72 remained. Here, the substrate 71 is placed on a hot plate not shown (atmospheric atmosphere).
By keeping the temperature at 350 ° C., the Al film 72 on the surface of the glass substrate 71 is completely Al ₂ O _{3 as} shown in FIG.
71A. Thereby, the glass surface was insulated.

As a result of the above process, good etching could be performed without the pattern being destroyed due to the infiltration of hydrofluoric acid between the glass substrate 71 and the resist 73. The effect is obtained even if the Al film 71 exists in an island shape on the glass substrate 71.

According to this embodiment, aluminum having good adhesion to the glass substrate 71 and the resist 73 is used.
Since the Al film 72 is interposed between the glass substrate 71 and the resist 73, the adhesion between the glass substrate 71 and the resist 73 can be enhanced. As a result, the resist 73 is patterned, and the glass substrate 71 can be subjected to predetermined etching using the resist 73 as a mask, and the Al film 72 can be used as it is after being modified into the Al ₂ O ₃ film 71A. . In addition, as conventional pre-processing,
The peeling of the resist, which is caused only by applying the silane coupling agent, is also prevented, and the substrate surface does not change in the air after radiation treatment as a conventional pretreatment in this embodiment.

Example 2 According to the second embodiment, as shown in FIG.
First, an extremely thin a-Si: H film 77 is formed on
By applying No. 8, the adhesion of the resist 78 was improved.

First, FIG. 2A shows that 10 m
in. This is a 5-inch glass substrate 71 subjected to ultrasonic cleaning. This glass substrate 71 is put into a vacuum chamber (not shown) and kept at 350 ° C., and then SiH ₄ 150SCC
M (Standard cc per minute: the same applies hereinafter), H ₂ 10
Keep the pressure at 200 mTorr by flowing 0 SCCM,
Plasma is generated by supplying 100 W of RF power of 3.56 MHz, and as shown in FIG.
An a-Si: H film 77 having a thickness of 2 nm was formed on the surface.

Subsequently, as shown in FIG. 2C, a positive type resist 10 is applied to the glass substrate 71 taken out of the vacuum chamber into the atmosphere to a thickness of 5.0 μm by a spin coater (not shown) to obtain a thickness of 110 μm. 10 min. Pre-baked. Subsequently, lithography was performed with a contact aligner using G line and development was performed to obtain a desired resist pattern 79 as shown in FIG. Generally, since the developing solution is a strong alkali, a-Si: H77 easily dissolves in the developing solution, and a-Si: H7 in a portion without a resist is used.
7 was removed, and the surface of the glass substrate 71 was exposed. Next, the glass substrate 71 was set at 130 ° C. for 10 min. Post-bake treatment was performed under the following conditions.

Next, this glass substrate 71 was treated with NH 3 at 23 ° C.
100 min. In a mixture of ₄ F and HF. Dipped. At this time, the ratio of NH ₄ F and HF was 10 μm / 100 min.
It was adjusted to be. As a result, as shown in FIG. 2E, an etched pattern 80 having a depth of 10 μm was formed on the glass substrate 71.

Next, the glass substrate 71 was treated in a resist stripping solution heated to 80 ° C. to remove the resist 78 as shown in FIG. 2 (f). The Si: H film 77 remained. Here, by keeping the substrate 71 at 500 ° C. on a hot plate (air atmosphere) not shown, the surface a-Si: H film 77 is completely changed to SiO ₂ as shown in FIG. And integrated with the glass substrate 71. Thereby, the glass surface was insulated.

As a result of the above process, good etching was able to be performed without the pattern being destroyed by the permeation of hydrofluoric acid between the glass substrate 71 and the resist 78. The effect is obtained even if the a-Si: H film 77 exists on the glass substrate 71 in an island shape.

According to this embodiment, as in the first embodiment, amorphous silicon having good adhesion to glass and resist is used, and an a-Si: H film 77 is interposed between the glass substrate 71 and the resist 78. Therefore, the adhesion between the two can be improved. As a result, the same effect as that of the first embodiment can be obtained, and the a-Si: H film 77 is modified and can be integrated with the substrate 71.

Example 3 According to the third embodiment, as shown in FIG.
1 was washed with plasma 83, and thereafter HMDS was applied without exposing the surface of the glass substrate 71 to the atmosphere to improve the adhesion.

First, FIG. 3A shows that 10 m
in. This is a 5-inch glass substrate 71 subjected to ultrasonic cleaning. As shown in FIG. 3B, the glass substrate 71 is put into a vacuum chamber 82 and kept at 350 ° C.
_By supplying 200 SCCM and maintaining the pressure at 300 mTorr and supplying 13.56 MHz RF power of 500 W, H ₂ plasma 83 was generated and 10 min.
For a while. As a result, excess adsorbed water on the surface of the glass substrate 71 was removed, and the Si—O bond was partially cut by irradiation of the substrate with H ⁺ ions, and a Si—H bond was generated.

Next, without breaking the vacuum, the glass substrate 7
3 is transported to another vacuum chamber 89, and as shown in FIG.
9 was introduced. As a result, the glass substrate 71 has the HMD
The S film 85 was formed. This HMDS was bonded to Si in a form of depriving H of Si—H bond, or was deprived of H from adsorbed H ₂ O molecules existing in almost one molecular layer and bonded to O atoms. As a result, the HMDS film 85 firmly adhered to the glass substrate 71.

In this state, as shown in FIG. 3D, the glass substrate 71 is exposed to the air, and then a positive type resist 21 is applied to a thickness of 5.0 μm by a spin coater (not shown). 10 min. Pre-baked. Subsequently, lithography was performed with a contact aligner using G-line and development was performed, and a desired resist pattern 87 was obtained as shown in FIG. At this time, the HMDS was removed almost in accordance with the pattern 87, and the surface of the glass substrate 71 was exposed in the portion without the resist. Next, this glass substrate 71
At 130 ° C for 10 min. Post-bake treatment was performed under the following conditions.

Next, this glass substrate 71 was treated with NH.sub.3 at 23.degree.
100 min. In a mixture of ₄ F and HF. Dipped. At this time, the ratio of NH ₄ F and HF was 10 μm / 100 min.
It was adjusted to be. As a result, as shown in FIG. 3F, an etched pattern 88 having a depth of 10 μm was formed on the glass substrate 71.

Next, the glass substrate 71 was treated in a resist stripping solution heated to 80 ° C. to remove the resist 86. At this stage, as shown in FIG. 3G, the HMDS film 85 under the resist was removed. Was also removed at the same time, and a desired pattern 88 could be obtained on the glass substrate 71.

As a result of the above process, good etching could be performed without the pattern being distorted due to the infiltration of hydrofluoric acid between the glass substrate 71 and the resist 86.

According to the present embodiment, the glass substrate 71 is irradiated with H ⁺ ions during the plasma discharge in the vacuum chamber 82, so that the glass substrate 71 is in a hydrophobic state or a hydrogenated state in which the HMDS is easily adhered. HM in a separate vacuum chamber without exposure to air while maintaining state
Since the DS film 85 is formed on the surface of the glass substrate 71 and the resist 86 is formed thereon, the glass substrate 71 and the resist 8 are interposed via the HMDS film 85 having an improved coupling property.
6 can be improved in adhesion. As a result, when etching is performed using the resist as a mask, the adhesiveness of the resist is sufficiently maintained, and the same effects as those of the other embodiments described above can be obtained.

Each of the above embodiments can be variously modified based on the technical idea of the present invention.

For example, the thickness of the metal film shown in the first embodiment,
The metal film material and the processing temperature can be changed without departing from the gist of the present invention. Further, the substrate is not limited to glass, and a substrate in which SiO ₂ or SiN _X is formed on a Si substrate can also be used.

The thickness and processing temperature of the a-Si: H film shown in the second embodiment can be changed without departing from the gist of the present invention. Further, a-Si, poly-Si, amorphous carbon, poly-C, or the like can be used instead of the a-Si: H film. In particular, when a C film is used, the film can be removed by being vaporized as CO or CO ₂ by heating in an oxygen atmosphere.
Further, the substrate is not limited to glass, and a substrate in which SiO ₂ or SiN _X is formed on a Si substrate can also be used.

The processing conditions such as the processing temperature shown in the third embodiment can be changed without departing from the gist of the present invention. Further, even if the vacuum is broken after the plasma treatment of the glass substrate, the resist application or the adhesion promoting agent can be applied while holding in a dry inert gas such as a rare gas. Further, the substrate is not limited to glass, and a substrate in which SiO ₂ or SiN _X is formed on a Si substrate can also be used.

[0090]

As described above, according to the first and second forming methods and the first and second processing methods of the present invention, a metal layer or a silicon layer (or a silicon layer) interposed between a substrate and a resist is provided. Since the carbon layer improves the adhesion to the substrate and the resist, and enhances the adhesion between the substrate and the resist, the peeling of the resist can be prevented and the substrate can be favorably processed. When a silicon layer is used as a base of the resist, a resist having good adhesion and effective as a filter of an optical device can be formed.

According to the third forming method of the present invention, a resist is applied to a substrate irradiated with high energy particles in a vacuum or an inert gas atmosphere, or a resist adhesion promoter or a resist solvent (such as Is applied during the baking process, the resist is cured, and the resist is further applied.Therefore, the surface of the substrate is modified by irradiation of high-energy particles, and the resist can be applied while maintaining the modified state. Further, since there is no adsorption of moisture and the like in the atmosphere, the adhesiveness of the resist can be improved.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram in which Al is formed into a film to improve the adhesion according to Example 1 of the present invention.

FIG. 2 is a manufacturing process diagram in which a-Si: H is formed into a film to improve the adhesion according to a second embodiment of the present invention.

FIG. 3 is a manufacturing process diagram in which the adhesion is improved using plasma according to a third embodiment of the present invention.

FIG. 4 is a manufacturing process diagram in which the present invention is applied to a color filter of a liquid crystal display device.

FIG. 5 is a schematic perspective view of a wafer.

FIG. 6 is a sectional view showing a micromirror device.

FIG. 7 is a plan view of the same micromirror device.

FIG. 8 is a perspective view of the same micro mirror device.

[Explanation of symbols]

71: glass substrate, 72: aluminum film, 72A: aluminum oxide, 73, 78, 86: resist, 74,
79, 87: resist pattern, 75, 80, 88: etching pattern, 77: amorphous silicon film, 8
2, 89 ... vacuum chamber, 83 ... plasma flow, 84 ...
Gaseous HMDS, 85 ... HMDS film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) G03F 7/11 503 G03F 7/11 503 7/38 501 7/38 501 7/40 521 7/40 521 7 / 42 7/42 H01L 21/3065 H01L 21/302 J F term (reference) 2H025 AA14 AB13 AB16 AC01 AD01 AD03 DA18 DA30 DA35 EA01 EA10 FA01 FA03 FA17 FA29 FA40 FA48 2H096 AA00 AA25 AA28 CA01 CA02 CA05 DA01 EA02 GA08 HA01 HA04 LA02 4K057 WB05 WB08 WB20 WE07 WN04 5F004 BA04 BA20 DB00 DB01 DB08 EA03 EB08 5F046 HA07

Claims (25)

[Claims] 2. A method for forming a resist, comprising: forming a specific metal layer on a surface of a substrate on which a resist is to be formed; and forming a resist on the metal layer. 2. The method of forming a resist according to claim 1, wherein the metal layer is made of a highly oxidizable metal having an absolute value of an oxide formation energy larger than that of molybdenum. 3. The method according to claim 1, wherein the metal layer comprises aluminum, titanium,
3. The method for forming a resist according to claim 2, wherein the method is selected from chromium, tungsten, and tantalum. 4. A specific metal layer is provided on the surface of a substrate on which a resist is to be formed, a resist is formed thereon, the resist is patterned, and the metal layer and the substrate are formed into a predetermined pattern using the resist as a mask. After the processing, a method for processing a substrate, wherein the resist is removed, and further, the metal layer is heated in an oxygen atmosphere to transform the metal layer into an oxide and passivate the metal layer. 5. The substrate processing method according to claim 4, wherein the metal layer and the substrate are etched after the resist is exposed and developed to form the resist into a predetermined pattern. 6. The resist processing method according to claim 4, wherein said metal layer is made of a highly oxidizable metal having an absolute value of an oxide formation energy larger than that of molybdenum. 7. The method according to claim 1, wherein the metal layer comprises aluminum, titanium,
The resist processing method according to claim 6, wherein the method is selected from chromium, tungsten, and tantalum. 8. A method for forming a resist, comprising: providing a silicon layer or a carbon layer on the surface of a substrate on which a resist is to be formed, and forming a resist thereon. 9. The method for forming a resist according to claim 8, wherein the silicon layer is used as a base of the resist as a filter material. 10. A silicon layer or a carbon layer is provided on a surface of a substrate on which a resist is formed, and the resist is formed thereon, and the resist and the silicon layer or the carbon layer are patterned to form a mask. After processing the substrate into a predetermined pattern using this, the resist is removed, and the silicon layer is oxidized and reformed by heating in an oxygen atmosphere, or the carbon layer is gasified and removed. Processing method. 11. The method according to claim 10, wherein the resist is exposed and developed to form the resist and the silicon layer or the carbon layer in a predetermined pattern, and then the substrate is etched. 12. A filter structure in which a silicon layer or a carbon layer is formed under a resist as a filter material. 13. The method according to claim 13, wherein the resist and the amorphous silicon layer or the carbon layer are laminated in the same pattern.
The filter structure according to claim 12. 14. The filter structure according to claim 12, which is used for a light transmission type or light reflection type optical device. 15. Irradiating the substrate with high-energy particles and then applying a resist on the substrate in a vacuum or inert gas atmosphere, or treating with a resist adhesion promoter or applying a solvent for the resist. And then applying a resist. 16. The method of forming a resist according to claim 15, wherein the irradiation of the high energy particles is performed in a plasma discharge or a corona discharge. 17. The method of forming a resist according to claim 16, wherein the substrate is washed with hydrogen gas plasma to remove organic substances on the surface of the substrate and modify the surface. 18. The method for forming a resist according to claim 15, wherein the resist is formed on the substrate in the air after the treatment with the resist adhesion promoter or the application of a solvent for the resist. 19. The method of forming a resist according to claim 15, wherein after the application of the resist, the solvent is removed by evaporating it by a heat treatment. 20. After irradiating the substrate with high energy particles, a resist is applied on the substrate in a vacuum or an inert gas atmosphere, or a treatment with a resist adhesion promoter or application of a solvent for the resist is performed. And then applying a resist, patterning the resist, processing the substrate using the resist as a mask, and removing the resist. 21. The substrate processing method according to claim 20, wherein the substrate is etched after the resist is exposed and developed to form the resist in a predetermined pattern. 22. The substrate according to claim 20, wherein the resist adhesion promoter is removed simultaneously with the dissolution and removal of the resist, or the solvent is evaporated and removed by a heat treatment after the application of the resist. Processing method. 23. The method according to claim 20, wherein the irradiation of the high energy particles is performed in a plasma discharge or a corona discharge. 24. The substrate processing method according to claim 23, wherein the substrate is washed with hydrogen gas plasma to remove organic substances on the surface of the substrate and modify the surface. 25. The substrate processing method according to claim 20, wherein the resist is formed on the substrate in the air after the treatment with the resist adhesion promoter or after the application of the resist solvent.