JPH10268526A - Production of semiconductor device and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To process a film to be processed with good dimensional controllability by integrally etching an intermediate layer and lower layer resister by using resist patterns as a mask, thereby decreasing the number of the necessary etching stages before processing of the film to be processed and decreasing the dimensional changes and differences which arise at the time of the etching. SOLUTION: A silicon org. film 3 contg. a compd. having an Si-Si bond on the main chain, a silicon film 4 and a photosensitive resin film 5 are formed on the film 2 to be processed (for example, a conductive film 2 formed on a silicon substrate 1). This photosensitive resin film 5 is irradiated with an energy beam of visible light, UV light, etc., which are exposure light, through a mask of the desired patterns to form the resist patterns 5a by patterning the photosensitive resin film 5. The silicon film 4 and the silicon org. film 3 are simultaneously etched by using such resist patterns 5a as an etching mask. Then, the silicon film 4 and silicon org. film 3 of the required film thicknesses may be etched with the resist patterns 5a of the small film thickness.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a semiconductor device, and more particularly to a method for processing a thin film formed on a surface of a wafer substrate.

[0002]

2. Description of the Related Art In the process of manufacturing a semiconductor element, there are many steps for processing a film to be processed such as an insulating film such as a silicon oxide film or a silicon nitride film, a wiring material, an electrode material and the like. Usually, the processing of these films to be processed involves forming a photosensitive resin film on the film to be processed, performing pattern exposure, forming a resist pattern through a development process, and further using this resist pattern as an etching mask. This is performed by dry-etching the film to be processed.

In recent years, with the miniaturization of patterns accompanying the increase in the degree of integration of LSIs, the resolution, exposure latitude, or focus latitude required for forming patterns has been insufficient, and the photosensitive resin has become insufficient. There is a need to reduce the film thickness as much as possible to improve these process margins. However, thinning of the photosensitive resin film causes a decrease in dry etching resistance of the resist, and causes a problem that the resist pattern is not removed during etching.

In order to solve this problem, a resin film such as a novolak resin is formed as a lower resist on a film to be processed, a resist pattern formed on the lower resist is transferred to the lower resist, and the lower resist is used as an etching mask. Conventionally, a pattern transfer method such as a three-layer resist method or a two-layer resist method for processing a film to be processed has been used.

[0005] Hereinafter, the three-layer resist method will be described with reference to FIGS.
This will be described with reference to FIG. First, a lower resist 23, an intermediate layer 24, and an upper resist 25 are sequentially formed on a film 22 to be processed formed on a substrate 21 (FIG. 5A), and pattern exposure is performed on the upper resist 25 to form a resist. A pattern 25a is formed (FIG. 5B). Next, the intermediate layer 24 is etched by a dry etching method using the upper resist pattern 25a as an etching mask (FIG. 5C), and the lower resist 23 is etched using the obtained intermediate layer pattern 24a as an etching mask. (FIG. 6A).

The upper resist pattern 25a is formed by the above method.
Is transferred to the lower resist 23, and the film 22 to be processed is etched using the lower resist pattern 23a as an etching mask (FIG. 6B). Then, the lower resist pattern 23a is selectively removed from the film to be processed (FIG. 6C).

However, in this three-layer resist method,
Two etching steps are required before the upper resist pattern 25a is transferred to the lower resist 23. Therefore, a process cost is required, and a dimensional conversion difference generated in each etching step cannot be ignored, and it has been difficult to process a film to be processed to a desired size.

In the two-layer resist method, a lower resist and a silicon-containing resist are sequentially formed on a film to be processed, and a pattern is formed on the silicon-containing resist by pattern exposure, and the resist pattern is masked. To etch the lower resist. In this method, the number of steps can be reduced as compared with the three-layer resist method. However, since a silicon-containing resist is used, there is a problem that the resolution is reduced as compared with the case where a normal resist is used.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and in the three-layer resist method, the number of etching steps has been reduced, and the dimensional change caused by etching has been reduced. It is an object of the present invention to provide a method for manufacturing a semiconductor device which can process a film.

Another object of the present invention is to reduce the number of etching steps in a three-layer resist method, reduce a dimensional change caused by etching, and process a film to be processed with good dimensional control. It is to provide a forming method.

[0011]

In order to solve the above-mentioned problems, the present invention (claim 1) provides (a) forming a silicon organic film containing a compound having a Si-Si bond in a main chain on a film to be processed; Forming; (b) forming a silicon film on the silicon organic film; (c) forming a photosensitive resin film on the silicon film; and (d) forming a photosensitive resin film. (E) using the resist pattern as an etching mask to collectively etch the silicon film and the silicon organic film; and (g) performing the etching by using the resist pattern as an etching mask. Etching the film to be processed using the formed pattern of the silicon film and the silicon organic film as an etching mask; and (h) removing the silicon organic film. To provide a method of manufacturing a semiconductor device including the steps of, a.

According to a second aspect of the present invention, in the above-described method for manufacturing a semiconductor device (the first aspect), the film to be processed is a silicon substrate, a conductive film, an insulating film made of an organic material, and a silicon atom. Characterized by being one kind selected from the group consisting of insulating films containing:

The present invention (claim 3) comprises: (a) forming a silicon organic film containing a compound having a siloxane bond on an insulating film containing silicon atoms; and (b) forming a silicon organic film on the silicon organic film. Forming a film; and (c) forming a photosensitive resin film on the silicon film.
(D) performing pattern exposure on the photosensitive resin film;
Forming a resist pattern, (e) etching the silicon film using the resist pattern as an etching mask, and (g) using the silicon film pattern formed by the etching as an etching mask. A method of manufacturing a semiconductor device, comprising: a step of collectively etching the silicon organic film and the insulating film containing the silicon atoms; and (h) a step of removing the silicon organic film.

According to the present invention (claim 4), in the above-mentioned method for manufacturing a semiconductor device (claim 3), the silicon organic film is coated with a solution obtained by dissolving a compound having a siloxane bond in an organic solvent. Thereafter, it is formed by baking.

According to a fifth aspect of the present invention, in the above-described method of manufacturing a semiconductor device (the third aspect), the silicon organic film is obtained by dissolving a compound having a Si—Si bond in a main chain in an organic solvent. The solution is formed by applying a coated solution, baking, and heating or irradiating with an energy beam in an atmosphere in which oxygen is present.

According to the present invention, in the method of manufacturing a semiconductor device described above (claims 1 to 5), the thickness of the silicon organic film is 10 to 5000 nm.

According to the present invention, in the method of manufacturing a semiconductor device described above (claims 1 to 5), the silicon film is made of amorphous silicon or polysilicon.

According to the present invention, in the above-described semiconductor device manufacturing method (claims 1 to 5), the thickness of the silicon film is
It is characterized by being 10 to 5000 nm.

According to the present invention, in the above-described method for manufacturing a semiconductor device (claims 1 to 5), the removal of the silicon organic film is performed using a solvent.

The present invention (claim 6) provides (a) a step of forming a first silicon organic film containing a compound having a siloxane bond on an insulating film containing silicon atoms, and (b) the silicon organic film. Forming a second silicon organic film including a compound having a Si-Si bond in a main chain thereon;
(C) forming a photosensitive resin film on the second silicon organic film, and (d) performing pattern exposure on the photosensitive resin film to form a resist pattern;
(E) etching the second silicon organic film using the resist pattern as an etching mask; and (g) etching the second silicon organic film.
Using the pattern of the silicon organic film as an etching mask to collectively etch the first silicon organic film and the insulating film containing silicon atoms;
(H) a step of removing the first silicon organic film.

According to the present invention (claim 7), in the above-described method for manufacturing a semiconductor device (claim 6), the first silicon organic film is obtained by dissolving a compound having a siloxane bond in an organic solvent. Is formed by applying and then baking.

According to the present invention (claim 8), in the above-mentioned method of manufacturing a semiconductor device (claim 6), the first silicon organic film is formed by dissolving a compound having a Si-Si bond in a main chain in an organic solvent. The solution is formed by applying the solution obtained by the above, baking, and heating or irradiating with ultraviolet light in an atmosphere in which oxygen is present.

According to the present invention, in the above-described method for manufacturing a semiconductor device (claims 1 to 8), the removal of the silicon organic film is performed using a solvent.

According to the present invention (claim 9), in the above-described method for manufacturing a semiconductor device (claims 1, 5, 6, and 8), the compound having a Si—Si bond in the main chain is polysilane or polysilene. It is characterized by the following.

According to a tenth aspect of the present invention, in the above-described method for manufacturing a semiconductor device (the first, third, or sixth aspect), the step (e) or (g) is performed by reactive plasma etching or magnetron reactive plasma. The etching is performed by etching, electron beam plasma etching, TCP etching, ICP etching, or ECR plasma etching.

According to the present invention (claim 11), in the above-described method for manufacturing a semiconductor device (claims 2, 3, and 6), the insulating film containing silicon atoms may be a silicon oxide film, a silicon nitride film, or a silicon oxynitride film. It is a film or a spin-on-glass film.

According to the present invention, in the method of manufacturing a semiconductor device described above (claims 1, 3, and 6), the pattern exposure in the step (d) includes at least an exposure step using an electron beam.

The present invention (claim 12) provides (a) a step of forming a silicon organic film containing a compound having a Si-Si bond in a main chain on a film to be processed; and (b) a step of forming a silicon organic film on the silicon organic film. Forming a photosensitive resin film, and (c) performing pattern exposure on the photosensitive resin film to form a resist pattern, wherein the silicon organic film is
A pattern forming method is provided in which a film is formed by applying a solution containing at least a compound having a Si—Si bond in the main chain and a solvent containing no unsaturated bond.

According to the present invention (claim 13), there is provided the above-mentioned pattern forming method (claim 12), wherein the main chain comprises Si-S
The compound having an i-bond is a compound in which hydrogen is bonded to silicon of the main chain.

Hereinafter, the method for manufacturing a semiconductor device of the present invention will be described in more detail.

First, a method for manufacturing a semiconductor device according to the first embodiment of the present invention will be described with reference to FIGS.

As shown in FIG. 1A, a film 2 to be processed (for example, a conductive film 2 formed on a silicon substrate 1) is
A silicon organic film 3, a silicon film 4, and a photosensitive resin film 5, each containing a compound having a Si-Si bond in the main chain, are sequentially formed. Hereinafter, each material and a film forming method will be described.

As the film to be processed, a silicon substrate, a conductive film formed of a wiring material and an electrode material formed on the silicon substrate, an insulating film of an organic material such as polyimide, SOG, or a blank mask material Can be used.

First, a silicon organic film 3 containing a compound having a Si--Si bond in the main chain is formed as a lower resist on the film to be processed 2 by the following procedure. That is, a compound having a Si-Si bond in the main chain is dissolved in an organic solvent to prepare a solution material. Examples of the compound having a Si—Si bond in the main chain include the following chemical formulas 1-1 to 1-19 and 2-
Examples thereof include polysilane and polysilene shown in 1-2-1-13. Note that n and m in these chemical formulas
Represents a positive integer. The molecular weight of these compounds is not particularly limited, but is preferably 200 to 100, 10
0, more preferably 500 to 30,000.

[0035]

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[0036]

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[0037]

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[0038]

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The compound is not limited to one kind, and several kinds of compounds may be mixed. If necessary, a thermal polymerization inhibitor may be added to improve storage stability, and an adhesion improver may be added to improve adhesion of a substrate or the like. The organic solvent is not particularly limited as long as it dissolves the compound.Examples include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and cellosolves such as methyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate. Solvents, polar solvents such as ester solvents such as butyl acetate and isoamyl acetate, ether solvents such as anisole, and non-polar solvents such as toluene, xylene, naphtha and cumene.

More preferably, the solvent containing no unsaturated bond is, for example, anisole, toluene, xylene, naphtha,
Cumene and the like are preferred. The reason is that the unsaturated bond is
Reacts with a compound having an i-Si bond in the main chain, oxygen in the solvent is bonded to silicon, and an oxidation reaction proceeds. Especially,
As the compound, for example, the above-mentioned chemical formulas 2-1 to 2-9
When a compound in which hydrogen is bonded to silicon in the main chain shown in (1) is used, oxidation is likely to occur because the reaction between the hydrogen group and the unsaturated bond contained in the solvent is high. Therefore, by using a solvent containing no unsaturated bond as a solvent, the progress of oxidation in a solution can be suppressed.

A solution material is prepared by the above-described method, applied to the film to be processed 2 by a spin coating method, and then baked to evaporate a solvent, thereby forming a silicon organic film 3.
The thickness of the silicon organic film 3 is preferably about 10 to 5000 nm.

Next, a silicon film 4 is formed on the silicon organic film 3 as an intermediate layer. The thickness of the silicon film 4 is 1
It is preferably about 0 to 5000 nm. The silicon film 4 includes, in addition to amorphous silicon and polysilicon, n-type polysilicon and p-type polysilicon in which these silicon films are doped with P, B, and As.

Next, a photosensitive resin film 5 is used as an upper resist.
Is formed on a silicon film. As the type of the photosensitive resin film 5, if it is a composition that can be patterned by an energy beam such as visible light, ultraviolet light, X-ray, and electron beam,
There is no particular limitation. The thickness of the photosensitive resin film 5 is preferably 10 to 5000 nm, more preferably 50 to 100 nm.
0 nm is preferable, but it is better to be as thin as possible in order to improve the resolution, focus latitude, or exposure latitude during exposure.

These photosensitive resin films can be used according to the purpose.
A positive type or a negative type can be selected and used.
Specifically, as the positive resist, for example, a resist (IX-770, manufactured by Nippon Synthetic Rubber Co., Ltd.) comprising naphthoquinonediazide and a novolak resin, a polyvinylphenol resin protected with t-BOC and an onium salt Chemically amplified resists (APEX-E, manufactured by Shipley Co., Ltd.) and the like. As the negative resist, for example, a chemically amplified resist (XP-89) composed of polyvinyl phenol, a melamine resin, and a photoacid generator is used.
131, manufactured by Shipley Co., Ltd.), a resist (RD-2000) comprising a polybirylphenol and a bisazide compound
D, manufactured by Hitachi Chemical Co., Ltd.), but are not limited thereto.

By the standing wave generated in the resist film 5,
In order to prevent the dimensional controllability of the resist pattern 5a from deteriorating, coumarin absorbing ultraviolet light is contained in the photosensitive resin.
The transparency of the resist film 5 may be reduced by adding a dye such as curcumin. Alternatively, a standing wave generated in the resist film may be suppressed by forming an upper antireflection film on the resist film 5 and reducing light reflection at an interface between the resist film and air. Examples of such an upper antireflection film include Aquatar manufactured by Hoechst and the like.

As shown in FIG. 1B, the photosensitive resin film 5
Is patterned to form a resist pattern 5a. An energy beam such as visible light or ultraviolet light as exposure light is applied to the photosensitive resin film 5 through a mask having a desired pattern.
Irradiation. As a light source for irradiating the exposure light, a mercury lamp, XeF (wavelength = 351 nm), XeCl
(Wavelength = 308 nm), KrF (wavelength = 248 nm),
KrCl (wavelength = 222 nm), ArF (wavelength = 193)
nm) and F2 (wavelength = 151 nm). Note that X-rays or an electron beam may be used as the exposure light.

The exposed photosensitive resin film 5 is developed using an organic alkali aqueous solution such as tetramethylammonium hydroxide or choline, an inorganic alkali aqueous solution such as sodium hydroxide or potassium hydroxide, or an organic solvent such as xylene or acetone. Is performed to form a resist pattern 5a.

As shown in FIG. 1C, the silicon film 4 is formed using the resist pattern 5a as an etching mask.
And the silicon organic film 3 are collectively etched.

As an etching apparatus, for example, a reactive plasma etching system, a magnetron reactive plasma etching system, an electron beam plasma etching system,
An etching apparatus such as a TCP etching method, an ICP etching method, or an ECR plasma etching method can be used.

As the source gas, SF ₆ , NF ₃ , F
₂ , CF ₄ , CF ₃ Cl, CF ₂ Cl ₂ , CF ₃ Br,
CCl ₄ , C ₂ F ₅ Cl ₂ , C ₂ F ₆ , CHF ₃ , Si
At least one of halogen-based gases such as F ₄ , Br ₂ , I ₂ , SF ₄ , HBr, HI, and Cl ₂ , or a gas system obtained by adding Ar, N ₂ , and H ₂ to these gas systems. be able to. By using these source gases as an etchant, the etching of the silicon film 4 and the silicon organic film 3 can be performed collectively.

By using these etchants, the etching selectivity of the silicon film 4 and the silicon organic film 3 with respect to the resist can be increased, and the etching of the silicon film 4 and the silicon organic film 3 can be performed with good dimensional control. Can do it. This is because these etchants are unlikely to react with atoms contained in the resist film and generate volatile products, whereas the silicon contained in the silicon film 4 and the silicon organic film 3 undergoes a chemical reaction. , Volatile products are generated and volatilized. In particular, it is preferable to use a source gas containing Cl ₂ or HBr, and by using these source gases, the silicon film 4 and the silicon organic film 3 can be etched with a high selectivity. As a result, the processed film 2
Silicon film 4 having a film thickness necessary for etching silicon
The silicon organic film 3 can be etched with the resist pattern 5a having a small thickness.

As shown in FIG. 2A, the film 2 to be processed is etched using the silicon organic film pattern 3a and the silicon film pattern 4a formed by the above method as an etching mask.

After the etching of the film to be processed 2 is completed, the silicon organic film pattern 3a is peeled off with an organic solvent. Even when the silicon film pattern 4a or the resist pattern 5a remains on the silicon organic film pattern 3a, by dissolving and removing the lower silicon organic film pattern 3a,
They can be peeled off together (FIG. 2 (b)).

Organic solvents that can be used for peeling the silicon organic film include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;
Methyl cellosolve, methyl cellosolve acetate, cellosolve solvents such as ethyl cellosolve acetate, ethyl solvents, ester solvents such as butyl acetate, isoamyl acetate, polar solvents such as ether solvents such as anisole, toluene, xylene, naphtha, cumene, etc. Non-polar solvents are mentioned.

When the silicon organic film is acidic,
It can be dissolved and removed with an alkaline solution such as an aqueous solution of an organic alkali such as tetramethylammonium hydroxide or choline or an aqueous solution of an inorganic alkali such as potassium hydroxide. In addition, the silicon organic film is irradiated with a high energy beam to change the Si-Si bond in the main chain into a siloxane bond, and is then hydrofluoric acid, buffered hydrofluoric acid, or a polar solvent such as acetone, methanol, ethanol, or isopropanol. It may be dissolved and removed.

In the method of the present invention, the organic silicon film used as the lower layer resist is an organic polymer similar to a resin film such as a novolak resin conventionally used as the lower layer resist of a three-layer resist. It is possible to selectively peel off the film to be processed by the organic solvent.

As described above, since the intermediate layer and the lower layer resist can be collectively etched, the number of etching steps required until the processing of the film to be processed can be reduced. As a result, not only the process cost is reduced, but also the dimensional conversion difference generated for each etching can be reduced, and the film to be processed can be etched with a desired dimension.

In the method of manufacturing a semiconductor device according to the second aspect of the present invention, an insulating film containing silicon atoms is used as a film to be processed, and each step is the same as in the first aspect. . In addition, as the insulating film containing silicon atoms,
A silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a spin-on-glass film can be used.

Here, a method for etching a silicon oxide film will be described. As an etching apparatus, for example,
Reactive plasma etching, magnetron reactive plasma etching, electron beam plasma etching, TCP etching, ICP etching,
Alternatively, an etching apparatus such as an ECR plasma etching method can be used.

The source gas is not particularly limited as long as it can provide an etching selectivity of the silicon oxide film with respect to the silicon film and the silicon organic film.
F ₆ , NF ₃ , CF ₄ , C ₄ F ₈ , CHF ₃ , C
₂ F _6, C ₃ F ₈ or the like at least one in the gas system containing fluorine, or Ar to these gas system, N _2, H _2, C
A gas system to which O and O ₂ are added can be given.

When etching is performed using these source gases, a polymer film is deposited on the surfaces of the silicon film and the silicon organic film, but is hardly deposited on the surface of the insulating film. It is easier to etch than an organic film.

As a result, by using these source gases for etching the silicon oxide film, a high selectivity required for processing the silicon oxide film can be easily obtained, the dimensional controllability is improved, and the etching of the silicon oxide film is performed. Can be performed. At this time, when a polymer film is remarkably deposited on the surface of the silicon film or the silicon organic film and the etching shape is deteriorated, for example, the polymer film is formed by adding argon or oxygen to the source gas. Removal is preferred.

The case where the film to be processed is a silicon oxide film has been described above. However, even in the case of a silicon nitride film, a silicon oxynitride film, and a spin-on-glass film, as in the case of the silicon oxide film, a silicon film and a silicon organic film are used. Can be increased.

Next, the silicon organic film can be peeled off in the same manner as in the method according to the first embodiment. At this time, even if the silicon film and the resist pattern remain on the silicon organic film, the silicon organic film is dissolved and removed,
Can be peeled together.

Next, a method of manufacturing a semiconductor device according to the third embodiment of the present invention will be described with reference to FIGS.

A silicon organic film 13 containing a compound having a siloxane bond is formed as a lower resist on an insulating film 12 containing silicon atoms, which is a film to be processed, formed on a wafer substrate 11, for example, a silicon oxide film or a silicon nitride film. Form. The thickness of the silicon organic film 13 is not particularly limited, but is preferably 10 to 5000 nm. The silicon organic film 13 can be formed by the following two methods 1) and 2).

1) A compound having a siloxane bond is dissolved in an organic solvent to prepare a solution material. As the compound having a siloxane bond in the main chain, for example, the following formulas 3-1 to 3-1
-24 can be mentioned. N in these chemical formulas is a positive integer. The molecular weight of these compounds is not particularly limited, but is preferably 200 to
100,000, particularly preferably 500 to 30,000
Is good. The compound is not limited to one kind, and several kinds of compounds may be mixed. If necessary, a thermal polymerization inhibitor may be added to improve storage stability, and an adhesion improver may be added to improve adhesion of a substrate or the like.

[0068]

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[0069]

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[0070]

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The organic solvent is not particularly limited as long as it can dissolve the compound, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and siloxane hexamethyl, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate and the like. And non-polar solvents such as toluene, xylene, naphtha, cumene and the like, and ester solvents such as ethyl acetate, butyl acetate and isoamyl acetate, ether solvents such as anisole and the like.

A silicon organic film can be formed by preparing a solution material by the above method, applying the solution material on a film to be processed by a spin coating method, and baking and evaporating a solvent.

2) A compound having a Si--Si bond in the main chain is dissolved in an organic solvent to prepare a solution material. Si-Si
As the compound having a bond in the main chain, for example, the following formula 4-
Examples thereof include polysilanes and polysilenes shown in 1 to 4-9. The molecular weight of these compounds is not particularly limited, but is preferably from 200 to 100,000, particularly preferably from 500 to 30,000. The compounds are not limited to one kind, and several kinds of compounds may be mixed. If necessary, a thermal polymerization inhibitor may be added to improve storage stability, and an adhesion improver may be added to improve adhesion of a substrate or the like.

The organic solvent is not particularly limited as long as it can dissolve the compound. Examples thereof include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate and the like. Cellosolve solvents, polar solvents such as ethyl acetate, butyl acetate, ester solvents such as isoamyl acetate, toluene,
Non-polar solvents such as xylene.

A solution material is prepared by the above-described method, and the solution material is applied on a film to be processed by a spin coating method, and then baked to evaporate a solvent, thereby forming a silicon organic film 13. Then, in an atmosphere where oxygen is present, 5
Baking is performed at a temperature in the range of 0 ° C. to 1000 ° C. or irradiation with a high energy beam in an atmosphere where oxygen is present to oxidize the bond between silicon and silicon,
A siloxane bond can be formed. High energy beams include ultraviolet light, electron beam, ion beam,
X-rays can be mentioned.

The silicon organic film 13 formed as described above
Is preferably about 10 to 5000 nm.

Next, a silicon film 14 is formed on the silicon organic film 13 as an intermediate layer. The thickness of the silicon film 14 is preferably about 10 to 5000 nm. Silicon film 1
Reference numeral 4 denotes amorphous silicon and polysilicon, and n in which P, B, and As are doped into these silicon films.
Type polysilicon and p-type polysilicon are also included.

Next, a photosensitive resin film 15 is formed on the silicon film 14 as an upper layer resist (FIG. 3A). Types of the photosensitive resin film 15 include visible light, ultraviolet light, X
The composition is not particularly limited as long as it is a composition that can be patterned by an energy beam such as a line or an electron beam. The thickness of the photosensitive resin film 15 is 10 to 5,000 nm, and more preferably 5 to 5 nm.
The thickness is preferably from 0 to 1000 nm, but is preferably as thin as possible in order to improve the resolution, focus latitude, or exposure latitude during exposure. Also, these photosensitive resin films are
Depending on the purpose, a positive type or a negative type can be selected and used.

Specific examples of the photosensitive resin include positive resists such as a resist (IX-770, manufactured by Nippon Synthetic Rubber Co., Ltd.) comprising naphthoquinonediazide and a novolak resin, and a polyvinyl resin protected by t-BOC. Chemically amplified resist composed of phenol resin and onium salt (A
PEX-E, manufactured by Shipley Co., Ltd.). As the negative resist, for example, a chemically amplified resist (XP-89131, manufactured by Shipley) comprising polyvinylphenol, a melamine resin, and a photoacid generator,
A resist (RD-2000D, manufactured by Hitachi Chemical Co., Ltd.) comprising a polybirylphenol and a bisazide compound is exemplified. However, it is not limited to these.

In order to prevent the dimensional controllability of the resist pattern from deteriorating due to the standing wave generated in the resist film,
The transparency of the resist film may be reduced by adding a dye such as kliman or curcumin which absorbs ultraviolet light to the photosensitive resin film. Alternatively, a standing wave generated in the resist film may be suppressed by forming an upper antireflection film on the resist film and reducing light reflection at an interface between the resist film and air. Examples of such an upper antireflection film include Aquatar manufactured by Hoechst and the like.

Next, the resist is irradiated with an energy beam such as visible light or ultraviolet light as exposure light through a mask having a desired pattern. As a light source for irradiating exposure light, a mercury lamp, XeF (wavelength = 351 n)
m), XeCl (wavelength = 308 nm), KrF (wavelength =
248 nm), KrCl (wavelength = 222 nm), ArF
(Wavelength = 193 nm) and excimer lasers such as F2 (wavelength = 151 nm). The exposure light is not limited to a laser, but may be an X-ray or an electron beam.

After exposure, the resist is made of an aqueous solution of an organic alkali such as tetramethylammonium hydroxide or choline,
Development processing is performed using an aqueous solution of an inorganic alkali such as sodium hydroxide or potassium hydroxide or an organic solvent such as xylene or acetone to form a resist pattern 15a (FIG. 3B).

Next, the silicon film 14 is etched using the resist pattern 15a as an etching mask (FIG. 3C). As an etching apparatus, for example,
Reactive plasma etching, magnetron reactive plasma etching, electron beam plasma etching, TCP etching, ICP etching,
Alternatively, an etching apparatus such as an ECR plasma etching method can be used.

As the source gas, SF ₆ , NF ₃ , F
₂ , CF ₄ , CF ₃ Cl, CF ₂ Cl ₂ , CF ₃ Br,
CCl ₄ , C ₂ F ₅ Cl ₂ , C ₂ F ₆ , CHF ₃ , Si
At least one of halogen-based gases such as F ₄ , Br ₂ , I ₂ , SF ₄ , HBr, HI, and Cl ₂ , or a gas system obtained by adding Ar, N ₂ , and H ₂ to these gas systems. be able to.

By using these source gases as an etchant, the etching selectivity of the silicon film 14 with respect to the resist can be increased, and the silicon film 14 can be etched with good dimensional control.
This is because these etchants are less likely to react with the atoms contained in the resist to produce volatile products, whereas they undergo a chemical reaction with the silicon contained in the silicon film 14 and the volatile products It is generated and volatilized.

In particular, it is preferable to use a source gas containing Cl ₂ or HBr, and by using these source gases, the silicon film can be etched with a high selectivity. As a result, when etching an insulating film such as a spin-on-glass, a silicon oxide film, or a silicon nitride film, the silicon film 14 having a thickness necessary to function as an etching mask is replaced with a thin resist pattern 15a. Etching can be performed using the mask.

The resist pattern 1 formed by the above method
The silicon organic film 13 and the silicon oxide film 12 are collectively etched using the 5a and the silicon film pattern 14a as an etching mask (FIG. 4A). As the etching apparatus, for example, an etching apparatus such as a reactive plasma etching method, a magnetron reactive plasma etching method, an electron beam plasma etching method, a TCR etching method, an ICP etching method, or an ECR plasma etching method can be used.

The source gas is not particularly limited as long as the etching selectivity of the silicon organic film 13 and the silicon oxide film 12 with respect to the silicon film 14 can be obtained. For example, SF ₆ , NF ₃ , CF ₄ , C ₄ F ₈ , CHF
₃ , C ₂ F ₆ , C ₃ F _8, etc., at least one of fluorine-containing gas systems, or these gas systems include Ar, N ₂ , H
₂ , a gas system to which CO and O ₂ are added.

When etching is performed using these source gases, a polymer film is deposited on the surfaces of the silicon film and the silicon organic film, but is hardly deposited on the surface of the insulating film. It is easier to etch than an organic film.

As a result, by using these source gases for etching the silicon organic film and the silicon oxide film, a high selectivity required for processing the silicon organic film and the silicon oxide film can be easily obtained, and the dimensional control can be performed. The silicon organic film and the silicon oxide film can be collectively etched with good efficiency. At this time, when a polymer film is remarkably deposited on the surface of the resist or the silicon film and the etching shape is deteriorated, the polymer film is removed by, for example, adding argon or oxygen to the source gas. Is preferred.

The case where the film to be processed is a silicon oxide film has been described above. However, when the film to be processed is a silicon nitride film, an oxynitride film, or a spin-on-glass film, etching is performed with a high selectivity using the silicon film as an etching mask. Can do it.

Next, the silicon organic film 13 is peeled off with a solvent. Since the silicon organic film used in the present invention contains a siloxane bond, when the silicon organic film is acidic, an alkaline solution such as an aqueous solution of an organic alkali such as tetramethylammonium hydroxide or choline or an aqueous solution of an inorganic alkali such as potassium hydroxide is used. Can be dissolved and removed. In addition, the silicon organic film is irradiated with a high energy beam to change the main chain Si-Si bond into a siloxane bond,
It may be dissolved and removed with hydrofluoric acid, buffered hydrofluoric acid, or a polar solvent such as acetone, methanol, ethanol, or isopropanol.

At this time, even if a resist pattern, a silicon film, or the like remains on the silicon organic film, the silicon organic film as a lower layer is dissolved and removed, so that the silicon organic film can be simultaneously removed.

As described above, according to the third aspect of the present invention, when the film to be processed is silicon oxide or silicon nitride, the silicon oxide film (silicon nitride film) is etched with respect to the etching mask including the intermediate layer and the lower resist. It is possible to increase the selectivity. As a result, the silicon oxide film (silicon nitride film) can be etched with good dimensional controllability without the etching mask receding during the etching of the silicon oxide film (silicon nitride film).

The method of manufacturing a semiconductor device according to the fourth aspect of the present invention is directed to a method of manufacturing a semiconductor device according to the first aspect, in which the silicon organic film (comprising the compound having a Si—Si bond in the main chain) used in the first aspect is used instead of the silicon film. 2 silicon organic film). In this case, the etching of the second silicon organic film performed using the resist pattern as a mask is performed in the first silicon organic film.
To the third embodiment.

[0096]

Embodiment 1 8 g of polysilane having an average molecular weight of 8000 represented by the above formula 2-2 was dissolved in 92 g of anisole to prepare a solution material for a lower resist. A solution material of a lower resist is applied on a 300 nm thick tungsten film 2 formed on a silicon wafer 1 by a spin coating method.
Baking was performed at 90 ° C. for 90 seconds to form a lower resist film 3. At this time, the thickness of the lower resist 3 is 300 nm. Subsequently, an amorphous silicon film 4 having a thickness of 200 nm is formed as an intermediate layer on the lower resist film 3 by LPCVD.
The film was formed by the method.

Next, a positive chemically amplified resist APEX-E manufactured by Shipley was applied onto the intermediate layer 4 and baked at 98 ° C. for 120 seconds to form an upper resist film 5 (FIG. 1A). At this time, the thickness of the upper resist film 5 is 200 nm. Next, pattern exposure was performed using a reduction optical stepper using a KrF excimer laser beam as a light source (exposure amount: 30 mJ / cm 2).
After baking for 0 second, TMA of 0.21 regulation
Development was performed with an H developer to form a 0.18 μm L / S pattern 5a (FIG. 1B).

The thickness of the resist pattern 5a is 180 nm.
It is. When the cross section of the resist pattern 5 was observed by SEM, it was confirmed that the pattern was formed in a good shape as shown in FIG.

The resist pattern 5 formed as described above
Is used as an etching mask and a magnetron type RIE
The intermediate film 4 and the lower resist 3 were collectively etched by the apparatus (FIG. 1C). Flow rate 20 as source gas
Using SCCM Cl ₂ , excitation power 300W, degree of vacuum 3
When the etching was performed under the etching condition of 0 mTorr, the intermediate layer 4 and the lower layer resist 3 could be etched at a time without the resist pattern 5a being cut off halfway.

The width a of the resist pattern 5a and the width b of the lower resist pattern 3a are measured by a cross-sectional SEM to obtain a dimensional conversion difference (= pattern width b of the lower resist 3) caused by the etching of the intermediate layer 4 and the lower resist 3. -The resist pattern width a) was found to be 10 nm. After the etching is completed, the remaining resist pattern 5a has a thickness of 130 nm.

Further, using the intermediate layer pattern 4a and the lower resist pattern 3a as an etching mask, the tungsten film 2 was etched using a magnetron reactive ion etching apparatus (FIG. 2A). CCl _{4 at} a flow rate of 30 SCCM and a flow rate of 20 SC as a source gas
Using O ₂ of CM, excitation power 350W, vacuum degree 15mT
When etching was performed under the etching conditions of orr,
The tungsten film 2 could be etched without the intermediate layer pattern 4a and the lower resist pattern 3a being cut off halfway. At this time, the tungsten film 2
Is vertically etched with good anisotropy. The width a of the resist pattern 5a before etching and the pattern width c of the tungsten film 2a after processing are measured by a cross section SEM to obtain the intermediate layer 4, the lower resist 3 And processed film 2
Conversion difference (tungsten film 2a)
Of the pattern width c−resist pattern width a) was 15 nm, which was within the allowable range (target processing dimension 180).
(within 10% of nm).

Next, the wafer substrate 1 was placed in ethyl lactate for 18 hours.
After permeating for 0 second, the surface of the wafer was washed with pure water to dissolve and remove the polysilane pattern 3a attached on the tungsten film 2a. At this time, the underlying polysilane pattern 3a
Was dissolved and removed, so that the silicon pattern 4a and the resist pattern 5a could be simultaneously removed (FIG. 2).
(B)). After the peeling, the thickness of the tungsten film 2a was measured. As a result, it was 300 nm, and it was found that the tungsten film 2a was not reduced in thickness.

Also, the silicon wafer portion located immediately below the tungsten opening was not dissolved, and the resist pattern, the silicon pattern, and the lower resist pattern could be selectively removed from the tungsten and the silicon wafer.

Comparative Example 1 As in Example 1, a 300 nm-thick tungsten film 22 formed on a silicon wafer 21 was
A solution material obtained by dissolving 10 g of Novolak resin No. 00 in 90 g of ethyl lactate was applied and baked at 220 ° C. for 180 seconds to form a lower resist film 23. The thickness of the lower resist film 23 after baking is 300 nm.
Next, a film thickness of 200 as an intermediate layer is formed on the lower resist 23.
An SiO ₂ film 24 of nm thickness was formed by the LPCVD method (FIG. 5).
(A)). Then, a resist pattern 25a was formed on the SiO ₂ film 24 in the same manner as in Example 1. FIG. 5 shows a cross-sectional SEM observation of the resist pattern 25a.
As shown in (b), it was found that patterning was performed in a good shape.

The resist pattern 2 formed as described above
The intermediate film was etched using 5a as an etching mask (FIG. 5C). As the etching apparatus, a magnetron type RIE apparatus was used, Cl ₂ at a flow rate of 20 SCCM was used as a source gas, and an excitation power of 300 was used.
The etching was performed under the etching conditions of W and a degree of vacuum of 30 mTorr. The resist pattern width g and the pattern width h of the intermediate layer were measured with a cross-sectional SEM, and the dimensional conversion difference (pattern width h of intermediate layer−resist pattern width g) generated by etching of the intermediate layer was found to be 15 nm. Do you get it.

Next, the lower resist 23 was etched using the intermediate layer pattern 24a as an etching mask (FIG. 6A). A magnetron type RIE apparatus was used as an etching apparatus, and a flow rate of 20 was used as a source gas.
Excitation power 300W, degree of vacuum 30 using O ₂ of SCCM
The etching was performed under the etching conditions of mTorr. The width d of the resist pattern and the width e of the pattern of the lower resist are measured by a cross section SEM, and the intermediate layer 24 and the lower resist 2 are measured.
When the dimensional conversion difference caused by the etching of No. 3 was obtained,
It was found to be 5 nm.

Next, using the intermediate layer pattern 24a and the lower resist pattern 23a as an etching mask, the tungsten film 22 was etched using a magnetron type reactive ion etching apparatus (FIG. 6).
(B)). CCl with a flow rate of 30 SCCM as a source gas
₄ and 20 SCCM of O ₂ , excitation power 35
When etching was performed under the etching conditions of 0 W and a degree of vacuum of 15 mTorr, the tungsten film 22 could be etched without the intermediate layer pattern 24a and the lower resist pattern 23a being cut off in the middle.

The pattern width d of the resist pattern 25a and the pattern width f of the tungsten film were measured by cross section SEM.
Intermediate layer 24, lower layer resist 23, and tungsten film 22
The dimensional conversion difference (pattern width f of tungsten film 22a-resist pattern width d) caused by the etching of a was found to be 35 nm, which was an allowable range (target processing dimension 1).
(10% of 80 nm).

Finally, the lower resist pattern 23a was removed to obtain a tungsten pattern 22a (FIG. 6C).

From the comparison between Example 1 and Comparative Example 1, the method of the present invention makes it possible to reduce the number of etching steps of the three-layer resist method by one. It can be seen that the dimensional conversion difference generated at the time of etching can be reduced, and the film to be processed can be processed to a desired size.

Comparative Example 2 Polysilane 8 having an average molecular weight of 800 shown in the above formula 2-2.
g was dissolved in 92 g of anisole to prepare a solution material for the lower resist. Tungsten film 22 formed in Example 1
After a solution material for the lower layer resist was applied thereon by spin coating, baking was performed at 80 ° C. for 90 seconds.
At this time, the thickness of the lower resist 26 is 300 nm.
Then, a resist pattern 27 was formed on the lower resist 26 in the same manner as in Example 1.

The cross-sectional shape of the resist pattern 27 was
Observation revealed that a resist residue was left as shown in FIG. This is because the silicon organic film and the resist reacted. As described above, the silicon organic film and the resist cause a reaction, and a normal resist profile may not be obtained.However, by interposing the silicon film between the silicon organic film and the resist, the resist and the silicon organic film can be separated. Can be prevented, and a good resist profile can be obtained.

Example 2 Polysilane 8 having an average molecular weight of 8000 represented by the above formula 1-1
g was dissolved in 92 g of toluene to prepare a solution material for the lower resist. Film thickness 5 formed on silicon wafer 1
After applying a solution material for the lower resist by spin coating on the 00 nm TEOS oxide film 2,
Baking was performed for 0 seconds. At this time, the thickness of the lower resist 3 is 100 nm. Subsequently, 100 nm-thick polysilicon is formed on the lower resist 3 as an intermediate layer 4 by LPC.
The film was formed by the VD method. Then, a negative chemically amplified resist TDUR-N009 manufactured by Tokyo Ohka Kogyo Co., Ltd. was applied on the intermediate layer 4 and baked at 98 ° C. for 120 seconds (FIG. 1).
(A)). At this time, the thickness of the resist 5 is 150 nm.

Next, pattern exposure was performed using a reduction optical stepper using KrF excimer laser light as a light source (exposure amount: 30 mJ / cm 2), baking was performed at 98 ° C. for 120 seconds, and then 0.27 normalization was performed. A development process was performed with a TMAH developer to form a resist pattern 5a of 0.18 μmL / S. The thickness of the resist pattern 5a is 13
0 nm. When the cross section of the resist pattern 5a was observed by SEM, it was confirmed that the pattern was formed in a good shape as shown in FIG.

Using the resist pattern formed as described above as an etching mask, a magnetron type RIE
The intermediate film 4 and the lower resist 3 were etched by the apparatus (FIG. 1C). Flow rate 20SC as source gas
Using HBr of CM, excitation power 300W, degree of vacuum 30m
When the etching was performed under Torr etching conditions, the intermediate layer 4 and the lower layer resist 3 could be etched at a time without the resist pattern 5a being cut off halfway (FIG. 1 (c)).

As shown in FIG. 1C, the processed shapes of the intermediate layer pattern 4a and the lower resist pattern 3a are vertically etched with good anisotropy, and the resist pattern width a and the pattern width of the lower resist pattern 4a are obtained. b is section S
The dimensional conversion difference caused by the etching of the intermediate layer 4 and the lower layer resist 3 was determined by measuring with EM.
It was found to be 10 nm. After the etching, the thickness of the remaining resist is 100 nm.

Further, using the intermediate layer pattern 4a and the lower layer resist pattern 3a as an etching mask, TEOS is performed by a magnetron type reactive ion etching apparatus.
The oxide film was etched (FIG. 2A). C ₄ F _{8 with} a flow rate of 30 SCCM and a flow rate of 30 SCC as source gas
When etching was performed under the etching conditions of M CO, Ar at a flow rate of 160 SCCM, and an excitation power of 350 W and a degree of vacuum of 15 mTorr, the intermediate layer pattern 4 a and the lower resist pattern 3 a were not cut off in the middle without being removed.
The etching of the TEOS oxide film 2 could be performed.
At this time, the TEOS oxide film 2 is vertically etched with good anisotropy, and the resist pattern width a and the processed T
By measuring the pattern width c of the EOS oxide film 2a with a cross-sectional SEM, the intermediate layer 4, the lower resist 3, and the TEO
When the dimensional conversion difference caused by the etching of the S oxide film 2 was obtained, it was found to be 15 nm, which was within the allowable range (target processing dimension 180).
(within 10% of nm).

Next, after penetrating the anisole for 180 seconds, the surface of the wafer 1 was washed with pure water to dissolve and remove the lower resist pattern 3a on the TEOS oxide film pattern 2a. At this time, the silicon film 4 and the resist pattern 5a were also removed at the same time because the lower resist pattern 3a as a base was dissolved and removed (FIG. 2B). After the lower resist pattern 3a was peeled off, the film thickness of the TEOS oxide film pattern 2a was measured to be 500 nm, and it was found that the TEOS oxide film pattern 2a was not dissolved and the film was not reduced.

The silicon wafer portion immediately below the opening of the TEOS oxide film pattern 2a is not dissolved, and the resist pattern, the silicon pattern, and the lower resist pattern are selectively peeled off from the TEOS oxide film pattern and the silicon wafer. We were able to.

COMPARATIVE EXAMPLE 3 A TEOS oxide film 32 formed on a silicon substrate 31 in the same manner as in Example 3 was coated on a silicon substrate 31 with a film thickness of 2 by LPCVD.
A 00 nm polysilicon film 33 was formed. Next, a resist 3 is formed on the polysilicon film 33 in the same manner as in the first embodiment.
4 (FIG. 8A), and then 0.18 μmL / S
The resist pattern 34a was formed (FIG. 8B).
Further, using the resist pattern 34a as an etching mask, the polysilicon film 33 was etched using a magnetron-type reactive ion etching apparatus (FIG. 9A).

That is, a flow rate of 30 SCCM was used as the source gas.
HBr, excitation power 500W, vacuum degree 40mTo
When etching was performed under rr etching conditions,
The polysilicon film 33 could be etched without the resist pattern 34a being removed during the etching.

Subsequently, using the patterned polysilicon film 33a as a mask, the TEOS oxide film 32 was etched by a magnetron type etching apparatus. When C ₄ F _{8 at} a flow rate of 20 SCCM and Ar at a flow rate of 40 SCCM were used as the source gas and the etching was performed under the etching conditions of an excitation power of 200 W and a degree of vacuum of 40 mTorr, the polysilicon film 33 a was not removed during the etching. The TEOS oxide film 32 was processed to form a TEOS oxide film pattern 32a (FIG. 9B).

Next, the polysilicon film 33a used as an etching mask was peeled off using a chemical dry etching apparatus. 30SC flow rate as source gas
Using CM HBr, excitation power 400W, vacuum degree 30m
When etching was performed under Torr etching conditions, the polysilicon film 33a could be peeled off (FIG. 9C).

However, TEOS oxide film pattern 3
It was found that the portion A of the silicon wafer located immediately below the opening 2a was also etched. As described above, when the polysilicon film 33a is used as an etching mask, a problem arises in that a portion of the underlying film that should not be etched is removed during peeling.

Example 3 8 g of polysilane having an average molecular weight of 8000 and represented by the above formula 2-5 was dissolved in 92 g of xylene to prepare a solution material for a lower resist. After a solution material for the lower resist is applied on the 500 nm-thick SiN film 2 formed on the silicon wafer 1 by a spin coating method, the solution material is applied at 80 ° C. for 9 hours.
Baking was performed for 0 seconds. At this time, the thickness of the lower resist 3 is 200 nm. Subsequently, a phosphorus-doped polysilicon having a thickness of 100 nm was formed as an intermediate layer 4 on the lower resist 3 by an LPCVD method. Subsequently, on the intermediate layer 4, a negative chemically amplified resist XP89131 manufactured by Shipley Co., Ltd.
And baked at 98 ° C. for 120 seconds (FIG. 1A). At this time, the thickness of the resist 5 is 150 n.
m.

Next, pattern exposure was performed using a reduction optical type stepper using KrF excimer laser light as a light source (exposure amount: 30 mJ / cm ² ), baking was performed at 98 ° C. for 120 seconds, and then 0.27 N Was performed to form a resist pattern 5a of 0.18 μmL / S. The thickness of the resist pattern 5a is 130 nm. When the cross section of the resist pattern 5a was observed by SEM, it was confirmed that the pattern was formed in a good shape as shown in FIG.

The resist pattern 5 formed as described above
a as an etching mask and a magnetron type RI
The intermediate film 4 and the lower resist 3 were collectively etched by the E apparatus (FIG. 1C). Flow rate 42 as source gas
When etching was performed using CF ₄ of 0 SCCM under the etching conditions of excitation power of 300 W and a degree of vacuum of 30 mTorr, the intermediate layer 4 and the lower layer resist 3 were collectively etched without the resist pattern 5 a being removed in the middle. (FIG. 1 (c)).

As shown in FIG. 1C, the processing shapes of the intermediate layer pattern 4a and the lower resist pattern 3a are vertically etched with good anisotropy, and the resist pattern width a
And the pattern width b of the lower resist pattern 3a by the
M, the dimensional conversion difference caused by etching of the intermediate layer 4 and the lower layer resist 3 was found to be less than the measurement limit (5 nm) observable by cross-sectional SEM. After completion of the etching, the thickness of the remaining resist pattern 5a is 100
nm.

Further, using the intermediate layer pattern 4a and the lower resist pattern 3a as an etching mask,
The film 2 was etched using a magnetron-type reactive ion etching apparatus (FIG. 2A). CHF _{3 at} a flow rate of 30 SCCM, CO at a flow rate of 80 SCCM, Ar at a flow rate of 80 SCCM, and a flow rate of 5 SCCM as source gases
Of O ₂ , excitation power of 350 W, vacuum degree of 3 mTorr
The etching was performed under the following etching conditions. As a result, the etching of the SiN film 2 could be performed without the intermediate layer pattern 4 and the lower layer resist pattern 3 being cut off halfway.

At this time, the SiN film 2 is vertically etched with good anisotropy, and the resist pattern width a before etching and the pattern width c of the SiN film pattern 2a after processing are measured by a cross section SEM. 4. When the dimensional conversion difference caused by the etching of the lower resist 3 and the SiN film 2 was determined, the measurement limit (5n
m) or less and within an allowable range (a target processing dimension of 180 nm).
Within 10%).

Next, the wafer substrate 1 is heated at 180 ° C. for 180
After baking for 2 seconds and measuring the infrared absorption spectrum, absorption due to a siloxane bond was observed at around 1100 cm ^-1 . This is because the bake
This is because the -Si bond was oxidized. Subsequently, after immersing the wafer substrate 1 in hydrofluoric acid for 120 seconds, the wafer was washed with pure water to dissolve and remove the silicon organic film 3. At this time, the polysilicon film 4 on the silicon organic film 3 also
The iN film and the wafer substrate could be selectively peeled without dissolving.

Example 4 Film thickness of 300 n formed on silicon wafer 11
m on the TEOS oxide film 12 as spin-on glass (trade name, manufactured by Dow Corning Toray Co., Ltd.)
FOX) was applied by a spin coating method, and then baked in air at 200 ° C. for 120 seconds. At this time, the film thickness of the spin-on glass is 100 nm. Subsequently, an amorphous silicon film 14 having a thickness of 300 nm was formed as an intermediate layer on the spin-on glass 13 by a sputtering method. Then, a positive chemically amplified resist TDUR-P007 manufactured by Tokyo Ohka Kogyo Co., Ltd. is formed on the amorphous silicon film 14.
And baked at 98 ° C. for 120 seconds (FIG. 3A). At this time, the thickness of the resist is 200 nm.
It is.

Next, pattern exposure was carried out using a reduction optical stepper using KrF excimer laser light as a light source (exposure amount: 30 mJ / cm 2), baking was performed at 98 ° C. for 120 seconds, and then 0.21 normalization was performed. Development was performed with a TMAH developer to form a resist pattern 15a of 0.18 μmL / S (FIG. 3B). The thickness of this resist pattern 15a is 170 nm. When the cross section of the resist pattern 15a was observed by SEM, it was confirmed that the pattern was formed in a good shape as shown in FIG.

The resist pattern 1 formed as described above
5a as an etching mask and a magnetron type R
The amorphous silicon film 14 was etched by the IE device (FIG. 3C). That is, the flow rate 2
When etching was performed using Cl ₂ of 0 SCCM under an etching power of 300 W and a vacuum degree of 30 mTorr, the resist pattern 15 a could be etched without being removed in the middle.

After the etching is completed, the remaining resist pattern 15a has a thickness of 100 nm. By measuring the width d of the resist pattern 15a before etching and the width e of the amorphous silicon pattern 14a by a cross-sectional SEM, the dimensional conversion difference (amorphous silicon pattern width e-resist pattern width d) caused by the etching of the amorphous silicon can be calculated. As a result, it was found that the thickness was 5 nm.

Further, the amorphous silicon pattern 1
4a as an etching mask, the spin-on-glass film 13 and T
The EOS oxide film 12 was etched all at once (FIG. 4
(A)). C ₄ F with a flow rate of 30 SCCM as a source gas
_8. Excitation power of 350 using 20 SCCM flow rate Ar
When etching was performed under the etching conditions of W and a vacuum degree of 15 mTorr, the amorphous silicon pattern 14 was obtained.
The etching could be performed without a being removed during the process.

By measuring the width d of the resist pattern 15a before etching and the pattern width f of the TEOS oxide film pattern 12a after processing by a cross-sectional SEM, the amorphous silicon film 14, the spin-on-glass film 13 and the T
The dimensional conversion difference (T
When the pattern width f of the EOS oxide film pattern 12a-the width d) of the resist pattern 15a was determined, it was found that the width was 10 nm, which was within the allowable range (within 10% of the target processing dimension of 180 nm).

Next, the wafer substrate 11 was immersed in a 0.27 N TMAH developer for 120 seconds, and then the surface of the wafer 11 was washed with pure water.
3a was dissolved and removed. At this time, the silicon film 14 and the resist pattern 15a could be removed at the same time because the underlying spin-on-glass film pattern 13a was removed (FIG. 4B). After peeling, TEOS oxide film pattern 12
a was 300 nm and the TEO
It was found that the S oxide film pattern 12a was not dissolved.

Also, the silicon wafer portion immediately below the opening of the TEOS oxide film pattern 12a is not dissolved, and the resist pattern, the silicon film, and the lower layer resist are selectively peeled off from the TEOS oxide film and the silicon wafer. Was completed.

Comparative Example 4 A solution of 10 g of a novolak resin having a molecular weight of 5000 dissolved in 90 g of ethyl lactate was applied onto a silicon wafer 41 on a TEOS oxide film 42 formed in the same manner as in Example 4. Was performed for 180 seconds to form a lower resist film 43. The thickness of the lower resist film 43 after baking is 300 nm.

Next, a 200 nm-thick SiO ₂ film 44 was formed as an intermediate layer on the lower resist 43 by LPCVD. Then, the SiO ₂ film 4 is formed in the same manner as in the fourth embodiment.
A resist film 45 was formed on the substrate 4 (FIG. 10A), and was patterned to form a resist pattern 45a (FIG. 10B). When the cross section of the resist pattern 45a was observed by SEM, it was found that the resist pattern 45a was patterned in a good shape as shown in FIG.

The resist pattern 4 formed as described above
The intermediate film 44 was etched using 5a as a mask (FIG. 10C). A magnetron type RIE apparatus was used as the etching apparatus, and the flow rate was 20 S as a source gas.
CCM of C ₄ F _8, CO flow 100 SCCM, the flow rate 2
Etching was performed using Ar of 00 SCCM under the etching conditions of an excitation power of 300 W and a degree of vacuum of 30 mTorr. The resist pattern width j and the pattern width k of the intermediate layer pattern 44a were measured by a cross-sectional SEM, and a dimensional conversion difference (pattern width k of the intermediate layer pattern−resist pattern width j) caused by etching of the intermediate layer 44 was obtained. 15 nm
I found something.

Next, lower layer resist 43 was etched using intermediate layer pattern 44a as a mask. A magnetron type RIE device was used as an etching device, and O ₂ at a flow rate of 20 SCCM was used as a source gas.
Etching was performed under the etching conditions of an excitation power of 300 W and a degree of vacuum of 30 mTorr. The resist pattern width j and the pattern width 1 of the lower resist pattern 43a are cross-sectional SEM
The dimensional conversion difference (pattern width 1 of lower layer resist—resist pattern width j) caused by etching of the intermediate layer and the lower layer resist was found to be 20 nm.

Further, using the intermediate layer pattern 44a and the lower resist pattern 43a as a mask, the TEOS oxide film 42 was etched by a magnetron reactive ion etching apparatus (FIG. 11A). C ₄ F _{8 with} a flow rate of 30 SCCM and a flow rate of 20 SCC as a source gas
When etching was performed using M CO and Ar at a flow rate of 100 SCCM under an etching condition of 350 W of excitation power and 15 mTorr of vacuum, the intermediate layer pattern 44 a and the lower resist pattern 43 a were not cut off in the middle, and the TEOS oxide film 42 was not removed. Was able to be etched.

The pattern width j of the resist pattern 45a and the pattern width m of the TEOS oxide film pattern 42a are defined by
Measured by EM, the intermediate layer 44, the lower resist 43 and TE
The dimensional conversion difference (the pattern width m of the TEOS oxide film 42 minus the resist pattern width j) caused by the etching of the OS oxide film 42 was 35 nm, which was not within the allowable range (within 10% of the target processing size of 180 nm). I understood that.

As described above, in the method of this comparative example, the number of etching steps is one more than that of the method of the present invention, that is, the number of etching steps of the three-layer resist method can be reduced by one according to the method of the present invention. I understand. As a result, not only the process cost can be reduced, but also the dimensional conversion difference generated at the time of etching can be reduced, and the film to be processed can be processed to a desired size.

Comparative Example 5 In the same manner as in Example 4, a film thickness of 20 was formed on a TEOS oxide film 52 formed on a silicon wafer 51 by LPCVD.
A 0 nm polysilicon film 53 was formed. Next, a resist 54 was applied on the polysilicon film in the same manner as in Example 4 (FIG. 12A), and a resist pattern 54a of 0.18 μmL / S was formed (FIG. 12B).

Further, using the resist pattern 54a as an etching mask, the polysilicon film 53 was etched using a magnetron type reactive ion etching apparatus. H at a flow rate of 30 SCCM as a source gas
Using Br, an excitation power of 500 W and a degree of vacuum of 40 mTorr
When the etching was performed under the above etching conditions, the polysilicon film 53 could be etched without the resist pattern 54 being removed during the etching (FIG. 12C).

Subsequently, using the patterned polysilicon pattern 53a as an etching mask,
The OS oxide film 52 was etched using a magnetron type etching device. Flow rate 20 SCCM as source gas
When etching was performed using C ₄ F ₈ and Ar at a flow rate of 40 SCCM under etching conditions of an excitation power of 200 W and a degree of vacuum of 40 mTorr, the polysilicon pattern 53 a was not removed during the etching.
A TEOS oxide film pattern 52a was formed (FIG. 13A).

Next, the polysilicon pattern 53a used as an etching mask was peeled off using a chemical dry etching apparatus. Flow rate 30 as source gas
Using HCM of SCCM, excitation power 400W, vacuum degree 3
When the etching was performed under the etching condition of 0 mTorr, the polysilicon pattern 53a could be peeled off (FIG. 13B. However, the silicon wafer 51 was removed).
It was also found that the exposed portion A of was also etched.

As described above, the polysilicon pattern 53a
It can be seen that the use of only an etching mask causes a problem in that a portion of the base film that should not be etched is removed during peeling.

Example 5 A film thickness of 300 n formed on a silicon wafer 11
m, a spin-on glass (trade name: FOX) manufactured by Toray Dow Corning Co., Ltd. was applied as a lower resist 13 on the SiO ₂ film 12 manufactured by Toray Dow Corning Co. as a lower resist 13 by a spin coating method. Thereafter, baking was performed at 350 ° C. for 120 seconds in a nitrogen atmosphere having an oxygen concentration of 30 ppm. At this time, the film thickness of the spin-on glass is 100 nm. Subsequently, a 300 nm-thick polysilane film 14 was formed as an intermediate layer on the spin-on glass 13. The polysilane film 14 has a chemical formula 2-1
A solution prepared by dissolving 5 g of polysilane having an average molecular weight of 30,000 shown in No. 3 in 95 g of anisole was applied by spin coating, and then baked at 160 ° C. for 120 seconds to form a film.

Then, a positive chemically amplified resist APEX-E manufactured by Shipley Co. was applied on the polysilane film 14, and
Baking was performed at 98 ° C. for 120 seconds (FIG. 3)
(A)). At this time, the thickness of the resist is 200 nm.

Next, pattern exposure was performed using a reduction optical type stepper using a KrF excimer laser beam as a light source (exposure amount: 24 mJ / cm ² ), baking was performed at 98 ° C. for 120 seconds, and then 0.21 standard. Was developed with a TMAH developer solution to form a 0.18 μmL / S pattern 15a (FIG. 3B). The thickness of the resist pattern 15a is 170 nm. Observation of the cross section of the resist pattern 15a confirmed that the pattern was formed in a good shape as shown in FIG.

The resist pattern 1 formed as described above
5a as an etching mask and a magnetron type R
The silicon organic film 14 was etched by the IE device (FIG. 3C). That is, the flow rate is 100 S as the source gas.
Using CCM Cl ₂ , excitation power 300W, vacuum degree 30
When etching was performed under the etching conditions of mTorr, etching could be performed without removing the resist pattern 15a in the middle.

After completion of the etching, the remaining resist pattern 15a has a thickness of 90 nm. By measuring the pattern width d of the resist pattern 15a before etching and the pattern width e of the polysilane pattern 14a with a cross-sectional SEM, a dimensional conversion difference (pattern width e of polysilane pattern−pattern of resist pattern) caused by etching of the organic silicon film is obtained. When the width d) was determined, it was found to be 7 nm.

Further, using the polysilane pattern 14a as an etching mask, a magnetron type RI is used.
Spin-on-glass film 13 and SiO ₂ film 1
2 were collectively etched (FIG. 4A). C ₄ F _{8 with} a flow rate of 10 SCCM and a flow rate of 100 SC as a source gas
When etching was performed using CO of CM and Ar at a flow rate of 200 SCCM under the etching conditions of an excitation power of 800 W and a degree of vacuum of 60 mTorr, the polysilane pattern 14a was obtained.
Was able to be etched without being removed in the middle.

By measuring the resist pattern width d before etching and the pattern width f of the SiO ₂ film pattern 12a after processing by a cross-sectional SEM, the polysilane film 14,
The dimensional conversion difference (SiO ₂ film pattern 12a) generated by etching the spin-on-glass film 13 and the SiO ₂ film 12
When the pattern width f) of the resist pattern 15a was determined, it was found that the pattern width f was within the allowable range at 12 nm (within 10% of the target processing dimension of 0.18 μm).

Next, after immersing the wafer substrate 11 in a 0.27 N TMAH developer for 120 seconds, the surface of the wafer 11 was washed with pure water to obtain a spin-on-glass film pattern 1.
3a was dissolved and removed. At this time, the polysilane pattern 14
a and the resist pattern 15a could be removed at the same time because the underlying spin-on-glass film pattern 13a was removed (FIG. 4B). After peeling, the thickness of the SiO ₂ film pattern 12a was measured, and was found to be 300 nm.
It was found that the SiO ₂ film pattern 12a was not dissolved.

Also, the silicon wafer portion located immediately below the opening of the SiO ₂ film pattern was not dissolved.
The resist pattern, polysilane pattern, and spin-on-glass film pattern could be selectively removed from the SiO ₂ film pattern and the silicon wafer.

Embodiment 6 In this embodiment, the case where the pattern exposure is performed by an electron beam in Embodiment 2 will be described. First, in the same manner as in Example 2, a TEOS oxide film 2, a lower resist 3, a polysilicon 4, and a resist 5 were sequentially formed on a silicon wafer 1. Next, an electron beam writing apparatus (JB
X-5DII, manufactured by JEOL) at an acceleration voltage of 50 k
Writing was performed at eV and a dose of 10 μC / cm ² . Next, heating and development after exposure were performed in the same manner as in Example 1. As shown in FIG. 1B, a 0.18 μm line and space pattern 5a having a good shape was formed. I understood.

After processing the TEOS oxide film 2 in the same manner as in Example 2, the resist pattern 5a, the polysilicon pattern 4a and the lower resist pattern 3a are removed by dissolving and removing the lower resist pattern 3a with anisole. The oxide film pattern 2a and the silicon wafer 1 were selectively peeled off.

As described above, according to the present invention, pattern exposure can be performed using not only ultraviolet light but also an electron beam. Since the area directly under the resist is made of a conductive silicon film, there is no charge-up during writing,
A resist pattern without displacement can be obtained.

Embodiment 7 In this embodiment, the case where pattern exposure is performed by an electron beam in Embodiment 4 will be described. First, in the same manner as in Example 2, a TEOS oxide film, a lower layer resist, polysilicon, and a resist were sequentially formed on a silicon wafer. Next, an electron beam writing apparatus (JBX-5DI)
I, manufactured by JEOL) at an acceleration voltage of 50 keV and a dose of 10 μC / cm ² . Next, Example 1
After heating and developing after exposure in the same manner as
As shown in FIG. 1B, it was found that a 0.18 μm line and space pattern was formed in a good shape.

Then, after processing the TEOS oxide film in the same manner as in Example 2, the lower resist is dissolved and removed with anisole to select a resist pattern, polysilicon and a lower resist with respect to the TEOS oxide film and the silicon wafer. Peeled off.

As described above, in the present invention, pattern exposure can be performed using not only ultraviolet light but also an electron beam. Since the area directly under the resist is made of a conductive silicon film, there is no charge-up during writing,
A resist pattern without displacement can be obtained.

Example 8 The above chemical formulas 1-1, 1-13, 2-1 and 2-12
Was dissolved in solvents such as anisole, xylene, toluene and cumene to prepare 16 kinds of polysilane solutions. The compounding amount was 8 g of polysilane and 9
2 g. The solution was then placed in a light tight bottle protected from ultraviolet light and stored at room temperature for one month. Then, each solution was applied on a silicon wafer and baked at 80 ° C. for 60 seconds to evaporate the solvent to form a silicon organic film.

Next, the amount of siloxane bonds formed in each film was examined by infrared spectroscopy. Table 1 shows the amount of siloxane bond generation (= area of absorption peak due to siloxane bond / area of absorption peak due to Si-phenyl bond) obtained by normalizing the absorption strength due to siloxane bond with the absorption strength due to Si-phenyl bond. .

[0169]

[Table 1]

Subsequently, the results of examining the etching selectivity between the resist formed by the same method as in Example 1 and the silicon organic film are shown in Table 2 below. The etching conditions were the same as in Example 1.
The conditions were the same as when the silicon organic film was etched using the resist pattern as an etching mask. The measurement of the etching rate was performed on a solid film. The etching rate of the resist is 75 nm / min. In addition,
The etching selectivity was defined as (etching rate of silicon organic film) / (etching rate of resist).

[0171]

[Table 2]

From Table 2, it can be seen that a silicon organic film with suppressed oxidation was formed, and thus a high etching selectivity with the resist was obtained.

Comparative Example 6 Four kinds of solution materials were prepared by dissolving four kinds of polysilanes of Example 4 in cyclohexanone. The blending amounts were 8 g of polysilane and 92 g of cyclohexanone in each solution. Then, the progress of oxidation is performed in the same manner as in Example 8,
And the etching selectivity with resist.

From Table 1 above, it can be seen that the oxidation of the film made with the solution prepared using the cyclohexanone solvent is advanced,
It can be seen that the oxidation of polysilane progressed during storage of the solution. This is presumably because cyclohexanone has an unsaturated bond that easily reacts with other compounds. Also, from Table 2 above, it can be seen that the oxidation selectivity with respect to the resist is lowered due to the progress of oxidation of the silicon organic film.

From a comparison between this comparative example and the example, it is found that the use of a solvent containing no unsaturated bond increases the storage stability and suppresses a silicon organic film in which the progress of oxidation is suppressed. As a result, the etching selectivity with the resist can be kept high, and the thickness of the resist can be reduced.

[0176]

As described above in detail, according to the first and second aspects of the present invention, in the three-layer resist method, the intermediate layer and the lower layer resist are collectively etched using the resist pattern as a mask. Accordingly, it is possible to reduce the number of etching steps required until processing of the film to be processed, reduce a dimensional change difference generated at the time of etching, and process the film to be processed with good dimensional control. Further, according to the third and fourth aspects of the present invention, in the three-layer resist method, the lower resist and the film to be processed are collectively etched using the intermediate layer as a mask, so that the processing of the film to be processed is performed. It is possible to reduce the number of etching steps required for etching, reduce the difference in dimensional change occurring during etching, and process the film to be processed with good dimensional control.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a method of manufacturing a semiconductor device according to first and second embodiments of the present invention in the order of steps.

FIG. 2 is a sectional view showing a method of manufacturing a semiconductor device according to first and second embodiments of the present invention in the order of steps.

FIG. 3 is a sectional view illustrating a method of manufacturing a semiconductor device according to third and fourth embodiments of the present invention in the order of steps.

FIG. 4 is a sectional view illustrating a method of manufacturing a semiconductor device according to third and fourth embodiments of the present invention in the order of steps.

FIG. 5 is a sectional view showing the method of manufacturing the semiconductor device according to Comparative Example 1 in the order of steps.

FIG. 6 is a sectional view showing the method of manufacturing the semiconductor device according to Comparative Example 1 in the order of steps.

FIG. 7 is a cross-sectional view showing the result of SEM observation of the cross-sectional shape of a resist pattern in Comparative Example 2.

FIG. 8 is a sectional view illustrating a method of manufacturing a semiconductor device according to Comparative Example 3 in the order of steps.

FIG. 9 is a sectional view illustrating a method of manufacturing a semiconductor device according to Comparative Example 3 in the order of steps.

FIG. 10 is a sectional view illustrating a method of manufacturing a semiconductor device according to Comparative Example 4 in the order of steps.

FIG. 11 is a sectional view illustrating a method of manufacturing a semiconductor device according to Comparative Example 4 in the order of steps.

FIG. 12 is a sectional view showing the method of manufacturing the semiconductor device according to Comparative Example 5 in the order of steps;

FIG. 13 is a sectional view showing the method of manufacturing the semiconductor device according to Comparative Example 5 in the order of steps.

[Explanation of symbols]

1, 11, 21, 31, 41, 51: silicon substrate 2, 22: tungsten film 2a, 22a: tungsten pattern 3, 23, 26, 43: lower resist film 3a, 23a, 26a, 43a: lower resist pattern 4, 14 ... amorphous silicon film 4a, 14a ... amorphous silicon pattern 5,25,45 ... top resist film 5a, 25a, 45a ... upper resist film pattern 24, 44 ... SiO ₂ film 24a, 44a ... SiO ₂ film pattern 15 and 27, 34, 54 ... resist 15a, 27a, 34a, 54a ... resist pattern 12, 32, 42, 52 ... TEOS oxide film 12a, 32a, 42a, 52a ... TEOS oxide film pattern 13 ... spin-on glass 13a ... spin-on glass pattern 33, 53 ... Polysilicon film 33a, 5 3a: polysilicon pattern

Claims (13)

[Claims] 1. (a) On a film to be processed, Si-Si is added to a main chain.
Forming a silicon organic film containing a compound having a bond; (b) forming a silicon film on the silicon organic film; and (c) forming a photosensitive resin film on the silicon film. (D) performing pattern exposure on the photosensitive resin film;
A step of forming a resist pattern; (e) a step of collectively etching the silicon film and the silicon organic film using the resist pattern as an etching mask; and (g) the silicon film formed by the etching. And (h) removing the silicon organic film by using the pattern of the silicon organic film as an etching mask; and (h) removing the silicon organic film. 2. The film to be processed is a kind selected from the group consisting of a silicon substrate, a conductive film, an insulating film made of an organic material, and an insulating film containing silicon atoms. 2. The method for manufacturing a semiconductor device according to item 1. 3. (a) On an insulating film containing silicon atoms,
Forming a silicon organic film containing a compound having a siloxane bond; (b) forming a silicon film on the silicon organic film; and (c) forming a photosensitive resin film on the silicon film. (D) performing pattern exposure on the photosensitive resin film,
Forming a resist pattern; (e) etching the silicon film using the resist pattern as an etching mask; and (g) using the silicon film pattern formed by the etching as an etching mask. A method of collectively etching the silicon organic film and the insulating film containing silicon atoms; and (h) removing the silicon organic film. 4. The method for manufacturing a semiconductor device according to claim 3, wherein the silicon organic film is formed by applying a solution obtained by dissolving a compound having a siloxane bond in an organic solvent and then baking. 5. The silicon organic film is coated with a solution obtained by dissolving a compound having a Si—Si bond in a main chain in an organic solvent, baked, and heated under an atmosphere in which oxygen is present, or heated or baked in an oxygen-containing atmosphere. 4. The method according to claim 3, wherein the semiconductor device is formed by irradiating a beam. 6. (a) On an insulating film containing silicon atoms,
Forming a first silicon organic film containing a compound having a siloxane bond; and (b) forming a main chain of Si—S on the first silicon organic film.
forming a second silicon organic film containing a compound having an i-bond; (c) forming a photosensitive resin film on the second silicon organic film; and (d) forming a photosensitive resin film on the photosensitive resin film. Pattern exposure,
A step of forming a resist pattern; (e) a step of etching the second silicon organic film using the resist pattern as an etching mask; and (g) a second silicon organic film formed by the etching. (H) using the pattern (1) as an etching mask to collectively etch the first silicon organic film and the insulating film containing silicon atoms; and (h) removing the first silicon organic film. A method for manufacturing a semiconductor device provided. 7. The semiconductor device according to claim 6, wherein the first silicon organic film is formed by applying a solution obtained by dissolving a compound having a siloxane bond in an organic solvent, and then baking. Production method. 8. The method according to claim 1, wherein the first silicon organic film is formed of Si—S
7. The method according to claim 6, wherein a solution obtained by dissolving a compound having an i-bond in the main chain in an organic solvent is applied, baked, and heated or irradiated with ultraviolet light in an atmosphere where oxygen is present. The manufacturing method of the semiconductor device described in the above. 9. The compound having a Si—Si bond in the main chain is polysilane or polysilene.
9. The method for manufacturing a semiconductor device according to any one of items 5, 6, and 8. 10. The method according to claim 1, wherein said step (e) or (g) is performed by reactive plasma etching, magnetron reactive plasma etching, electron beam plasma etching, TCP etching, ICP etching, or ECR plasma etching. 7. The method of manufacturing a semiconductor device according to any one of the above items. 11. The insulating film containing silicon atoms includes a silicon oxide film, a silicon nitride film, a silicon oxynitride film,
Or a spin-on-glass film.
13. The method for manufacturing a semiconductor device according to any one of the above items. 12. (a) On the film to be processed, Si—S is added to the main chain.
forming a silicon organic film containing a compound having an i-bond; (b) forming a photosensitive resin film on the silicon organic film; and (c) performing pattern exposure on the photosensitive resin film. ,
Forming a resist pattern, wherein the silicon organic film is formed by applying a solution containing at least a compound having a Si-Si bond in the main chain and a solvent containing no unsaturated bond. A pattern forming method, characterized in that: 13. The pattern forming method according to claim 12, wherein the compound having a Si—Si bond in the main chain is a compound in which hydrogen is bonded to silicon in the main chain.