JPH10209134A - Pattern-forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the etching selection ratio of the resist and polysilane film, by etching an organic silicon film and transferring a resist pattern to the organic silicon film, by using etching gas which contains at least one kind of specific atoms. SOLUTION: A film 2 to be worked is formed on a wafer substrate 1, on the film an organic silicon film 3 containing silicon and organic silicon compound having bonds to silicon in a main chain is formed. The thickness of the film 3 is preferably 0.005-5μm. The glass transition temperature of the film 3 is at least 0 deg.C. Resist solution is spread on the film 3, and resist 4 is formed by heat treatment. The film thickness of the resist 4 is preferably 0.01-10μm. A resist pattern 5 is formed by development using an alkali developer such as TMAH and choline. The resist pattern 5 is used as an etching mask, the organic silicon film 3 is subjected to dry-etching, and the resist pattern 5 is transferred to the film 3. As the etching gas, at least one or more kinds of gas containing chlorine or bromine or iodine atoms are used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pattern forming method using an organic silicon film pattern as an etching mask.

[0002]

2. Description of the Related Art A method for manufacturing a semiconductor device includes many steps of depositing a plurality of substances on a semiconductor wafer and patterning a film formed by the deposition into a desired pattern. This patterning process is performed by depositing a photosensitive material, generally called a resist, on a film to be processed on a wafer, pattern-exposing the resist film selectively using ultraviolet light as a light source, and developing the resist film. .

In such a patterning step, it is important to prevent the reflected light of the exposure light from the film to be processed. In Japanese Patent Application Laid-Open No. 49-55280, the antireflection A method for forming a film is disclosed.
Various materials are used for the anti-reflection film, but the following materials that can be applied by a spin coating method with low process cost are mainly used.

(1) A material obtained by adding a dye to a spin glass (Jpn. J. Appl. Phys. Vol. 35 (1)
996) pp. L2257-L1259) (2) Plasma decomposition type resin such as polysulfone (JP-A-59-93448) (3) Polysilane (US Pat. No. 5,401,614)

[0005]

However, (1)
However, when a chemically amplified resist having a high resolution is used, there is a problem that footing or erosion occurs and a good resist profile cannot be obtained. Also,
In the case of the material (2), when the resist pattern is transferred by the dry etching method, since the etching rates of the antireflection film and the resist are substantially equal to each other, the resist pattern completely disappears during the etching of the antireflection film, and the desired size is obtained. This causes a problem that the antireflection film cannot be processed. In particular, when the thickness of the resist is reduced to the same level as that of the anti-reflection film in order to increase the resolution, this problem becomes more remarkable.

Further, in the case of the material (3), when the resist pattern is transferred by the dry etching method, the polysilane film may be deteriorated, and it is difficult to perform normal etching of the polysilane film. Further, when the polysilane film is etched with a halogen-based gas, there is a problem that the resist pattern is thickened by deposits and cannot be etched with good dimensional control.

It is an object of the present invention to provide a pattern forming method capable of improving the etching selectivity between a resist and a polysilane film without causing deterioration of the polysilane film.

Another object of the present invention is to provide a pattern forming method capable of preventing a resist pattern from being thickened when patterning a polysilane film.

Another object of the present invention is to provide a pattern forming method capable of forming a pattern with good dimensional control.

It is a further object of the present invention to provide a pattern forming method capable of removing an antireflection film without generating a residue.

[0011]

In order to solve the above-mentioned problems, the present invention (claim 1) comprises an organic silicon compound having a bond between silicon and silicon in a main chain on a film to be processed; A step of forming an organic silicon film having a transition temperature of 0 ° C. or higher, a step of forming a resist pattern on the organic silicon film, and at least one atom selected from the group consisting of chlorine, bromine and iodine. Transferring the resist pattern to the organic silicon film by etching the organic silicon film using an etching gas.

According to the present invention (claim 2), in the above-described pattern forming method (claim 1), the method further comprises a step of etching the film to be processed by using the resist pattern and the organic silicon film as an etching mask. It is characterized by the following.

According to the present invention (claim 3), in the above-mentioned pattern forming method (claim 1), a step of removing the resist pattern and a step of etching a film to be processed using the organic silicon film as an etching mask. Is further provided.

According to the present invention (claim 4), in the pattern forming method (claim 1), the organic silicon film is
A coating film is formed from a solution material containing an organic silicon compound having a bond between silicon and silicon in a main chain, and the coating film is formed by heating the coating film.

According to the present invention (claim 5), in the pattern forming method (claim 1), the organic silicon film is
The coating is formed by forming a coating film with a solution material containing an organic silicon compound having a bond between silicon and silicon in a main chain, and crosslinking the organic silicon compound.

The present invention (Claim 6) is characterized in that, in the above-described pattern forming method (Claim 5), the crosslinking is performed by heating the coating film.

According to the present invention (claim 7), in the above-mentioned pattern forming method (claim 5), the crosslinking heats the coating film, irradiates the coating film with an energy beam; The method is characterized by being performed by a method selected from the group consisting of irradiating the coating film with an energy beam while heating the coating film.

The present invention (claim 8) is characterized in that, in the above-described pattern forming method (claim 1), the organic silicon compound is represented by the following general formula.

[0019]

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 3 or less carbon atoms, and R ⁶ is a hydrogen atom or a carbon atom having 1 to 3 carbon atoms. 20 represents a substituted or unsubstituted aliphatic hydrocarbon group or an aromatic hydrocarbon group.) In the present invention (claim 9), in the above-described pattern forming method (claim 1), the film to be processed may be a metal. It is one type selected from the group consisting of a wiring layer and a silicon-based material film.

The present invention (Claim 10) is characterized in that, in the above-described pattern forming method (Claim 1), the film to be processed is a silicon-based insulating film.

The present invention (Claim 11) is characterized in that in the above-described pattern forming method (Claim 1), the etching of the silicon-based insulating film is performed using an etching gas containing a fluorine-based gas. .

According to a twelfth aspect of the present invention, in the above-described pattern forming method (the first aspect), the silicon-based insulating film comprises a silicon oxide film, a silicon nitride film, a silicon oxynitride film, and a spin-on-glass film. It is characterized by being one kind selected from the group.

According to a thirteenth aspect of the present invention, in the above-described pattern forming method (the first aspect), the organic silicon film contains a conductive substance or a substance which becomes conductive when irradiated with light. Features.

According to the present invention (claim 14), in the pattern forming method (claim 1) described above, the organic silicon film uses an etching gas containing at least one selected from the group consisting of Cl ₂ and HBr. And etched.

The present invention (claim 15) provides a step of forming an organic silicon film having a glass transition temperature of 0 ° C. or more on a film to be processed, containing an organic silicon compound having a bond between silicon and silicon in a main chain. Forming a resist pattern on the organic silicon film; and etching the organic silicon film using an etching gas containing at least one atom selected from the group consisting of chlorine, bromine and iodine. A process of oxidizing the organic silicon film; and a step of etching the film to be processed using a pattern including the oxidized organic silicon film as an etching mask. I will provide a.

According to the present invention (claim 16), in the above-mentioned pattern forming method (claim 15), the oxidizing treatment includes irradiation with an energy beam, irradiation with plasma, and immersion in a solution containing an oxidizing agent. It is characterized by being performed by one kind selected from the group consisting of:

According to the present invention (claim 17), in the above-mentioned pattern forming method (claim 15), the film to be processed is one kind selected from the group consisting of silicon nitride, a silicon-based material and a metal wiring layer. There is a feature. Law.

The present invention (claim 18) provides a step of forming an organic silicon film having a glass transition temperature of 0 ° C. or more on a film to be processed, which contains an organic silicon compound having a bond between silicon and silicon in a main chain. Forming a resist pattern on the organic silicon film; and etching the organic silicon film using an etching gas containing at least one atom selected from the group consisting of chlorine, bromine and iodine. Etching the film to be processed using the pattern as an etching mask; and forming the pattern including the organic silicon film into a gas containing at least one atom selected from the group consisting of chlorine, bromine, and fluorine. Stripping using a mixed gas of a gas containing oxygen atoms. The present invention (Claim 19) includes a step of forming an organic silicon film having a glass transition temperature of 0 ° C. or more on a film to be processed, containing an organic silicon compound having a bond between silicon and silicon in a main chain. Forming a resist pattern on the organic silicon film, etching the organic silicon film using an etching gas containing at least one atom selected from the group consisting of chlorine, bromine, and iodine; Etching the film to be processed using as an etching mask, and forming a pattern including the organic silicon film by using at least one solution selected from the group consisting of a solution containing an amine-based solvent and a solution containing a fluorine atom. And a step of separating by processing. The present invention (Claim 20) is characterized in that in the above-described pattern forming method (Claims 18 and 19), the organic silicon compound has a structure represented by the following general formula in the main chain.

[0029]

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 3 or less carbon atoms, and R ⁶ is a hydrogen atom or a carbon atom having 1 to 3 carbon atoms. 20 represents a substituted or unsubstituted aliphatic hydrocarbon group.) Hereinafter, the pattern forming method of the present invention will be described more specifically with reference to the drawings.

FIGS. 1A to 1F are sectional views showing a pattern forming method according to one embodiment of the present invention in the order of steps.

First, as shown in FIG. 1A, a film to be processed 2 is formed on a wafer substrate 1. The film 2 to be processed is not particularly limited. For example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a silicon-based insulating material such as spin-on glass or a blank material used in manufacturing a mask. Examples include films, amorphous silicon, polysilicon, silicon materials such as silicon substrates, and wiring materials such as aluminum, aluminum silicide, copper, and tungsten.

Next, as shown in FIG. 1B, an organic silicon film 3 containing an organic silicon compound having a bond between silicon and silicon in a main chain is formed on the film 2 to be processed. The thickness of the organic silicon film 3 is preferably 0.005 to 5 μm. The reason is that when the film thickness is less than 0.005 μm, when forming a pattern by light exposure, the reflected light from the underlying substrate cannot be sufficiently suppressed. When the film thickness is more than 5 μm, the resist pattern is formed by dry etching. This is because a dimensional conversion difference is remarkably generated when the pattern is transferred to the silicon film.

The glass transition temperature of the organic silicon film 3 is 0
It should be above ° C. The reason is that if the glass transition temperature of the organic silicon film 3 is low, when the resist pattern is transferred to the organic silicon film 3 by the dry etching method, the organic silicon film 3 is deteriorated and the etching of the organic silicon film 3 is performed normally. Because it cannot be done.

The method of forming the organic silicon film 3 may be either a method of applying a solution or a method of forming a film by a gas phase method such as a CVD method (chemical vapor deposition method). It is preferable to form a silicon film. The reason is that the coating method is simpler than the CVD method,
This is because the process cost can be reduced. Here, a method for forming an organic silicon film by a coating method will be described in detail. First, an organic silicon compound having a bond between silicon and silicon in its main chain is dissolved in an organic solvent to prepare a solution material. Examples of the organic silicon compound having a bond between silicon and silicon in its main chain include, for example, a compound represented by the general formula (SiR ₁₁
R ₁₂ ), wherein R ₁₁ and R ₁₂ are a hydrogen atom or a carbon atom
To 20 substituted or unsubstituted aliphatic hydrocarbons or aromatic hydrocarbons). The polysilane may be a homopolymer or a copolymer, or may have a structure in which two or more polysilanes are bonded to each other via an oxygen atom, a nitrogen atom, an aliphatic group, or an aromatic group.

Specific examples of the organosilicon compound used in the present invention are shown in the following formulas [1-1] to [1-114]. In the formula, m and n represent positive integers.

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

Embedded image The weight average molecular weight of the above compounds is not particularly limited, but is preferably from 200 to 100,000. The reason is that if the molecular weight is less than 200, the organic silicon film is dissolved in the solvent of the resist, while if it exceeds 100,000, it is difficult to dissolve in the organic solvent and it is difficult to prepare a solution material. . The organic silicon compound is not limited to one kind, and several kinds of compounds may be mixed.

For the organosilicon compound, if necessary, a thermal polymerization inhibitor for measuring storage stability, an adhesion improver for improving the adhesion to the film to be processed, and a resist for the film to be processed. Crosslinks UV-absorbing dyes, polysulfone, polybenzimidazole or other UV-absorbing polymers, conductive substances, substances that become conductive by light or heat, or organic silicon compounds to prevent light reflected into the film A crosslinker which can be added may be added.

Examples of the conductive substance include organic sulfonic acid, organic carboxylic acid, polyhydric alcohol, polyhydric thiol (for example, iodine and bromine), SbF ₅ , PF ₅ , B
F ₅ , SnF _{5 and the} like. As a substance that becomes conductive by applying energy such as light or heat,
Carbon clusters (C ₆₀ , C ₇₀ ), cyanoanthracene, dicyanoanthracene, triphenylpyrium, tetrafluoroborate, tetracyanoquinodimethane, tetracyanoethylene, phthalimide triflate, perchloropentacyclododecane, dicyanobenzene, benzonitrile , Trichloromethyltriazine, benzoyl peroxide, benzophenonetetracarboxylic acid, t-butyl peroxide and the like. More specifically, there can be mentioned compounds represented by the following formulas [2-1] to [2-106].

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

Embedded image When a crosslinking agent is added, the organosilicon compound is preferably a compound in which hydrogen is bonded to silicon in the main chain. As such organosilicon compounds, for example, the formulas [1-1] to [1]
-26].

The cross-linking agent is added to cross-link the organic silicon compound to prevent mixing between the resist and the organic silicon compound, and to improve heat resistance.

As the crosslinking agent, an organic substance having a multiple bond can be used. The organic substance having a multiple bond is
A compound having a double bond or a triple bond, more specifically, a compound having a vinyl group, an acrylic group, an aryl group, an imide group, an acetylenyl group, or the like. The organic substance having such a multiple bond may be any of a monomer, an oligomer, and a polymer.

The organic substance having such a multiple bond causes an addition reaction with the Si—H bond of the organic silicon compound by heat or light to crosslink the organic silicon compound. Note that the organic substance having a multiple bond may be self-polymerized. Specific examples of the organic substance having a multiple bond are shown below.

[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

Embedded image As described above, when an organic substance having a multiple bond is mixed with the organic silicon compound, a radical generator or an acid generator may be added as a catalyst. These radical generators or acid generators are composed of an organic substance having a multiple bond and S
It has a role of assisting i-H addition reaction or self-polymerization.

Examples of the radical generator include azo compounds (for example, azobisisobutyronitrile), peroxides, alkylaryl ketones, silyl peroxides, and organic halides. The radical generator generates a radical by decomposing an O—O bond or a C—C bond in a molecule by light irradiation or heating. Examples of the radical generator include those represented by chemical formulas [4-1] to [4-24]. Benzoyl peroxide [4-1] di-tert-butyl peroxide [4-2] benzoin [4-3] benzoin alkyl ether [4-4] benzoin alkylaryl thioether [4-5] benzoyl aryl ether [4-6] benzylalkylaryl Thioether [4-7] Benzyl aralkyl ethanol [4-8] Phenylglyoxal alkyl acetal [4-9] Benzoyl oxime [4-10] Triphenyl-t-butylsilyl peroxide [4-11]

[0077]

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[0078]

Embedded image Among the radical generators, the organic halide is preferably a trihalomethyl-s-triazine represented by the general formula [4-18] (for example, see US Pat. No. 3,779,778). In the general formula [4-18], Q is bromine or chlorine, and R ¹¹ is -CQ ₃ , -NH ₂ , -NH
R ¹³ , —OR ¹³ or a substituted or unsubstituted phenyl group, R ¹² represents —CQ ₃ , —NH ₂ , —NHR ¹³ , —N (R
¹³ ) ₂ , -OR ¹³ ,-(CH = CH) _n -W or a substituted or unsubstituted phenyl group, wherein R ¹³ is a phenyl group, a naphthyl group or a lower alkyl group having 6 or less carbon atoms, and n is And W is an aromatic ring, a heterocyclic ring, or a group represented by the following general formula. These may crosslink the polysilane by light or heat in some cases without the presence of a compound having multiple bonds.

[0079]

Embedded image In the formula, Z represents oxygen or sulfur, and R ¹⁴ represents a lower alkyl group or a phenyl group. Among the trihalomethyl-s-triazines represented by the general formula [4-18], particularly, R ¹²
Is preferably-(CH = CH) _n- W (see, for example, U.S. Patent No. 3987037). Vinyltrihalomethyl-s-
Triazine is an s-triazine having a trihalomethyl group and an ethylenically unsaturated bond conjugated to a triazine ring, and showing photodegradability.

The following substituents may be introduced into the aromatic or heterocyclic ring represented by W. Examples thereof include chlorine, bromine, phenyl group, lower alkyl group having 6 or less carbon atoms, nitro group, phenoxy group, alkoxy group, acetoxy group, acetyl group, amino group and alkylamino group.

The trihalomethyl-s-triazine represented by the general formula [4-18] is converted to a compound represented by any of the chemical formulas [4-25] to [4-3]
4] and other radical generators represented by the chemical formula [4-35]
To [4-39]. In some cases, these halides can crosslink the polysilane by light or heat without the presence of a compound having a multiple bond.

[0082]

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[0083]

Embedded image Examples of the acid generator include onium salts, halogen-containing compounds, orthoquinonediazide compounds, sulfone compounds,
Sulfonic acid compounds and nitrobenzyl compounds are exemplified. Of these, onium salts and orthoquinonediazide compounds are preferred.

The onium salts include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and ammonium salts. Preferably, the chemical formula [4-4]
0] to [4-42].

Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing hydrocarbon compound, and a haloalkyl group-containing heterocyclic compound. In particular, the chemical formulas [4-43] and [4-
44] is preferred.

Examples of the dinindiazide compound include a diazobenzoquinone compound and a diazonaphthoquinone compound. Particularly, compounds represented by chemical formulas [4-45] to [4-48] are preferable.

Examples of the sulfone compound include β-ketosulfone and β-sulfonylsulfone. Especially,
The compound represented by the chemical formula [4-49] is preferable.

Examples of the nitrobenzyl compound include a nitrobenzylsulfonate compound and a dinitrobenzylsulfonate compound. In particular, the chemical formula [4-5]
0] are preferred.

Examples of the sulfonic acid compound include an alkylsulfonic acid ester, a haloalkylsulfonic acid ester, an arylsulfonic acid ester, and iminosulfonate. In particular, the chemical formulas [4-51] to [4-53]
The compound represented by is preferred.

[0090]

Embedded image (Wherein, R ^{14 to} R ¹⁶ may be the same or different, and each represents a hydrogen atom, an amino group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group or an alkoxyl group, and X represents SbF ₆ , PF ₆ , BF ₄ , CF ₃ CO
₂ , ClO ₄ , CF ₃ SO ₃ ,

[0091]

Embedded image R ¹⁷ is a hydrogen atom, an amino group, an anilino group, a substituted or unsubstituted alkyl group or an alkoxyl group, R ¹⁸ , R ¹⁹
May be the same or different, and each represents a substituted or unsubstituted alkoxyl group, and R ²⁰ represents a hydrogen atom, an amino group, an anilino group, a substituted or unsubstituted alkyl group or an alkoxyl group.

[0092]

Embedded image (In the formula, R ²¹ represents a trichloromethyl group, a phenyl group, a methoxyphenyl group, a naphthyl group or a methoxynaphthyl group.)

[0093]

Embedded image (In the formula, R ^{22 to} R ²⁴ may be the same or different and each represents a hydrogen atom, a halogen atom, a methyl group, a methoxy group or a hydroxyl group.)

[0094]

Embedded image (Wherein R ²⁵ represents —CH ₂ —, —C (CH ₃ ) ₂ —,
C (= O) - or -SO ₂ - indicates, q is an integer from 1 to 6, r is an integer of 0 to 5, the sum of q and r is 1-6. )

[0095]

Embedded image (Wherein, R ²⁶ is a hydrogen atom or a methyl group, and R ²⁷ is —C
_{H 2 -, - C (CH} 3) 2 -, - C (= O) - or -
SO ₂ - indicates, s is an integer from 1 to 6, t is an integer of 0 to 5, the sum of s and t is 1-6. )

[0096]

Embedded image (Wherein, R ^{28 to} R ₃₁ may be the same or different from each other, and each represents a substituted or unsubstituted alkyl group or a halogen atom, and Y represents —C (＝ O) — or —SO
Represents _2- , and u is an integer of 0 to 3. )

[0097]

Embedded image (Wherein R ³² is a substituted or unsubstituted alkyl group, R
³³ is a hydrogen atom or a methyl group, and R ³⁴ is

[0098]

Embedded image (However, R ³⁵ is a hydrogen atom or a methyl group, R ³⁶ , R
³⁷ may be the same or different, and each represents a substituted or unsubstituted alkoxyl group;
-3. )

[0099]

Embedded image (In the formula, R ³⁸ and R ³⁹ may be the same or different from each other, and a hydrogen atom or a substituted or unsubstituted alkyl group, R ⁴⁰ and R ⁴¹ may be the same or different from each other. And each represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group.)

[0100]

Embedded image (In the formula, R ⁴² represents a hydrogen atom or a substituted or unsubstituted alkyl group, R ⁴³ and R ⁴⁴ may be the same or different, and each represents a substituted or unsubstituted alkyl group or an aryl group; R ⁴³ and R ⁴⁴ may combine with each other to form a ring structure.

[0101]

Embedded image (In the formula, Z represents a fluorine atom or a chlorine atom.) In the present invention, as a crosslinking agent for the organosilicon compound, the following substances can be used in addition to the above-described organic substance having a multiple bond. For example, an organic substance having a hydroxyl group, an organic substance having an epoxy group, an organic substance having an amino group, pyridine oxide, an alkoxysilyl group, a silyl ester group, an oximusilyl group, an ethoxysilyl group, an aminosilyl group, an amidosilyl group, an aminoxysilyl group, or halogen , Organometallic compounds, compounds containing halogen, and the like.

As the compound having a hydroxyl group,
Examples include polyhydric alcohols, novolak resins, compounds having a carboxyl group, and silanols. These compounds react with Si—H by light or heat to crosslink the organosilicon compound. Specific examples of such compounds are shown in chemical formulas [5-1] to [5-28].

Examples of the compound having an epoxy group include those generally called epibis type epoxy resins or alicyclic epoxy resins. In these resins, a hydroxyl group may be partially added. Further, the above-mentioned acid generator may be added together with these resins. A specific example of such a compound is represented by a chemical formula [6-1].
To [6-12].

Examples of the compound having an amino group include those represented by the chemical formulas [7-1] to [7-9].

Examples of the pyridine oxide include those represented by chemical formulas [8-1] to [8-6].

An alkoxysilyl group, a silyl ester group,
Examples of the silicon compound having an oximesilyl group, an enoxysilyl group, an aminosilyl group, an amidosilyl group, an aminoxysilyl group, or a halogen include a compound represented by the chemical formula [9-
1] to [9-52]. In these chemical formulas, X represents the above substituent. In addition, together with these compounds, platinum usually used as a condensation catalyst for silicone, metal catalysts such as organotin compounds,
A base may be used.

The organometallic compound means a metal salt or a metal complex substituted by an organic group. B, Mg,
Al, Ca, Ti, V, Mn, Fe, Co, Ni, C
u, Zn, Zr, Mo, Rh, Pd, Cd, In, Sn
Is used. Specific examples of such compounds are shown in chemical formulas [10-1] to [10-9].

Examples of the compounds containing halogen include those represented by the chemical formulas [11-1] to [11-9].

[0109]

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[0115]

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[0116]

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[0118]

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[0119]

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[0120]

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[0121]

Embedded image As the organic solvent, either a polar solvent or a non-polar solvent may be used, but a solvent having a multiple bond is likely to react with an organic silicon compound, and a solution material is likely to change with time. Is more preferred.

A coating material is prepared by the above method, and a solution material is coated on the film to be processed by, for example, a spin coating method, and then heated to evaporate the solvent, thereby forming an organic silicon film. At this stage, it is only necessary to obtain a glass transition temperature that provides a sufficient selectivity to the resist, but if not, it is necessary to further heat or irradiate the energy beam to the coating to crosslink the coating. It is.

Therefore, according to the present invention, if the heat resistance is improved by crosslinking and a glass transition temperature of 0 ° C. or higher is obtained, the glass transition temperature of a compound having a bond between silicon and silicon in the main chain is necessarily 0 ° C. There is no need to be above.

Examples of the energy beam include ultraviolet light, X-ray, electron beam, ion beam and the like. In particular, simultaneous heating and energy beam irradiation can accelerate the progress of the crosslinking reaction, and can significantly improve the glass transition temperature in a practical processing time.
In addition, the bond between silicon and silicon in the main chain in the organic silicon compound having the bond between silicon and silicon in the main chain by heating or irradiation with an energy beam is expanded, combined with oxygen, and easily oxidized. In some cases, the etching selectivity between the resist and the silicon organic film decreases. In such a case, the heating and the irradiation with the energy beam are preferably performed in an atmosphere having a lower oxygen concentration than in air.

Next, a resist pattern is formed on the organic silicon film 3. First, as shown in FIG. 1C, a resist solution is applied on the organic silicon film 3 and heat treatment is performed to form a resist 4. If the thickness of the resist 4 is reduced, the exposure latitude, the focus latitude, or the resolution can be improved. for that reason,
The thickness of the resist 4 is preferably as thin as possible so long as the organic silicon film 3 can be etched with good dimensional controllability, and preferably 0.01 to 10 μm.

The type of the resist is not particularly limited, and a positive type or a negative type can be selected and used according to the purpose. Specifically, as the positive resist, for example, a resist (IX-770, manufactured by Nippon Synthetic Rubber Co., Ltd.) composed of naphthoquinonediazide and a novolak resin, a chemical composed of a polyvinylphenol resin protected with t-BOC and an onium salt Amplification type resist (APEX
-E, manufactured by Shipley Co., Ltd.). Examples of the negative resist include, for example, a chemically amplified resist (SNR248, manufactured by Shipley Co., Ltd.) composed of polyvinyl phenol, a melamine resin and a photoacid generator, and a resist (R) composed of polyvinyl phenol and a bisazide compound.
D-2000D, manufactured by Hitachi Chemical Co., Ltd.).
It is not limited to these.

These resist solutions are applied to the organic silicon film 3
The resist 4 is formed on the upper surface by, for example, spin coating, and then heating to vaporize the solvent.
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. Exposure light source: mercury lamp, XeF
(Wavelength = 351 nm), XeCl (wavelength = 308 n)
m), KrF (wavelength = 248 nm), KrCl (wavelength =
Excimer lasers such as 222 nm), ArF (wavelength = 193 nm), and F ₂ (wavelength = 151 nm). Note that an X-ray, an electron beam, or an ion beam may be used as an exposure light source.

Then, as shown in FIG.
A resist pattern 5 is formed by performing a development process using an alkali developer such as H or choline. Also, if necessary, an upper antireflection film in order to reduce multiple reflections in the resist generated when performing light exposure, or an upper antireflection film in order to prevent charge-up that occurs when performing electron beam exposure. An antistatic film may be formed on the resist.

Next, as shown in FIG. 1E, the resist pattern 5 is transferred to the organic silicon film 3 by dry-etching the organic silicon film 3 using the resist pattern 5 as an etching mask. . As an etching method, for example, reactive ion etching, magnetron type reactive ion etching, electron beam ion etching, ICP etching, or ECR
There is no particular limitation as long as it can be finely processed, such as ion etching.

In order to maintain the selectivity with the resist, the power density applied to the electrode on which the wafer is placed is 10 W / cm.
It is desirable to keep it to ² or less. The reason is that the etching of the organic silicon film is close to the chemical etching, and the sputterability is increased, so that the etching rate of the resist is increased and the selectivity is prevented from being lowered. In addition, when using an apparatus that can perform plasma generation and bias generation independently, it is necessary to lower the bias for the above-described reason and to suppress the power used for plasma generation so that the number of ions is not excessive. . Therefore, it is desirable that the power used for plasma generation be suppressed to 10 W / cm ² or less with respect to the area of the wafer to be processed.

Further, by maintaining the temperature of the wafer at 20 ° C. or higher during the etching of the organic silicon film, it is possible to achieve processing without a dimensional conversion difference. As the etching gas, it is preferable to use at least one gas containing a chlorine, bromine, or iodine atom.
HCl, CF ₃ Cl, CF ₂ Cl ₂ , CF ₃ Br, CC
l ₄ , C ₂ F ₅ Cl ₂ , Cl ₂ , SiCl ₄ , Br ₂ ,
Gases such as I ₂ , HBr, HI, and BCl ₃ can be used. One type of these gases may be used, or a plurality of types may be mixed and used. Further, CO, H ₂ , O ₂ , He, N ₂ , Ar, SO _{2 and the} like other than the halogen-based gas may be added.

As described above, by etching the organic silicon film, the organic silicon film is not deteriorated, a high selectivity can be obtained with respect to the resist, and the processing has high dimensional controllability. Is achieved.

Next, as shown in FIG. 1F, the film to be processed 2 is processed using the resist pattern 5 and the organic silicon film pattern 6 as an etching mask. Since the etching selectivity of the organic silicon film pattern 6 to the resist pattern 5 (the etching rate of the organic silicon film / the etching rate of the resist) is high, the remaining of the resist pattern 5 and the organic silicon film pattern 6 is sufficient, so that the etching mask is insufficient. , And the pattern 7 can be formed by processing the film to be processed 2 with good dimensional controllability.

When the film to be processed is made of a metal wiring film or a silicon-based material, the film to be processed can be processed by a gas used for etching the organic silicon film in a continuous process in the same apparatus. Preferably, the organic silicon film and the film to be processed can be collectively etched, so that the number of steps can be simplified.

Also, as shown in FIGS. 2A and 2B, the resist pattern 5 is removed, and as shown in FIG. 2C, only the organic silicon film pattern 6 is used as an etching mask. The pattern 7 may be formed by etching the processing target film 2. When processing the ultra-fine processing target film 2 having a high aspect ratio, after processing the silicon organic film, the resist pattern 5 on the silicon organic film is removed by another device or the same device. It is preferable to reduce the aspect ratio. In this case, the etching mask is only the organic silicon film pattern 6 transferred by the resist pattern 5, whereby the aspect ratio can be kept small and the microloading effect can be kept down.

According to the pattern forming method of the present invention described above, etching can be performed at a high selectivity with respect to the resist without deteriorating the organic silicon film. It is possible to process the film to be processed with good efficiency. When the glass transition temperature of the organic silicon film is low, or when the organic silicon film is etched with a fluorine-based gas, the organic silicon film is transformed into a sponge shape. This is probably because halogen radicals in the plasma easily penetrate into the interior of the organic silicon film, become a silicon halide compound, volatilize from the film, and hardly volatilizable organic components remain without being etched.

Therefore, in the method of the present invention, by increasing the glass transition temperature of the organic silicon film or by crosslinking the organic silicon film, it is difficult for the halogen radicals generated in the plasma to penetrate into the organic silicon film. It is considered that the alteration was able to be suppressed by doing so.

Next, various preferred embodiments of the present invention will be described.

(1) In the method of the present invention, a compound having a structure represented by the following general formula [12] in the main chain is used as the organosilicon compound.

[0140]

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 3 or less carbon atoms, and R ⁶ is a hydrogen atom or a carbon atom having 1 to 3 carbon atoms. 20 represents a substituted or unsubstituted aliphatic hydrocarbon group or aromatic hydrocarbon group.) As specific examples of the organosilicon compound having the structure represented by the above formula [12], the following formulas 13-1 to 13-54] Can be mentioned.

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

[0146]

Embedded image

[0147]

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[0148]

Embedded image When a compound having a structure represented by the general formula [12] is used as the organic silicon compound, the resist pattern and the organic silicon film pattern do not become thick when etching the organic silicon film, and the The organic silicon film can be etched with a high selectivity, and the film to be processed can be processed to a desired size even if the thickness of the resist is reduced.

This is probably because the organosilicon compound having the structure represented by the above general formula, when etched with a gas containing chlorine, bromine, or iodine atoms, has a product that adheres to the resist and the side wall of the organosilicon film. It is considered that the resist pattern is not thick because it is difficult to form.

(2) In the method of the present invention, a silicon-based insulating film is used as a film to be processed.

As the silicon-based insulating film, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, spin-on-glass, or the like can be used. Further, a blank material used in manufacturing a photomask may be used.

An organic silicon film containing an organic silicon compound having a silicon-to-silicon bond in its main chain has a low etching rate in plasma suitable for etching a silicon-based insulating film and has etching resistance. As a result, it is possible to prevent the etching mask material composed of the resist pattern and the organic silicon film or the etching mask material composed of only the organic silicon film pattern from being receded during the etching of the silicon-based insulating film. It becomes possible to process a system insulating film.

As described above, according to the pattern forming method of the present invention, when a silicon-based insulating film is used as a film to be processed,
Particularly excellent effects can be obtained.

(3) In the method of the present invention, after forming the organic silicon film pattern, oxidizing the organic silicon film pattern.

The film to be processed is preferably a silicon-based material such as amorphous silicon or polysilicon, a wiring material such as aluminum, aluminum silicide, copper, or tungsten, or silicon nitride.

As a preferable oxidation treatment method, a method of irradiating the organic silicon film pattern with an energy beam such as an electron beam, an ion beam, ultraviolet light, or X-rays, or irradiating oxygen radicals to the organic silicon film pattern with oxygen plasma. Method, H ₂ O ₂ solution, Fe ₂ (CN ₆ ) solution,
KMnO ₄ solution, mixed solution of H ₂ O ₂ and H ₂ SO ₄ ,
A mixed solution of Cr ₂ O and H ₂ SO ₄ , HClO ₄ and H ₂
Mixed solution with SO ₄ , mixed solution of KMnO ₄ and H ₃ PO ₄ , mixed solution of K ₂ S ₂ O ₈ and H ₂ SO ₄ , (NH
₄ ) a mixed solution of ₂ S ₂ O ₈ , H ₂ O ₂ and H ₂ SO ₄ ,
A mixed solution of HNO ₃ and H ₂ SO ₄ , (NH ₄ ) ₂ S ₂
There is a method in which an object to be processed is permeated into a solution containing an oxidizing agent such as a mixed solution of O ₈ and H ₂ SO ₄ .

When the oxidation treatment is performed in the state shown in FIG. 1E, the organic silicon film pattern 6 is oxidized to become an oxidation treatment film pattern 8 as shown in FIG. At that time, depending on the oxidation treatment method, the resist pattern 5 is incinerated and disappears. However, as shown in FIG. 3C, the resist pattern 5 may remain.

After the oxidizing process is performed, as shown in FIG. 3C, the film to be processed 2 is etched using the oxidized film pattern 8 as an etching mask. Note that FIG.
FIG. 3A shows a case where the film to be processed 2 is etched using only the oxidized film pattern 8 as an etching mask, but as shown in FIG. The film to be processed 2 may be processed using the film pattern 8 as an etching mask.

As for the source gas in this case, when the film to be processed is a wiring material or a silicon-based material, it is desirable to etch the film to be processed using a bromine-based gas or a chlorine-based gas. When the film to be processed is a SiN film, it is preferable to use a gas system containing at least a fluorine-based gas and a nitrogen gas, or a mixed gas system containing at least a fluorine-based gas and a chlorine-based gas.

As described above, when the organic silicon film pattern is oxidized, the obtained oxidized film pattern acts as an anti-reflection film at the time of pattern exposure, and at the time of etching the film to be processed, Since it acts as a hard mask, it is not necessary to interpose an antireflection film between the hard mask and the resist. As a result, the resist pattern can be faithfully transferred to the hard mask, and the film to be processed can be processed with good dimensional control.

(4) In the method of the present invention, after patterning the film to be processed, the pattern of the organic silicon film used as the etching mask may be at least one selected from the group consisting of chlorine atoms, bromine atoms and fluorine atoms. (Removal) using a gas containing oxygen and a gas containing oxygen atoms.

That is, the organic silicon film pattern after patterning the film to be processed is obtained by adding an oxygen atom-containing gas to at least one gas selected from the group consisting of chlorine, bromine and fluorine atoms.
By exposing the organic silicon film pattern to plasma generated by using a gas to which a gas containing a small amount of atoms is added, the organic silicon film pattern can be completely removed without leaving.
At this time, the film to be processed is not removed.

At the time of peeling, chlorine, bromine or fluorine radicals in the plasma accelerate the etching of the film to be processed, so that a small amount of the gas containing these atoms is required. The shaving amount of the film to be processed can be reduced. This is probably because the organic silicon film tends to take in chlorine, iodine, or bromine atoms into the film when etching the organic silicon film, and accordingly, when peeling the organic silicon film, chlorine, bromine, or fluorine is removed. It is believed that the amount of atoms can be reduced.

In particular, when an organic silicon compound having the structure represented by the above general formula [12] is used for the main chain, the peeling rate of the organic silicon film can be increased,
The organic silicon film can be peeled off while reducing the amount of shaving of the film to be processed. Probably, the organosilicon compound having the structure represented by the general formula 12 reacts with chlorine, bromine, or fluorine radical and is easily vaporized.

A preferred embodiment of the mode (4) will be exemplified below.

(A) In the step of removing the organic silicon film, a gas containing CF ₄ , SF ₆ , or NF ₃ is used.

(B) a step of treating the organic silicon film with a gas containing oxygen atoms and a step of treating the organic silicon film with a gas containing at least one selected from the group consisting of chlorine, bromine and fluorine atoms; Or alternate.

(C) a step of treating the organic silicon film with a gas containing oxygen atoms, CF ₄ , SF ₆ and NF
_And a step of treating with a gas containing at least one selected from the group consisting of ₃ or alternately.

(D) Keeping the temperature of the processing substrate at about 100 ° C. or less when the organic silicon film is peeled off. When the temperature of the processing substrate is 100 ° C. or lower, the reaction of vitrifying the organic silicon film due to oxygen radicals is less likely to occur, and the peeling rate of the organic silicon film is improved.

(E) After exposing the organosilicon film to a plasma generated using a gas containing at least one selected from the group consisting of chlorine, bromine and fluorine atoms and oxygen atoms, an amine-based film is formed. Perform treatment with a solution containing a solvent.

(F) The organic silicon film is formed by using an amine solvent,
Exfoliation by immersion in a solution containing at least one of hydrogen fluoride, ammonium fluoride, sodium hydroxide, sulfuric acid, and hydrogen peroxide, or after such immersion, an amine-based solvent, hydrogen fluoride , Ammonium fluoride,
Immersion in a solution containing one of sodium hydroxide, sulfuric acid, and hydrogen peroxide, which is different from the above solution, and stripping.

In particular, when the organosilicon compound has the structure represented by the general formula 12 in the main chain,
The solution easily permeates into the film, and the peeling rate is improved.

(G) In (f), after the organic silicon film is immersed in the above solution, the film is exposed to plasma generated using a gas containing oxygen atoms. Further, the gas containing an oxygen atom can include a gas containing any of a chlorine atom, a bromine atom, and a fluorine atom. Examples of the gas containing any of a chlorine atom, a bromine atom and a fluorine atom include CF ₄ , SF ₆ and NF ₃ .

(H) In (f), the organic silicon film is immersed in a solution containing sulfuric acid and hydrogen peroxide, and then immersed in a solution containing hydrogen fluoride or ammonium fluoride.

The organic silicon film is stripped using the method according to the preferred embodiment described above. At this time, the resist pattern may be stripped at the same time.

Example 1 First, an organic silicon film containing an organic silicon compound represented by the formula [1-1] was formed on a silicon wafer by the methods shown in the following (A1) to (A10). Further, a resist and a conventional antireflection film for comparison were formed on a silicon wafer by the following methods (R1) to (R4).

(A1): A solution material prepared by dissolving 10 g of an organosilicon compound having a weight-average molecular weight of 5,000, represented by the formula [1-1], in 90 g of toluene was applied onto a base substrate by spin coating. . Next, the base substrate was heated at 100 ° C. for 90 seconds using a hot plate,
The solvent was evaporated and dried to form an organic silicon film.

(A2): In (A1), an organosilicon compound having a weight average molecular weight of 2,500 was used.

(A3): In (A1), an organosilicon compound having a weight average molecular weight of 1,000 was used.

(A4): In (A1), an organosilicon compound having a weight average molecular weight of 500 was used.

(A5): The solution material prepared as in (A1) was applied on an undersubstrate by a spin coating method, and then heated to 500 ° C. in a nitrogen atmosphere (oxygen concentration: 50 ppm or less) using a hot plate. For 1 hour to crosslink the organic silicon film.

(A6): The solution material prepared as in (A1) was applied on an undersubstrate by spin coating, and then heated at 100 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. After that, the entire surface of the organic silicon film is irradiated with a KrF excimer laser at an exposure dose of 400 mJ / cm ² under a nitrogen atmosphere (oxygen concentration 50 ppm or less),
The organic silicon film was crosslinked.

(A7): The solution material prepared as in (A1) was applied on an undersubstrate by spin coating, and then 90 ° C. at 160 ° C. using a hot plate under a nitrogen atmosphere (oxygen concentration 50 ppm or less). While heating for seconds
The entire surface of the organic silicon film was irradiated with a KrF excimer laser at an exposure amount of 80 mJ / cm ² to crosslink the organic silicon film.

(A8): 10 g of an organosilicon compound having a weight average molecular weight of 5,000 represented by the formula [1-1] and a compound of the formula [3-
61], and a solution material prepared by dissolving 1 g of a cross-linking agent and 0.1 g of silyl peroxide as a radical generator in 89.9 g of toluene was applied onto a base substrate by spin coating. Then, under a nitrogen atmosphere (oxygen concentration 50
(ppm or less) using a hot plate at 180 ° C. for 1 hour to crosslink the organic silicon film.

(A9) 10 g of an organosilicon compound having a weight average molecular weight of 5,000 represented by the formula [1-1] and a compound of the formula [3-
61], a solution material prepared by dissolving 1 g of a crosslinking agent and 0.1 g of silyl peroxide as a radical generator in 89.9 g of toluene was applied onto a base substrate by spin coating. Then, using a hot plate, 100
After heating at 90 ° C. for 90 seconds to evaporate and dry the solvent, the entire surface of the organic silicon film was exposed to a KrF excimer laser under a nitrogen atmosphere (oxygen concentration: 50 ppm or less) at a dose of 150 mJ / cm.
Irradiation was performed at ² to crosslink the organic silicon film.

(A10) 10 g of an organosilicon compound having a weight average molecular weight of 5,000 represented by the formula [1-1] and a compound of the formula [3]
-61], and a solution material prepared by dissolving 1 g of a crosslinking agent and 0.1 g of a silyl peroxide as a radical generator in 88.9 g of toluene was applied on a base substrate by a spin coating method. Then, under a nitrogen atmosphere (oxygen concentration 50
ppm or less) at 160 ° C. using a hot plate at 90 ° C.
While heating for 2 seconds, the entire surface of the organic silicon film was irradiated with a KrF excimer laser at an exposure amount of 10 mJ / cm ² to crosslink the organic silicon film.

(R1): 10 g of an inhibitor resin in which 50% of hydroxyl groups of polyvinyl phenol having a weight average molecular weight of 11,000 were substituted with a tertiary butoxycarbonyl group, 0.01 g of sulfonimide as an acid generator was mixed with 89 l of ethyl lactate. A resist solution prepared by dissolving the resist solution in 99 g was applied onto a base substrate by a spin coating method. Then
The resist was formed by heating at 120 ° C. for 60 seconds using a hot plate.

(R2): A solution material prepared by dissolving 10 g of polysulfone in 90 g of cyclohexanone was applied on a base substrate by spin coating, and then heated at 220 ° C. for 90 seconds using a hot plate.

(R3): 10 g of polybenzimidazole
Was dissolved in 90 g of cyclohexanone, and applied to a base substrate by a spin coating method, and then heated at 220 ° C. for 90 seconds using a hot plate.

(R4): A solution material prepared by dissolving 10 g of novolak resin in 90 g of toluene was applied on a base substrate by spin coating, and then heated at 320 ° C. for 90 seconds using a hot plate.

The glass transition temperature of the organic silicon film formed by the above-described methods (A1) to (A10) was measured. The results are shown in Table 1 below.

Next, (A1) to (A10) and (R1) were obtained using a magnetron-type reactive ion etching apparatus.
The films obtained by the methods (1) to (R4) were etched under the following etching conditions (P1) to (P4), and the etching characteristics were examined.

(P1) Etching gas: flow rate 120S
CF _{4 of} CCM, power density: 2 W / cm ² , degree of vacuum: 2
0 mTorr, substrate temperature: 50 ° C. (P2) etching gas: Cl at a flow rate of 200 SCCM
₂ , power density: 1.5 W / cm ² , degree of vacuum: 30 mTo
rr, substrate temperature: 80 ° C. (P3) etching gas: HB at a flow rate of 150 SCCM
r, power density: 1.7 W / cm ² , degree of vacuum: 12 mTo
rr, substrate temperature: 50 ° C. (P4) etching gas: flow rate 20/180 SCCM
CF ₄ / Cl ₂ , power density: 2 W / cm ² , degree of vacuum:
12 mTorr, substrate temperature: 50 ° C. As a result of observing the state of the organic silicon film after etching with a scanning electron microscope (SEM), the films (A1) and (A2) were obtained under any of the conditions (P1) to (P4). Figure 4
As shown in (b), it was found that the material was changed into a sponge shape and the etching was not performed normally. Also, (A3)
The films (A10) to (A10) were also deteriorated when etched under the condition of (P1), and it was found that etching was not performed properly even if the film had a high glass transition temperature when etched with a fluorine-based gas.

On the other hand, when the films (A3) to (A10) were etched under the conditions of (P2) to (P4), there was no alteration as shown in FIG. I confirmed that

The etching rate of the resist, the etching selectivity between the resist and the organic silicon film (= the etching rate of the organic silicon film / the etching rate of the resist), and the etching selectivity between the resist and the conventional antireflection film for comparison (= Etching rate of conventional antireflection film / etching rate of resist) is shown in Table 1 below.

As shown in Table 1 below, (A3) to (A1)
The selectivity of the film 0) is about 2 or more, which is higher than that of the conventional antireflection film. Therefore, even if the film thickness of the resist is reduced, the resist is not removed in the middle,
It becomes possible to etch the antireflection film.

[0197]

[Table 1]

[0198]

[Table 2]

[0199]

[Table 3]

[0200]

[Table 4] Example 2 This example shows a case in which fullerene (C60) was added in Example 1 in order to generate photoconductivity in the organic silicon film.

(B1): A solution material prepared by dissolving 10 g of an organosilicon compound having a weight average molecular weight of 5,000 represented by the formula [1-1] and 0.01 g of fullerene in 89.99 g of toluene was used as a base material by a spin coating method. Coated on substrate. Next, 9 hours at 100 ° C. using a hot plate.
The solvent was vaporized and dried by heating for 0 second to form an organic silicon film.

(B2): In (B1), an organosilicon compound having a weight average molecular weight of 2,500 was used.

(B3): In (B1), an organosilicon compound having a weight average molecular weight of 1,000 was used.

(B4): In (B1), an organosilicon compound having a weight average molecular weight of 500 was used.

(B5): The solution material prepared as in (B1) was applied on a base substrate by a spin coating method, and then was heated at 500 ° C. for 1 hour using a hot plate under a nitrogen atmosphere (oxygen concentration: 50 ppm or less). Heat was applied to crosslink the organic silicon film.

(B6): The solution material prepared as in (B1) was applied on an underlying substrate by spin coating, and then heated at 100 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. Under nitrogen atmosphere (oxygen concentration 5
(0 ppm or less), the entire surface of the organic silicon film was irradiated with a KrF excimer laser at an exposure dose of 400 mJ / cm 2 to crosslink the organic silicon film.

(B7): The solution material prepared as in (B1) was applied on an underlying substrate by spin coating, and then heated at 160 ° C. for 90 seconds using a hot plate in a nitrogen atmosphere (oxygen concentration: 50 ppm). While KrF
Excimer laser is applied over the entire surface of the organic silicon film with a light exposure of 80 m.
Irradiation was performed at J / cm 2 to crosslink the organic silicon film.

(B8): 10 g of an organosilicon compound having a weight average molecular weight of 5,000 represented by the formula [1-1] and a compound of the formula [3-
61], a solution material prepared by dissolving 1 g of a cross-linking agent, 0.1 g of silyl peroxide as a radical generator, and 0.01 g of fullerene in 88.89 g of toluene was applied onto a base substrate by spin coating. Next, the organic silicon film was cross-linked by heating at 180 ° C. for 1 hour using a hot plate in a nitrogen atmosphere (oxygen concentration: 50 ppm or less).

(B9): The solution material prepared as in (B8) was applied on an underlying substrate by a spin coating method, and then heated at 100 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. Irradiating the entire surface of the organic silicon film with a KrF excimer laser at a light exposure of 150 mJ / cm 2 under a nitrogen atmosphere (oxygen concentration 50 ppm or less)
The organic silicon film was crosslinked.

(B10): The solution material prepared as in (B8) was applied on a base substrate by a spin coating method, and then was heated at 160 ° C. for 90 seconds using a hot plate under a nitrogen atmosphere (oxygen concentration: 50 ppm or less). While heating
The organic silicon film was cross-linked by irradiating the entire surface of the organic silicon film with a KrF excimer laser at an exposure amount of 10 mJ / cm 2.

The glass transition temperatures of the organosilicon films formed by the methods (B1) to (B10) were measured. The results are shown in Table 2 below.

Next, the organic silicon film obtained by (B1) to (B10) was etched under the conditions of (P1) to (P4) in Example 1 using a magnetron type reactive ion etching apparatus. The etching characteristics were examined. As a result of observing the state of the organic silicon film after the etching with a scanning electron microscope, (B1) was obtained under any of the conditions (P1) to (P4).
It was found that the films of 1) and (B2) were altered and the etching was not performed normally. Also, (B3)-
Even if the film of (B10) is etched under the condition of (P1), the film is deteriorated, and it can be seen that even if the film has a high glass transition temperature, etching is not performed properly when etching is performed with a fluorine-based gas.

The films of (B3) to (B10) were replaced with (P2) to
When etched under the condition of (P4), there is no deterioration,
It was confirmed that etching was performed normally. Table 2 below shows the etching selectivity between the resist and the organic silicon film at this time. As is clear from Table 2 below, (B
The selectivity of the films 3) to (B10) is almost 2 or more;
The selectivity is higher than that of a conventional antireflection film. Therefore,
Even if the film thickness of the resist is reduced, the antireflection film can be etched without the resist being scraped in the middle.

The results of calculating the etching selectivity between the resist and the organic silicon film are shown in Table 2 below. From Table 2 below, it can be seen that the selectivity is improved as compared with Example 1. This is probably because the plasma emission during etching caused conductivity in the anti-reflection film, and radicals in the plasma reacted with silicon in the anti-reflection film to easily generate volatile products.

[0215]

[Table 5]

[0216]

[Table 6] Example 3 First, an organosilicon compound (m / m) represented by the formula [1-82] was obtained by the following methods (C1) to (C10).
An organic silicon film containing (n = 4/1) was formed on a base substrate.

(C1): A solution material prepared by dissolving 10 g of an organosilicon compound having a weight-average molecular weight of 2,000 represented by the formula [1-82] in 90 g of anisole was applied on a base substrate by spin coating. Next, the solvent was vaporized and dried by heating at 160 ° C. for 90 seconds using a hot plate to form an organic silicon film.

(C2): In (C1), an organosilicon compound having a weight average molecular weight of 4,000 was used.

(C3): In (C1), an organosilicon compound having a weight average molecular weight of 8,000 was used.

(C4): In (C1), an organosilicon compound having a weight average molecular weight of 16,000 was used.

(C5): The solution material prepared as in (C2) was applied on a base substrate by a spin coating method, and then heated at 350 ° C. using a hot plate under a nitrogen atmosphere (oxygen concentration: 50 ppm or less). By heating for an hour, the organic silicon film was crosslinked.

(C6): The solution material prepared as in (C2) was applied on an underlying substrate by a spin coating method, and then heated at 160 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. Next, an ArF excimer laser is applied to the entire surface of the organic silicon film at a light exposure of 150 mJ / cm 2.
To crosslink the organic silicon film.

(C7): The solution material prepared as in (C2) was applied on an undersubstrate by spin coating, and then 90 ° C. at 160 ° C. using a hot plate under a nitrogen atmosphere (oxygen concentration 50 ppm or less). While heating for seconds
The entire surface of the organic silicon film was irradiated with an ArF excimer laser at an exposure amount of 10 mJ / cm 2 to crosslink the organic silicon film.

(C8) 10 g of an organosilicon compound having a weight average molecular weight of 4,000 represented by the formula [1-82] and a compound of the formula [4
-12] to 0.1 g of anisole 8
A solution material prepared by dissolving the solution in 9.9 g was applied on a base substrate by a spin coating method. Next, the organic silicon film was cross-linked by heating at 180 ° C. for 1 hour using a hot plate in a nitrogen atmosphere (oxygen concentration: 50 ppm or less).

(C9): The solution material prepared as in (C8) was applied on an underlying substrate by a spin coating method, and then heated at 160 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. Next, an ArF excimer laser was irradiated onto the entire surface of the organic silicon film at an exposure amount of 60 mJ / cm 2 to crosslink the organic silicon film.

(C10): The solution material prepared as in (C8) was applied on an undersubstrate by a spin coating method, and then 90 ° C. at 160 ° C. using a hot plate under a nitrogen atmosphere (oxygen concentration: 50 ppm or less). An ArF excimer laser was irradiated on the entire surface of the organic silicon film at an exposure amount of 10 mJ / cm 2 while heating for 2 seconds to crosslink the organic silicon film.

The glass transition temperatures of the organosilicon films formed by the methods (C1) to (C10) were measured. The results are shown in Table 3 below.

Next, using a magnetron type reactive ion etching apparatus, the resists (C1) to (C10), the resists formed by the methods (R1) to (R4) of Example 1, and the conventional antireflection The film was etched under the following etching conditions (P
Etching was performed in each of 5) to (P8), and the etching characteristics of those films were examined.

(P5) Etching gas: flow rate 120S
CF _{4 of} CCM, power density: 1.8 W / cm ² , degree of vacuum: 20 mTorr, substrate temperature: 80 ° C. (P6) Etching gas: flow rate 20/180 SCCM
Cl ₂ / BCl ₃ , power density: 1.5 W / cm ² , vacuum degree: 30 mTorr, substrate temperature: 80 ° C. (P7) etching gas: flow rate 180/20 SCCM
Of Cl ₂ / HBr, power density: 1.2 W / cm ^2, the degree of vacuum: 12 mTorr, substrate temperature: 50 ° C. (P8) Etching gas: flow rate 200 SCCM CF
₃ Cl, power density: 1.2 W / cm ² , degree of vacuum: 12 m
Torr, substrate temperature: 50 ° C. As a result of observing the state of the organic silicon film after etching with a scanning electron microscope, the films (C1) and (C2) were deteriorated under any of the conditions (P5) to (P8). It was found that the etching was not performed normally. Also, (C
The films 3) to (C10) are also deteriorated when etched under the condition (P5), and it can be seen that even if the film has a high glass transition temperature, etching is not performed properly when etching with a fluorine-based gas.

The films of (C3) to (C10) were replaced with (P6) to
When etched under the condition of (P8), there is no deterioration,
It was confirmed that etching was performed normally. Further, the etching rate of the resist, the etching selectivity of the resist and the organic silicon film (= the etching rate of the organic silicon film / the etching rate of the resist), and the etching selectivity of the resist and the conventional antireflection film (for comparison) = Etching rate of conventional anti-reflective coating /
The etching rate of the resist is similarly shown in Table 3 below.

As apparent from Table 3 below, (C3) to
The selectivity of the film (C10) is about 2 or more, which is higher than that of the conventional antireflection film. Therefore, even if the thickness of the resist is reduced, the antireflection film can be etched without the resist being scraped in the middle.

[0232]

[Table 7]

[0233]

[Table 8] Example 4 This example shows a case in which fullerene was added in Example 3 to cause photoconductivity in the organic silicon film.

(D1): A solution material prepared by dissolving 10 g of an organosilicon compound having a weight average molecular weight of 2,000 represented by the formula [1-82] and 0.01 g of fullerene in 89.99 g of anisole was used as a base material by a spin coating method. Coated on substrate. Then, using a hot plate at 160 ° C.
For 90 seconds to evaporate and dry the solvent to form an organic silicon film.

(D2): In (D1), an organosilicon compound having a weight average molecular weight of 4,000 was used.

(D3): In (D1), an organosilicon compound having a weight average molecular weight of 8,000 was used.

(D4): In (D1), an organosilicon compound having a weight average molecular weight of 16,000 was used.

(D5): The solution material prepared as in (D2) was applied on an underlying substrate by a spin coating method, and then heated at 350 ° C. using a hot plate under a nitrogen atmosphere (oxygen concentration: 50 ppm or less). By heating for an hour, the organic silicon film was crosslinked.

(D6): The solution material prepared as in (D2) was applied on an underlying substrate by a spin coating method, and then heated at 160 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. Next, an ArF excimer laser is applied to the entire surface of the organic silicon film at a light exposure of 150 mJ / cm 2.
To crosslink the organic silicon film.

(D7): The solution material prepared as in (D2) was applied on an undersubstrate by spin coating, and then 90 ° C. at 160 ° C. using a hot plate under a nitrogen atmosphere (oxygen concentration 50 ppm or less). While heating for seconds
The entire surface of the organic silicon film was irradiated with an ArF excimer laser at an exposure amount of 10 mJ / cm 2 to crosslink the organic silicon film.

(D8): 10 g of an organosilicon compound having a weight average molecular weight of 4,000 represented by the formula [1-82] and a compound of the formula [4
-12], a solution material prepared by dissolving 0.1 g of the radical generator and 0.01 g of fullerene in 89.89 g of anisole was applied to the underlying substrate by spin coating. Next, the organic silicon film was cross-linked by heating at 180 ° C. for 1 hour using a hot plate in a nitrogen atmosphere (oxygen concentration: 50 ppm or less).

(D9): The solution material prepared as in (D8) was applied on an underlying substrate by a spin coating method, and then heated at 160 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. Next, an ArF excimer laser was irradiated onto the entire surface of the organic silicon film at an exposure amount of 60 mJ / cm 2 to crosslink the organic silicon film.

(D10): The solution material prepared as in (D8) was applied on an undersubstrate by spin coating, and then 90 ° C. at 160 ° C. using a hot plate under a nitrogen atmosphere (oxygen concentration 50 ppm or less). An ArF excimer laser was irradiated on the entire surface of the organic silicon film at an exposure amount of 10 mJ / cm 2 while heating for 2 seconds to crosslink the organic silicon film.

The glass transition temperature of the organic silicon film formed by the above methods (D1) to (D10) was measured. The results are shown in Table 4 below.

Next, (D1) to (D10) and the resist were etched under the conditions of (P5) to (P8) in Example 3 using a magnetron type reactive ion etching apparatus, and the films were etched. The etching characteristics were examined.

The state of the organic silicon film after etching was observed with a scanning electron microscope. As a result, under any of the conditions (P5) to (P8), the films (D1) and (D2) were altered and the etching was normal. Turned out not to be done.
Also, the films (D3) to (D10) are deteriorated when etched under the condition of (P5), and it can be seen that even if the film has a high glass transition temperature, etching is not performed properly when etching is performed with a fluorine-based gas. .

The films of (D3) to (D10) were replaced with (P6) to
When etched under the condition of (P8), there is no deterioration,
It was confirmed that etching was performed normally. Table 4 shows the etching selectivity between the resist and the organic silicon film.
Shown in As is clear from Table 4 below, the selectivity is almost 2
As described above, the selectivity is higher than that of the conventional antireflection film. Therefore, even if the thickness of the resist is reduced, the antireflection film can be etched without the resist being scraped in the middle.

The results of measuring the etching selectivity between the resist and the organic silicon film are also shown in Table 4 below. Table 4 below
From this, it can be seen that the selectivity is improved as compared with Example 3. This is probably because the plasma emission during etching caused conductivity in the anti-reflection film, and radicals in the plasma reacted with silicon in the anti-reflection film to easily generate volatile products.

[0249]

[Table 9] Example 5 First, an organic silicon film containing an organic silicon compound represented by the formula [1-95] was formed on a silicon wafer by the following methods (E1) to (E10). However, n / m in the copolymer represented by the formula [1-95] is (E
In all of 1) to (E10), n / m = 1/4.

(E1): A solution material prepared by dissolving 10 g of an organosilicon compound having a weight average molecular weight of 1,000 represented by the formula [1-95] in 90 g of anisole was applied on a base substrate by spin coating. Next, the solvent was vaporized and dried by heating at 160 ° C. for 90 seconds using a hot plate to form an organic silicon film.

(E2): In (E1), an organosilicon compound having a weight average molecular weight of 3,000 was used.

(E3): In (E1), an organosilicon compound having a weight average molecular weight of 6,000 was used.

(E4): In (E1), an organosilicon compound having a weight average molecular weight of 12,000 was used.

(E5): The solution material prepared as in (E2) was applied on an underlying substrate by a spin coating method, and then was heated at 400 ° C. for 1 hour using a hot plate in a nitrogen atmosphere (oxygen concentration: 50 ppm). Heat was applied to crosslink the organic silicon film.

(E6): The solution material prepared as in (E2) was applied on an underlying substrate by spin coating, and then heated at 160 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. Next, an i-line (wavelength 365 nm) of a mercury lamp was applied to the entire surface of the organic silicon film at an exposure amount of 500 mJ.
/ Cm 2 to crosslink the organic silicon film. (E7): After applying the solution material prepared as in (E2) on a base substrate by spin coating, the solution is heated at 160 ° C. for 90 seconds using a hot plate in a nitrogen atmosphere (oxygen concentration: 50 ppm). Then, i-line of a mercury lamp was irradiated on the entire surface of the organic silicon film at an exposure amount of 10 mJ / cm 2 to crosslink the organic silicon film.

(E8): 10 g of an organosilicon compound having a weight average molecular weight of 3,000 represented by the formula [1-95] and a compound of the formula [1]
-1], a solution material prepared by dissolving 2 g of an organic silicon compound having a weight average molecular weight of 1,000 in 88 g of anisole was applied onto a base substrate by a spin coating method. Next, the organic silicon film was crosslinked by heating at 180 ° C. for 1 hour using a hot plate under a nitrogen atmosphere (oxygen concentration: 50 ppm).

(E9): The solution material prepared as in (E8) was applied on an undersubstrate by spin coating, and then heated at 160 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. Next, the entire surface of the organic silicon film was irradiated with i-rays from a mercury lamp at an exposure amount of 100 mJ / cm 2 to crosslink the organic silicon film.

(E10): The solution material prepared as in (E8) was applied on a base substrate by a spin coating method, and then was heated at 160 ° C. for 90 seconds using a hot plate under a nitrogen atmosphere (oxygen concentration: 50 ppm). While heating, apply i-line of a mercury lamp over the entire surface of the organic silicon film with an exposure amount of 80 mJ / c.
Irradiation at m2 crosslinked the organic silicon film.

The glass transition temperature of the organic silicon film formed by the above methods (E1) to (E10) was measured. The results are shown in Table 5 below.

Next, using a magnetron-type reactive ion etching apparatus, the resists formed by the methods (E1) to (E10) and the methods (R1) to (R4) of Example 1 and the conventional antireflection The film was etched under the following etching conditions (P9) to (P12), respectively,
The etching characteristics of the films 1) to (E10) were examined.

(P9) Etching gas: flow rate 120S
CF _{4 of} CCM, power density: 3 W / cm ² , degree of vacuum: 7
5 mTorr, substrate temperature: 50 ° C. (P10) etching gas: flow rate 180/20 SCC
M Cl ₂ / He, power density: 1.5 W / cm ² , degree of vacuum: 30 mTorr, substrate temperature: 80 ° C. (P11) Etching gas: flow rate 190/10 SCC
M Cl ₂ / O ₂ , power density: 1.2 W / cm ² , degree of vacuum: 12 mTorr, substrate temperature: 50 ° C. (P12) Etching gas: C at a flow rate of 200 SCCM
F ₃ Cl, power density: 1.1 W / cm ² , degree of vacuum: 12
mTorr, substrate temperature: 50 ° C. As a result of observing the state of the organic silicon film after etching with a scanning electron microscope, the films (E1) and (E2) were deteriorated under any of the conditions (P9) to (P12). It was found that the etching was not performed normally. Also, (E
The films 3) to (E10) were also deteriorated when etched under the conditions of (P9), and it was found that etching was not performed properly when etching was performed with a fluorine-based gas even in a film having a high glass transition temperature.

On the other hand, when the films (E3) to (E10) were etched under the conditions of (P10) to (P12), it was confirmed that there was no deterioration and the etching was performed normally. The etching rate of the resist, the etching selectivity of the resist and the organic silicon film (= etching rate of the organic silicon film / etching rate of the resist), and the etching selectivity of the resist and the conventional antireflection film (= conventional) Table 5 shows the etching rate of the anti-reflection film of the mold / the etching rate of the resist.

As shown in Table 5 below, the selectivity is almost 2 or more, which is higher than that of the conventional antireflection film. Therefore, even if the thickness of the resist is reduced, the antireflection film can be etched without the resist being scraped in the middle.

[0264]

[Table 10]

[0265]

[Table 11] Example 6 First, an organic silicon film containing an organic silicon compound represented by the formula [1-34] was formed on a silicon wafer by the following methods (F1) to (F10).

(F1): A solution material prepared by dissolving 10 g of an organosilicon compound having a weight average molecular weight of 1,000 represented by the formula [1-34] in 90 g of toluene was applied to a base substrate by a spin coating method. Next, the solvent was vaporized and dried by heating at 160 ° C. for 90 seconds using a hot plate to form an organic silicon film.

(F2): In (F1), an organosilicon compound having a weight average molecular weight of 3,000 was used.

(F3): In (F1), an organosilicon compound having a weight average molecular weight of 6,000 was used.

(F4): In (F1), an organosilicon compound having a weight average molecular weight of 12,000 was used.

(F5): The solution material prepared as in (F2) was applied on a base substrate by a spin coating method, and then heated at 300 ° C. using a hot plate under a nitrogen atmosphere (oxygen concentration: 50 ppm or less). By heating for an hour, the organic silicon film was crosslinked.

(F6): The solution material prepared as in (F2) was applied on an underlying substrate by spin coating, and then heated at 160 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. Next, an ArF excimer laser is applied to the entire surface of the organic silicon film at a light exposure of 200 mJ / cm 2.
To crosslink the organic silicon film.

(F7): The solution material prepared as in (F2) was applied on an undersubstrate by a spin coating method, and then 90 ° C. at 160 ° C. using a hot plate under a nitrogen atmosphere (oxygen concentration: 50 ppm or less). While heating for seconds
The entire surface of the organic silicon film was irradiated with an ArF excimer laser at an exposure amount of 30 mJ / cm 2 to crosslink the organic silicon film.

(F8): 10 g of an organosilicon compound having a weight average molecular weight of 3,000 represented by the formula [1-34], a compound of the formula [3
A solution material prepared by dissolving 1 g of a crosslinking agent represented by -49] and 0.01 g of a radical generator represented by the formula [4-1] in 88.99 g of toluene was applied onto a base substrate by a spin coating method. Then, under a nitrogen atmosphere (oxygen concentration 50
(ppm or less) using a hot plate at 180 ° C. for 1 hour to crosslink the organic silicon film.

(F9): The solution material prepared as in (F8) was applied on an underlying substrate by a spin coating method, and then heated at 100 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. Next, the entire surface of the organic silicon film was irradiated with an ArF excimer laser at an exposure amount of 80 mJ / cm 2 to crosslink the organic silicon film.

(F10): The solution material prepared as in (F8) was applied on an undersubstrate by spin coating, and then heated at 160 ° C. using a hot plate in a nitrogen atmosphere (oxygen concentration: 50 ppm or less) at 160 ° C. An ArF excimer laser was irradiated on the entire surface of the organic silicon film at an exposure amount of 10 mJ / cm 2 while heating for 2 seconds to crosslink the organic silicon film.

The glass transition temperature of the organic silicon film formed by the above-mentioned methods (F1) to (F10) was measured. The results are shown in Table 6 below.

Next, using a magnetron type reactive ion etching apparatus, the films (F1) to (F10) were etched under the conditions (P1) to (P4) of Example 1, respectively, and the films were etched. The characteristics were investigated. That is, as a result of observing the state of the organic silicon film after etching with a scanning electron microscope, under any of the conditions (P1) to (P4),
It was found that the films of (F1) and (F2) were altered and the etching was not performed normally. (F3) ~
Even when the film of (F10) was etched under the condition of (P1), the film was deteriorated, and it was found that even if the film had a high glass transition temperature, etching was not performed properly when etching was performed with a fluorine-based gas.

On the other hand, when the films (F3) to (F10) were etched under the conditions of (P2) to (P4), there was no deterioration and it was confirmed that the etching was performed normally. Table 6 below similarly shows the etching selectivity between the resist and the organic silicon film.

As apparent from Table 6 below, (F3) to
The selectivity of the film (F10) is about 2 or more, which is higher than that of the conventional antireflection film. Therefore, even if the thickness of the resist is reduced, the antireflection film can be etched without the resist being scraped in the middle.

[0280]

[Table 12] Example 7 First, an organic silicon film containing an organic silicon compound represented by the formula [1-18] was formed on a silicon wafer by the following methods (G1) to (G10).

(G1): A solution material prepared by dissolving 10 g of an organosilicon compound having a weight average molecular weight of 1,000 represented by the formula [1-18] in 90 g of toluene was applied on a base substrate by a spin coating method. Next, the solvent was vaporized and dried by heating at 160 ° C. for 90 seconds using a hot plate to form an organic silicon film.

(G2): In (G1), an organosilicon compound having a weight average molecular weight of 3,000 was used.

(G3): In (G1), an organosilicon compound having a weight average molecular weight of 6,000 was used.

(G4): In (G1), an organosilicon compound having a weight average molecular weight of 12,000 was used.

(G5): The solution material prepared as in (G2) was applied on a base substrate by a spin coating method, and then heated at 400 ° C. using a hot plate under a nitrogen atmosphere (oxygen concentration: 50 ppm or less). By heating for an hour, the organic silicon film was crosslinked.

(G6): The solution material prepared as in (G2) was applied on an underlying substrate by spin coating, and then heated at 160 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. Next, a KrF excimer laser is applied to the entire surface of the organic silicon film at an exposure amount of 400 mJ / cm 2.
To crosslink the organic silicon film.

(G7): The solution material prepared as in (G2) was applied on an undersubstrate by spin coating, and then heated at 160 ° C. using a hot plate in a nitrogen atmosphere (oxygen concentration: 50 ppm or less) at 160 ° C. While heating for seconds
The organic silicon film was irradiated with a KrF excimer laser at an exposure amount of 100 mJ / cm 2 to crosslink the organic silicon film.

(G8): 10 g of an organic silicon compound having a weight average molecular weight of 3,000 represented by the formula [1-18] and a compound of the formula [3
A solution material prepared by dissolving 1 g of the crosslinking agent shown in [-8] and 0.01 g of the radical generator shown in the formula [4-8] in 88.99 g of toluene was applied on the base substrate by spin coating. Then, under a nitrogen atmosphere (oxygen concentration 50p
(pm or less) using a hot plate at 180 ° C. for 1 hour to crosslink the organic silicon film.

(G9): The solution material prepared as in (G8) was applied on an underlying substrate by a spin coating method, and then heated at 100 ° C. for 90 seconds using a hot plate to evaporate and dry the solvent. Next, a KrF excimer laser is applied to the entire surface of the organic silicon film at an exposure amount of 100 mJ / cm 2.
To crosslink the organic silicon film.

(G10): The solution material prepared as in (G8) was applied on an undersubstrate by a spin coating method, and then heated at 180 ° C. using a hot plate under a nitrogen atmosphere (oxygen concentration: 50 ppm or less). While heating for 2 seconds, the entire surface of the organic silicon film was irradiated with a KrF excimer laser at an exposure amount of 10 mJ / cm 2 to crosslink the organic silicon film.

The glass transition temperature of the organic silicon film formed by the above methods (G1) to (G10) was measured. The results are shown in Table 7 below.

Next, the films (G1) to (G10) were etched under the conditions (P5) to (P8) of Example 3 using a magnetron type reactive ion etching apparatus, and the etching characteristics were examined. . That is, as a result of observing the state of the organic silicon film after etching with a scanning electron microscope, (P
Under any of the conditions 5) to (P8), (G1) and (G8)
It was found that the film of 2) was deteriorated and the etching was not performed normally. Further, the films (G3) to (G10) are also deteriorated when etched under the condition (P5).
It was found that even if the film had a glass transition temperature of 0 ° C. or more, etching was not performed properly when etching was performed with a fluorine-based gas.

On the other hand, when the films (G3) to (G10) were etched under the conditions of (P6) to (P8), there was no such alteration, and it was confirmed that the etching was performed normally. did. Table 7 below similarly shows the etching selectivity between the resist and the organic silicon film at this time.

As shown in Table 7 below, the selectivity is about 2 or more, which is higher than that of the conventional antireflection film. Therefore, even if the thickness of the resist is reduced, the antireflection film can be etched without the resist being scraped in the middle.

[0295]

[Table 13] Example 8 The average molecular weight 15000 (n / m = 4 /
5 g of the polysilane of 1) was dissolved in 95 g of anisole to prepare a solution material for the organic silicon film. A solution material of an organic silicon film was applied on a silicon wafer to be processed by a spin coating method, baked at 200 ° C. for 90 seconds, and the solvent was dried. At this time, the thickness of the organic silicon film is 950 angstroms. The glass transition temperature is 125 ° C.

[0296]

Embedded image The thickness of the organic silicon film was determined as follows. That is, the complex refractive index at λ = 248 nm measured by the spectroscopic ellipsometer is n = 2.10 and k = 0.30. Using the values shown in Table 8 below as the complex refractive index at λ = 248 nm of the antireflection film, the resist, and the silicon substrate, the light reflectance at the interface between the resist and the organic silicon film was calculated, and the organic silicon film after baking was calculated. Was applied so that the film thickness became 950 angstroms, which is the minimum point of the reflectance.

[0297]

[Table 14] Next, a chemically amplified positive resist (APEX-E, manufactured by Shipley) was applied onto the organic silicon film, and baked at 98 ° C. for 120 seconds. The resist film thickness after baking is 1500 angstroms. Further, exposure was performed with a reduction optical stepper using a KrF excimer laser as a light source (exposure amount: 78 mJ / cm ² ).
For 120 seconds. And 0.2
Development was performed for 90 seconds with a 1N TMAH developer to form a 0.18 μm line and space pattern.

When the shape of the resist pattern thus obtained was observed, no tailing or erosion was observed, and a good resist profile was obtained. The thickness of the resist was changed in the range of 500 Å to 1500 Å, and the resist pattern dimension was measured at each resist thickness. As a result, it was found that the dimensional variation caused by the standing wave generated in the resist film was negligible.

Next, the organic silicon film was etched using the formed resist pattern as a mask.
As the etching apparatus, a magnetron type RIE apparatus was used, and Cl ₂ was flowed as a source gas at a flow rate of 80 SCCM, and etching was performed at an excitation power of 200 W. As a result, even after the etching of the organic silicon film was completed, the resist pattern was not completely removed, and the organic silicon film was not changed in quality by the etching, and was normally etched. As a result, etching could be performed with good dimensional control.

Example 9 Polysilane 8 having an average molecular weight of 17000 represented by the following formula 14
g was dissolved in 92 g of cyclohexanone to prepare a solution material for the organic silicon film. 5000 angstrom thick Si film formed by sputtering on a silicon substrate
The solution material of the organic silicon film was applied on the O ₂ film by a spin coating method, and then baked at 200 ° C. for 300 seconds to crosslink the organic silicon compound to obtain an organic silicon film having a glass transition temperature of 153 ° C. The thickness of the organic silicon film is 5000 angstroms.

[0301]

Embedded image Next, a chemically amplified positive resist (Shipley,
UV6), and baked at 135 ° C. for 120 seconds. The resist film thickness after baking is 3000 angstroms. Further, exposure was performed with a reduction optical stepper using a KrF excimer laser as a light source (exposure amount 2).
Baking was performed at 135 ° C. for 120 seconds at 8 mJ / cm ² . Then, a development process was performed for 90 seconds using a 0.21 N TMAH developer to form a 0.18 μm line and space pattern. When the dimensions of the resist pattern were measured by changing the thickness of the resist,
No dimensional change due to standing waves generated in the resist film was observed, and it was found that the reflected light to the resist was sufficiently suppressed.

Next, the organic silicon film was etched using the resist pattern as a mask. As the etching apparatus, a magnetron type RIE apparatus was used, and Cl ₂ was flowed as a source gas at a flow rate of 200 SCCM, and the etching was performed under the conditions of an excitation power of 200 W. In addition, the organic silicon film was normally etched without deterioration. When the dimensional conversion difference after the end of the etching of the organic silicon film is defined by YX in FIGS. 1D and 1E, the dimensional conversion difference generated at this time is −0.005 μm, which is within an allowable range. I understood.

Furthermore, the SiO ₂ film was etched using the etched organic silicon film and the resist pattern remaining after the etching on the organic silicon film as a mask. As an etching apparatus, a magnetron type RIE apparatus was used, and CF ₄ and H ₂ were supplied at a flow rate of 20%, respectively.
When etching was performed under the conditions of SCCM and 30 SCCM and an excitation power of 0.8 kW, the SiO ₂ film could be etched without the organic silicon film being eliminated halfway. Then, after infiltrating into xylene for 300 seconds, ashing treatment was performed with oxygen plasma to remove the resist and the organic silicon film. SE of the surface of SiO ₂ film
When observed with M, there was no residue, and the resist and the organic silicon film could be selectively removed from SiO ₂ .

Embodiment 10 A description will be given of a case where a source gas shown in Table 9 below is used for etching an organic silicon film in Embodiment 9.
As an etching apparatus, a magnetron type RIE apparatus was used. Table 9 below shows the etching conditions and the selectivity when the organic silicon film could be etched without the resist pattern being removed halfway. The selectivity in the table is based on the etching rate of the organic silicon film / the etching rate of the resist.
Defined in

[0305]

[Table 15] Example 11 10 g of the organic silicon compound (n / m = 1/4) according to the formula [1-97] having a weight average molecular weight of 18000 was dissolved in 90 g of anisole to prepare a solution material for an organic silicon film. A solution material of an organic silicon film is applied on a silicon wafer to be processed by a spin coating method.
Baking was performed at 60 ° C. for 90 seconds to dry the solvent. At this time, the thickness of the organic silicon film is 1100 angstroms, and the glass transition temperature is 145 ° C. The complex refractive index at λ = 248 nm as measured by spectroscopic ellipsometry is n
= 2.10, k = 0.38.

Next, in the same manner as in Example 8, a resist was applied on the organic silicon film to form a resist pattern. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained. The thickness of the resist was changed in the range of 500 Å to 1500 Å, and the resist pattern dimension was measured at each resist thickness. As a result, it was found that the dimensional variation caused by the standing wave generated in the resist film was negligible.

Next, using the formed resist pattern as a mask, a flow rate of 180 SCCM was used as an etching gas.
Example 8 except that a mixed gas of Cl ₂ and SF _{6 at} a flow rate of 20 SCCM was used, and the excitation power was set to 200 W.
When the organic silicon film was etched in the same manner as in the above, the resist pattern was not completely removed even after the etching of the organic silicon film was completed, and the organic silicon film was normally etched without being deteriorated. As a result, the organic silicon film could be etched with good dimensional control.

Example 12 8 g of poly (phenylsilene) having an average molecular weight of 13000,
Poly (phenylmethylsilane) with an average molecular weight of 12000
3 g was dissolved in 89 g of anisole to prepare a solution material for the organic silicon film. A solution material of an organic silicon film was applied on a silicon wafer to be processed by a spin coating method, baked at 160 ° C. for 90 seconds, and the solvent was dried. At this time, the thickness of the organic silicon film is 200
nm, and the glass transition temperature was 158 ° C. The complex refractive index at λ = 248 nm measured by spectroscopic ellipsometry was n = 2.10 and k = 0.42.

Next, in the same manner as in Example 8, a resist was applied on the organic silicon film to form a resist pattern. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained. The thickness of the resist was changed in the range of 50 nm to 150 nm, and the dimension of the resist pattern was measured at each resist thickness. As a result, it was found that the dimensional variation caused by the standing wave generated in the resist film was negligible.

Next, using the formed resist pattern as a mask, the source gas was flown into HB at a flow rate of 200 SCCM.
Example 8 except that the excitation power was 150 W
When the organic silicon film was etched in the same manner as in the above, the resist pattern was not completely removed even after the etching of the organic silicon film was completed, and the organic silicon film was normally etched without being deteriorated. As a result, the organic silicon film could be etched with good dimensional control.

Comparative Example 1 R ₁ , R ₂ , R ₃ ＣC in the structure represented by the following general formula (16)
H ₃ , a solution prepared by dissolving 10 g of polysilane having an average weight molecular weight of 6,000 in 90 g of anisole was applied on a silicon substrate by a spin coating method, and heated at 160 ° C. for 90 seconds using a hot plate, An organic silicon film was formed. The glass transition temperature of the organic silicon film was −20 ° C.

The etching conditions (P1) of Examples 1 to 7
When the organic silicon film was etched in (P12),
Under any of the conditions, deterioration as shown in Example 1 was observed, and normal etching could not be performed.

The average weight molecular weight of the polysilane was 500, 1
An organic silicon film was formed in the same manner as described above while changing the temperature to 500, 13,000, and 40,000, and the glass transition temperatures were measured.
A glass transition temperature of 0 ° C. or higher could not be obtained by changing the average weight molecular weight at −20 ° C., −12 ° C., and −12 ° C.

When the organic silicon film was etched under the etching conditions (P1) to (P12) of Examples 1 to 7, deterioration was observed and normal etching could not be performed. Further, R ₁ , R ₂ , and R ₃ are represented by C ₂ H ₅ , C ₃ H
Even if it was replaced with ₈ , the glass transition temperature was 0 ° C. or less, and etching could not be performed normally.

[0315]

Embedded image From the results of Examples 1 to 12 and Comparative Example 1, the organosilicon film having a glass transition temperature of about 0 ° C. or higher or the crosslinked organosilicon film is a gas containing atoms containing chlorine, bromine and iodine. When etched with, without deterioration
It can be seen that the resist can be etched with a high selectivity. The sponge-like transformation of the organic silicon film is due to the fact that the halogen radicals in the plasma easily penetrate into the interior of the organic silicon film, become a silicon halide compound, evaporate from the film, and the organic components that are difficult to volatilize are not etched It is thought that it was left in the form of a sponge.

On the other hand, in an organic silicon film having a high glass transition temperature of an organic silicon compound or a cross-linked organic silicon film, halogen radicals hardly penetrate into the inside of the organic silicon film and are etched sequentially from the surface. It is considered that the alteration could be suppressed.

The following Examples 13 to 44 are examples according to the second embodiment of the present invention in which a silicon-based insulating film is etched using an organic silicon film pattern as a mask.

Example 13 In this example, the results of examining the etching resistance when etching a silicon-based insulating film using the organic silicon films (A1) to (A10) as a mask will be described. First, a silicon-based insulating film is formed by the following (S1), (S
It was formed by the method of 2). As the resist and the conventional antireflection film for comparison, the resist formed by the method (R1) of Example 1 was used.

(S1): An SiO ₂ film was formed on a base substrate by LPCVD.

(S2): An SiN film was formed on the underlying substrate by LPCVD.

Next, the etching resistance of the organic silicon film was examined. Using a magnetron-type reactive plasma etching apparatus, an organic silicon film of (A1) to (A10), a resist and an antireflection film of (R1) to (R4),
The silicon-based insulating film of (S1) and (S2) was
Etching was performed under the conditions 1) to (Q6).

(Q1) Etching gas: flow rate 45/1
55 SCCM CHF ₃ / CO, excitation power: 700 W,
Degree of vacuum: 40 mTorr, substrate temperature: 50 ° C. (Q2) Etching gas: flow rate 45/155 / 7SC
CM CHF ₃ / CF ₄ / O ₂ , excitation power: 700 W,
Vacuum degree: 40 mTorr, substrate temperature: 50 ° C. (Q3) Etching gas: flow rate 12/100/240
SCCM C ₄ F ₈ / CO / Ar, excitation power: 700
W, degree of vacuum: 40 mTorr, substrate temperature: 50 ° C. (Q4) Etching gas: CHF ₃ / CF _{4 at} a flow rate of 74/78 SCCM, excitation power: 700 W, degree of vacuum: 40
mTorr, substrate temperature: 50 ° C. (Q5) etching gas: flow rate 80/20 / 160S
CF ₄ / O ₂ / Ar of CCM, excitation power: 800 W, degree of vacuum: 40 mTorr, substrate temperature: 50 ° C. (Q6) Etching gas: flow rate 45/155 / 10S
CHF ₃ / CO / O _{2 of} CCM, excitation power: 800 W,
Degree of vacuum: 40 mTorr, substrate temperature: 50 ° C. (A3) to (A10), (R1) to (R4), (S1)
And the etching rates of (S2) were measured. The results of calculating the etching selectivity of the (S1) SiO ₂ film to the organic silicon film (= etching rate of the SiO ₂ film / etching rate of the organic silicon film) are shown in Table 1 above. For comparison, the conventional mask material (R1)-
Table 1 also shows the results of calculating the etching selectivity (= etch rate of silicon-based insulating film / etch rate of etching mask material) with respect to (R4).

From Table 1 above, it can be seen that, under any of the etching conditions, any of the films (A1) to (A10) has a lower etching rate than the conventional etching mask material, and the organic silicon film is formed of the conventional resist and the antireflection film It can be seen that the film has better dry etching resistance than an etching mask material such as a film.

Example 14 In this example, the results of examining the etching resistance when etching a silicon-based insulating film using the organic silicon films (B1) to (B10) as an etching mask will be described. First, the results of examining the etching resistance of the organic silicon film in the same manner as in Example 13 are shown in Table 2 above. From Table 2 above, any of the films (B1) to (B10) has a lower etching rate than the conventional etching mask materials (R1) to (R4), and the organic silicon film has better dry etching resistance than the resist. I understood that.

(C1) to (C10), (D1) to (D1)
0), (E1) to (E10), (F1) to (F10),
The etching resistance when the silicon-based insulating film was etched using the organic silicon films (G1) to (G10) as an etching mask was also examined in the same manner, and (A1) to (A10), (B1) to Like the organic silicon film of (B10), it was found that the dry etching resistance was superior to that of the conventional etching mask material.

Example 15 In this example, an experiment was performed to measure the etching selectivity between the resist and the organic silicon film and the optical constant of the organic silicon film.

First, twelve kinds of organic silicon film solution materials shown in the following (A) to (L) were prepared.

(A) A solution material obtained by dissolving 10 g of polysilane having a weight average molecular weight of 1000 represented by the following formula [17-1] in 90 g of cyclohexanone.

(B) A solution material obtained by dissolving 10 g of polysilane having a weight average molecular weight of 12,000 represented by the following formula [17-2] in 90 g of cyclohexanone.

(C) Polysilane having a weight average molecular weight of 12,000 (n / m = 1/1) represented by the following formula [17-3] 10
g solution in 90 g of cyclohexanone.

(D) Polysilane (n / m = 4/1) 10 having a weight average molecular weight of 13000 represented by the following formula [17-4]
g solution in 90 g of cyclohexanone.

(E) 10 g of polysilane having a weight average molecular weight of 12,000 represented by the following formula [17-5] was added to 90 g of xylene.
Solution material obtained by dissolving in water.

(F) 10 g of polysilane having a weight average molecular weight of 12,000 represented by the following formula [17-6] was added to 90 g of xylene.
Solution material obtained by dissolving in water.

(G) 10 g of a polysilane (n / m = 1/4) having a weight average molecular weight of 9000 represented by the following formula [17-7]
Is dissolved in 90 g of xylene to obtain a solution material.

(H) 10 g of polysilane having a weight average molecular weight of 13000 represented by the following formula [17-8] was added to 90 g of xylene.
Solution material obtained by dissolving in water.

(I) 10 g of a polysilane having a weight average molecular weight of 16,000 represented by the following formula [17-9] was added to 90 g of xylene:
Solution material obtained by dissolving in water.

(J) 5 g of a polystyrene having a weight average molecular weight of 13000 represented by the following formula [17-10] and
-1] polysilane 10 having a weight average molecular weight of 1000
g in 85 g of xylene to obtain a solution material.

(K) Polysilene (n / m = 1/2) 5 having a weight average molecular weight of 12000 represented by the following formula [17-11]:
g and 10 g of polysulfone having a weight average molecular weight of 4000
Is dissolved in 85 g of xylene to obtain a solution material.

(L) Polysilane (n / m = 1/1) 1 having a weight average molecular weight of 15,000 and represented by the following formula [17-12]
A solution material obtained by dissolving 0 g and 1 g of a coumarin dye in 89 g of xylene.

[0340]

Embedded image

[0341]

Embedded image The above-mentioned solution materials (A) to (L) are applied to a silicon wafer by a spin coating method,
Was performed for 60 seconds to form an organic silicon film having a thickness of 500 nm. The glass transition temperature of this organic silicon film is shown in Table 10 below. Similarly, a positive chemically amplified resist APEX-E manufactured by Shipley using polyhydroxystyrene as a component resin, a negative chemically amplified resist SNR200 manufactured by Shipley, and a positive resist using a novolak resin as a component resin (products) Name: IX-770,
(Manufactured by Nippon Synthetic Rubber Co.) was applied onto a silicon wafer. Next, the film and the resist obtained using the solution materials (A) to (L) were respectively etched using a magnetron type RIE apparatus, and the etching rates of the respective films were measured. Etching conditions were as follows: Cl ₂ gas at a flow rate of 200 SCCM was used as a source gas, and the degree of vacuum was 80.
mTorr, excitation power 200W. All of the organic silicon films were etched normally without deterioration. Table 10 shows the measurement results of the etching rate.

Next, the complex refractive index of the organic silicon film at wavelengths of 248 nm and 193 nm was measured. Also,
The reflectance of the 500 nm-thick organic silicon film at each wavelength was measured with an ultraviolet spectrometer. The measurement results are shown in Table 11 below.

[0343]

[Table 16]

[0344]

[Table 17]

[0345]

[Table 18]

[0346]

[Table 19]

[0347]

[Table 20]

[0348]

[Table 21] From Table 10 above, the etching rate of the organic silicon film is at least 3.6 times faster than the etching rate of the resist. Therefore, the organic silicon film obtained in this example is obtained by using the resist as a mask.
It can be seen that etching can be performed with a high selectivity.

Further, from Table 11, it can be seen that the reflectance of each of the organic silicon films is 5% or less, and effectively functions as an antireflection film.

Comparative Example 2 A carbon film, a novolak resin film, a polysulfone film, and a polyimide film were formed on a silicon wafer. The carbon film was formed by using a DC magnetron sputtering method using a graphite plate as a target in an Ar atmosphere. The formation conditions are a substrate temperature of 250 ° C., a pressure of 4 × 10 ⁻³ Torr, a power density of 3.5 W / cm ² , and an argon flow rate of 40 SCCM.

The novolak resin film has a weight average molecular weight of 60
A solution material obtained by dissolving Novolak resin No. 00 in ethyl lactate was applied onto a silicon wafer by a spin coating method, and baked at 320 ° C. for 180 seconds to form a film.

A polysulfone resin film is formed by dissolving a polysulfone resin having a weight average molecular weight of 5,000 in cyclohexanone and applying a solution material on a silicon wafer.
A film was formed by baking at 20 ° C. for 90 seconds.

The polyimide resin film has a weight average molecular weight of 50
A solution material obtained by dissolving polyimide resin No. 00 in cyclohexanone was applied on a silicon wafer, and baked at 220 ° C. for 90 seconds to form a film.

In the same manner as in Example 15, a resist film was formed on a silicon wafer.

At the wavelengths of 248 nm and 193 nm, the complex refractive indexes of the carbon film, novolak resin film, polysulfone film and polyimide film were measured. A carbon film having a thickness of 500 nm at each wavelength;
The surface reflectance of the novolak resin film, polysulfone film and polyimide film was measured with an ultraviolet spectrometer. Table 11 also shows the measurement results.

From Table 11 above, it can be seen that the surface reflectances of the carbon film, the novolak resin film, the polysulfone film and the polyimide film are all 7% or less, and effectively act as antireflection films.

Next, each film was formed by magnetron type RI.
Etching was performed with an E apparatus, and the etching rate of each film was determined. The etching conditions are optimum conditions for etching the carbon film, the novolak resin film, the polysulfone film and the polyimide film, that is, CF ₄ gas at a flow rate of 50 SCCM, O ₂ gas at a flow rate of 8 SCCM, and Ar gas at a flow rate of 20 SCCM as a source gas. Used, the degree of vacuum is 10 mTorr, and the excitation power is 200 W. The measurement results are shown in Table 12 below.

[0358]

[Table 22] From the above Table 12, the etching rates of the carbon film, the novolak resin film, the polysulfone film and the polyimide film are 0.37 times, 0.91 times and 1.39 times the etching rates of the resist having the highest dry etching resistance.
It is 1.33 times, which indicates that the etching selectivity with the resist cannot be obtained.

As described above, the carbon film, the novolak resin film, the polysulfone film, and the polyimide film have an excellent antireflection effect, but do not have an etching selectivity with the resist. It can be seen that the pattern cannot be transferred to the mask.

Comparative Example 3 A polysilicon film was formed on a silicon wafer, and this polysilicon film was etched by a magnetron type RIE apparatus, and the etching rate was determined. The etching conditions are the same as in Example 15. Table 1 shows the measurement results.
It is shown in FIG.

From Table 11, it can be seen that the etching rate of the polysilicon film is 8.9 times faster than that of the resist.

The complex refractive index of the polysilicon film was measured at wavelengths of 248 nm and 193 nm. Further, the surface reflectance of the 500 nm-thickness polysilicon film formed on the silicon wafer was measured at each wavelength by an ultraviolet spectrometer. These results are shown in Table 11 above.
Shown in

According to Table 11, the surface reflectance of the polysilicon film is as high as 45% or more, and a wavy shape is seen on the side wall of the resist on the polysilicon film, making it difficult to pattern the resist with good dimensional control. You can see that.

As described above, it can be seen that the polysilicon film can have a high etching selectivity with respect to the resist, but cannot be used as an etching mask for the insulating film because of its high surface reflectance with ultraviolet light.

Example 16 In this example, an experiment for measuring the selectivity between an organic silicon film, a silicon oxide film, and a silicon nitride film was performed as follows.

In the same manner as in Example 15, various organic silicon films were formed on a silicon wafer, respectively.
An SiO ₂ film and a SiN film were formed on a silicon wafer, and each of these films was etched by a magnetron type RIE apparatus, and the etching rate of each film was determined. Etching conditions were as follows: flow rate 50 SC as source gas
CM C ₄ F ₈ gas, CO gas at a flow rate of 10 SCCM, Ar gas at a flow rate of 100 SCCM, O ₂ gas at a flow rate of 3 SCCM are used, the degree of vacuum is 10 mTorr, and the excitation power is 800 W. Table 10 shows the measurement results.

From Table 10 above, it can be seen that the etching rate of the SiO ₂ film is 15 times or more the etching rate of the organic silicon film. Further, it can be seen that the etching rate of the SiN film is 14 times or more the etching rate of the organic silicon film.

Comparative Example 4 Under the same etching conditions as in Example 16, the etching rates of the resist film, carbon film, novolak resin film, polysulfone film, polyimide film and polysilicon film were measured. As the resist film, 3 used in Example 15 was used.
Different types of resist films were used. Table 10 shows the measurement results.
Shown in

From the above Table 10, it can be seen that the etching rate of the SiO ₂ film and the SiN film is only 2.7 times and 2.6 times at the maximum with respect to the etching rate of the resist film. In addition, the carbon film and the polysilicon film are S
When the iO ₂ film and the SiN film are etched, they have the same etching resistance as the organic silicon film used in the present invention, but have the problems shown in Comparative Examples 2 and 3,
It is difficult to use the SiO ₂ film and the SiN film as etching masks.

The novolak resin film, polysulfone film, and polyimide film have only the same etching resistance as that of the resist, and are insufficient as etching masks for the SiO ₂ film and the SiN film as compared with the organic silicon film.
Further, novolac resin film, polysulfone film and polyimide film, which as shown in Comparative Example 1, the etching selection ratio of the resist can not be taken, SiO ₂ film and Si
It cannot be used as an etching mask for the N film.

Therefore, from Examples 15 and 16, and Comparative Examples 1 to 3, it can be seen that the organic silicon film is most excellent as the etching mask for the SiO ₂ film and the SiN film. Further, since the organic silicon film according to the present invention can be formed by a spin coating method, the process cost is lower than that of an etching mask such as a polysilicon film or a carbon film which can be formed only by a CVD method or a sputtering method. There is also an advantage that dust is not generated during film formation.

The following Examples 17 to 44 have the general formula [1]
This is an example in which an organic silicon film made of an organic silicon compound shown in [2] is etched using a resist pattern as an etching mask.

Example 17 As shown in FIG. 1A, an SiO ₂ film 2 having a thickness of 500 nm was formed on a silicon wafer 1 by a CVD method. Next, on the SiO ₂ film 2, 8 g of polysilane having an average molecular weight of 1000 represented by the above formula [17-1] and the formula [3-79]
A solution material prepared by dissolving 1.8 g of a cross-linking agent and 0.2 g of trihalomethyl-s-triazine as a radical generator in 90 g of cyclohexanone shown in (1) above was applied, and heated at 180 ° C. in a nitrogen atmosphere (oxygen concentration 50 ppm or less). Baking was performed for 600 seconds to crosslink the polysilane to obtain an organic silicon film 3 having a glass transition temperature of 153 ° C. The thickness of the organic silicon film 3 is 250 nm (FIG. 1B).

The complex refractive index of the organic silicon film 3 at an exposure wavelength of 248 nm measured by spectroscopic ellipsometry is n = 2.
At 10, k = 0.38, the light intensity reflectance at the interface between the resist and the organic silicon film 3 was calculated with respect to the thickness of the organic silicon film using the obtained value of the complex refractive index. The result is shown in FIG. The values shown in Table 8 above were used as the complex refractive index at the exposure wavelength used in the calculation.

FIG. 5 shows that the return light of the resist film 4 is reduced by forming the organic silicon film 3 on the SiO ₂ film 2.

Subsequently, a resist 4 was applied on the organic silicon film and baked at 98 ° C. for 120 seconds (FIG. 1).
(C)). At this time, the thickness of the resist 4 is 200 nm. The resist used in Example 1 was (R
The one obtained by the method of 1) was used.

Next, pattern exposure was performed using a reduction optical type stepper using a KrF excimer laser beam as a light source (exposure amount: 30 mJ / cm ² ), baking was performed at 98 ° C. for 120 seconds, and then 0.21 standard. Was developed using a TMAH developer of No. 1 to form a 0.18 μm line and space pattern 5 (FIG. 1D). At this time, the thickness of the resist pattern 5 is 180 nm.

When the cross section of the resist profile was observed by SEM, the resist pattern did not show any tailing or erosion, a good resist profile was obtained, and no wavy shape due to a standing wave was found on the side wall. .

The resist film thickness is set to 100 to 200 nm.
And the resist pattern dimensions were measured.
FIG. 6 shows the result. Next, the thickness of the SiO ₂ film 2 is set to 4
The dimensions of the resist pattern 5 were measured by changing the size from 50 to 550 nm. FIG. 7 shows the result.

[0380] When the resist film and the amount of dimensional variation due to multiple reflections generated in the SiO ₂ film is defined as shown Fig. 6 and Fig 7, the amount of dimensional variation due to multiple reflections that occur in the resist film is 6 nm, SiO ₂ film Is 5 nm, which is within the allowable range of 9 nm or less. Therefore, since the organic silicon film acts as an anti-reflection film, the resist pattern is less dependent on variations in the thickness of the resist and the thickness of SiO _2, and a resist pattern with good dimensional control can be obtained.

Using the resist pattern formed as described above as a mask, the organic silicon film was etched using a magnetron type RIE apparatus as shown in FIG. Using Cl ₂ at a flow rate of 200 SCCM as a source gas, an excitation power of 300 W and a degree of vacuum of 30 mTorr
When the organic silicon film was etched under the etching condition of r, the organic silicon film could be etched without the resist pattern being removed halfway.

When the processed shape of the organic silicon film was observed, the organic silicon film was vertically etched with good anisotropy. Further, when the dimension of the organic silicon film pattern after the etching is defined by the bottom of the pattern, that is, Y in FIG. 1E, the dimensional conversion difference (= Y−X) caused by the etching of the organic silicon film is: At -2 nm, the organic silicon film could be etched without shifting from the resist pattern before etching.

[0383] Further, by using the remaining resist pattern on the patterned organic silicon film and an organic silicon film as a mask, using a magnetron-type reactive ion etching apparatus, as shown in FIG. 1 (f), SiO ₂ film Was etched. 30S flow rate as etching gas
When etching was performed using C ₄ F ₈ gas of CCM, Ar gas at a flow rate of 160 SCCM, and O ₂ gas at a flow rate of 3 SCCM under an etching condition of 800 W of excitation power and a degree of vacuum of 30 mTorr, the organic silicon film could not be removed in the middle. The etching of the SiO ₂ film could be performed without any problem.

As described above, SiO 2_TwoEtch film
As a result, the organic silicon film and SiO_TwoMembrane etchin
The dimensional conversion difference (= ZX) generated by the
Within the allowable range of -9 nm to +9 nm.
The size of the pattern is faithful to SiO _TwoCan be transferred to the membrane
SiO with good dimensional control_TwoThe film can be processed
Was.

[0385] Under these etching conditions, the etching rates of the resist film and the organic silicon film were measured with the solid film. The etching rate of the resist film was 25 nm / min, the organic silicon film was 165 nm / min, and the etching rate of the organic silicon film was resist film. 6.6 times faster. Therefore, it is considered that the organic silicon film could be etched anisotropically and with good dimensional control without any regression of the resist pattern.

Under these etching conditions, a resist film, an organic silicon film and a SiO
_When the etching rates of the _two films were measured, the resist film was 72 nm / min and the organic silicon film was 9 nm / mi.
n, SiO ₂ film is 230nm / min, SiO ₂
The etching rate of the film is 25.6 than that of the organic silicon film.
Times, the organic silicon film is 3.3 times faster than the resist film.
It can be seen that the etching mask has more dry etching resistance than the resist used when etching the iO ₂ film.

For this reason, it is possible to obtain a Si pattern that is vertically anisotropic without deviation from the resist pattern dimension before etching.
It is considered that the O ₂ film could be etched.

Example 18 In Example 17, after processing the SiO ₂ film, the resist and the organic silicon film as an etching mask were sequentially peeled off using a downflow etching apparatus. When O ₂ gas at a flow rate of 20 SCCM was used as a source gas and the etching was performed under the etching conditions of an excitation power of 200 W and a vacuum degree of 8 mTorr, the resist could be completely removed.

[0389] The infrared absorption spectrum of the organic silicon film after the resist was removed was measured.
An absorption due to the Si—O—Si bond was observed at 00 cm ⁻¹ . This means that the organic silicon film was glassed by exposure to oxygen plasma.

Next, hydrofluoric acid and pure water were mixed in a weight ratio of 1: 500.
When the solution was infiltrated into a diluted hydrofluoric acid solution mixed for 90 seconds, the vitrified organic silicon film could be selectively removed from the silicon oxide film.

Example 19 In Example 17, after processing the SiO ₂ film, the resist and the organic silicon film serving as an etching mask were sequentially peeled off using a down-flow etching apparatus. Using O ₂ at a flow rate of 20 SCCM as a source gas,
When the resist was etched under the etching conditions of an excitation power of 200 W and a degree of vacuum of 8 mTorr, the resist could be completely removed. Although the organic silicon film was glassed by exposure to oxygen plasma, the source gas CF ₄ = 30 SCCM, O ₂ = 40 SCCM,
When the glassy organic silicon film was etched under the etching conditions of an excitation power of 800 W and a degree of vacuum of 35 mTorr, the silicon oxide film could be selectively peeled off without shaving.

Comparative Example 5 As in Example 17, 500 nm
Thick SiO ₂ film is formed, it followed to form a carbon film having a thickness of 200nm which is a thickness required to etch the SiO ₂ film on the SiO ₂ film. Further, a resist was applied on the carbon film and baked at 98 ° C. for 120 seconds. At this time, the thickness of the resist is 200 nm. The resist used in Example 1 was (R
The one obtained by the method of 1) was used.

Next, exposure and development were performed in the same manner as in Example 17 to form a 0.18 μm line-and-space resist pattern. Carbon film has a wavelength of 248n
Since the light absorption at m was high, reflection from the underlying film was suppressed and a resist pattern having a good resist profile and good dimensional controllability was obtained as in Example 17.
Further, since the resist film thickness was reduced, the focus margin at the optimum exposure amount was 0.7 μm, and a value of 0.6 μm or more required at the time of device manufacture could be obtained.

When the carbon film was etched under the same conditions as in Comparative Example 2 using the resist pattern formed as described above as a mask, the resist pattern was not removed during the etching of the carbon film. Failed to etch the SiO ₂ film.

When the etching rate of the solid film was measured for the resist film and the carbon film in the same manner as in Comparative Example 2, the etching rate of the carbon film was 185 nm / min for the resist film and 65 nm / min for the carbon film. Was only 0.35 times that of the resist film, and it was found that the selectivity between the resist film and the carbon film was not high. Therefore, it is considered that the resist pattern did not collapse during the etching of the carbon film because the selection ratio between the resist film and the carbon film could not be obtained.

Comparative Example 6 An SiO ₂ film having a thickness of 500 nm and a carbon film having a thickness of 200 nm were sequentially formed on a silicon wafer. Next, a resist is applied on this carbon film,
Baking was performed for seconds. The thickness of the resist film thus obtained is 700 nm. As the resist, a resist obtained by the method (R1) used in Example 1 was used. The resist film was exposed and developed in the same manner as in Example 17 to form a 0.18 μm line and space resist pattern.

The carbon film was etched under the same conditions as in Comparative Example 2 using the resist pattern formed as described above as a mask. As a result, although the carbon film could be etched, as shown in FIG. 8, the processed shape of the carbon film 12 was a tapered shape and could not be etched with good anisotropy. This is presumably because, as shown in Comparative Example 4, since the etching selectivity between the resist pattern and the carbon film was not sufficient, the resist pattern receded during carbon etching.

Also, in this comparative example, since the film thickness of the resist is as thick as 700 nm, the margin of furcus at an optimum exposure amount is as small as 0.3 μm, which is 0.6 μm which is a value required at the time of device manufacture. Farcus margin could not be obtained.

Comparative Example 7 As shown in FIG. 9A, an SiO ₂ film 22 having a thickness of 500 nm was formed on a silicon wafer 21. Next, a solution material prepared by dissolving polysulfone having an average molecular weight of 6000 in cyclohexanone was applied by a spin coating method, and baked at 225 ° C. for 90 seconds.
As shown in (b), an antireflection film 23 was formed.

The film thickness of the antireflection film 23 thus obtained was 115 nm. The light intensity reflectance at the interface between the resist and the antireflection film was calculated, and the film thickness was set so that the reflectance was minimized. The complex refractive index of the antireflection film 23 at an exposure wavelength of 248 nm is n = 1.74 and k = 0.24.

Next, a resist is applied on the anti-reflection film 23 and baked at 98 ° C. for 120 seconds to obtain a resist as shown in FIG.
As shown in FIG. 7, a resist film 24 was formed. The thickness of the resist film 24 thus obtained is 300 nm. As the resist, a resist obtained by the method (R1) used in Example 1 was used.

Thereafter, exposure and development were carried out in the same manner as in Example 17, and as shown in FIG.
An m-line and space resist pattern 24 was formed.

Using the resist pattern 24 formed as described above as a mask, under the same etching conditions as in Comparative Example 1, as shown in FIG.
Was etched. When the etching rate of the solid film was measured, the etching rate of the antireflection film 23 was
Since the etching rate of the carbon film was 200 nm / min, which was faster than that of the carbon film, and the film thickness was smaller than that of the carbon film, the tapered shape was not so large as the carbon film.

The dimensional conversion difference (= YX) caused by the etching of the antireflection film was -12 nm, which was larger than that in the case of using the organic silicon film in Example 17. This is presumably because the etching selectivity between the resist and the anti-reflection film was not high, and the resist pattern receded during the etching of the anti-reflection film.

Subsequently, the SiO ₂ film was etched under the same etching conditions as in Example 17. The dimensional conversion difference (= Z−Y) generated by the etching of the SiO ₂ film is −20 n
m, and the dimensional conversion difference (= ZX) caused by the etching of the organic silicon film and the SiO ₂ film was −23 nm, which was beyond the allowable range of −9 nm to +9 nm.

Also, the processed shape of the SiO ₂ film 22 is shown in FIG.
As shown in the figure, the film was tapered and could not be vertically etched with good anisotropy. When the etching rate at the time of etching the SiO ₂ film was measured using a solid film, the etching rate of the antireflection film 23 was found to be 152 n
m / min, which is less resistant to dry etching than the resist. Therefore, during the etching of the SiO ₂ film 22, the resist pattern
It seems that the pattern size of the SiO ₂ film 22 was reduced and the etched shape became tapered.

From the comparison with this comparative example, according to the present invention,
Since the organic silicon film has a resistance to dry etching with high etch mask of the SiO ₂ film, without deviation the dimensions of the resist pattern before etching, and to be able to etch the SiO ₂ film with perpendicular highly anisotropic Recognize.

Example 20 As shown in FIG. 1A, an SiO ₂ film 2 having a thickness of 500 nm is formed on a silicon wafer 1 and then, as shown in FIG.
As shown in Example by the method of 1 (A1) ~ (A10) , the SiO ₂ film organosilicon film 3 having a thickness of 100 nm 2
Formed on top. Next, as shown in FIG. 1C, a 200 nm-thick resist 4 was formed on each organic silicon film 3 by the method (R1) of Example 1. Subsequently, after pattern exposure was performed using a reduction optical type stepper using a KrF excimer laser as a light source, the substrate was heated at 110 ° C. for 90 seconds on a hot plate. Further, as shown in FIG.
Development processing was performed using a 0.21 N TMAH developer to form a 0.18 μm line and space pattern. The thickness of the resist pattern 5 obtained after the development treatment is 180 nm.

As a result of observing the resist profile using a scanning electron microscope, it was found that there was no wavy shape due to a standing wave in the resist film on any of the organic silicon films, and a good resist profile was obtained. Was.
There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained. At this time, the focus margin at the optimum exposure amount (18 mJ / cm2) is 0.8 μm. Next, the resist pattern 5 was transferred to the organic silicon film 3. Example 1 A magnetron-type reactive ion etching apparatus was used as an etching apparatus.
Etching was performed under the conditions (P1) to (P4). To determine the etching time, end point detection by light emission was used, and overetching was performed by 50% with respect to the just time.

When the organic silicon films (A1) and (A2) are etched, the processed organic silicon film pattern 6 swells under any of the conditions (P1) to (P4), and the anisotropic etching can be performed. I knew it wasn't. In the organic silicon films (A3) to (A10), (P
Under the condition (1), the organic silicon film pattern swells. These are considered to be due to the sponge-like transformation of the organic silicon film due to the etching, as can be seen from Example 1.

In the case where no swelling occurred, the dimension of the resist pattern before etching was X in FIG. 1D, and the dimension of the organic silicon film pattern after etching was FIG.
Table 1 shows the results of measuring the dimensional conversion difference (= YX) defined by Y in (e) and caused by the etching of the organic silicon film. From Table 1, regarding (A3) to (A10), under the etching conditions of (P2) to (P4), the organic silicon film could be etched with almost no deviation from the resist pattern dimensions before etching. I understand.

Next, as shown in FIG. 1E, the condition (P
The SiO2 film was etched using the organic silicon film and the resist pattern etched in 2) as an etching mask. As the etching conditions, (Q1) of Example 13 was used. As the etching device, a magnetron-type reactive ion etching device was used. To determine the etching time, end point detection by light emission was used, and overetching was performed by 50% with respect to the just time.
The dimensions of the SiO ₂ film pattern after etching are shown in FIG.
Table 1 shows the results of measurement of the dimensional conversion difference (= Z−Y) caused by the etching of the SiO ₂ film.

Also, when the dimensional conversion difference (= ZX) generated by etching the organic silicon film and the SiO ₂ film was calculated, it was within the allowable range of -9 nm to +9 nm, and the SiO ₂ film had good dimensional controllability. _Two films could be processed.

Comparative Example 8 In this comparative example, a case will be described in which the antireflection film formed by the methods (R2) to (R4) of Example 1 is used.

As shown in FIG. 9A, a 500 nm-thick SiO ₂ 22 film was formed on a silicon wafer 21. Next, as shown in FIG. 9B, (R
2) Antireflection film 2 having a thickness of 100 nm by the method of (R4)
3 were formed on the SiO ₂ film 22, respectively. Next, FIG.
As shown in (c), a resist 24 having a thickness of 150 nm was formed on each organic silicon film 23 by the method (R1) of Example 1. Subsequently, after pattern exposure was performed using a reduction optical type stepper using a KrF excimer laser as a light source, the substrate was heated at 110 ° C. for 90 seconds on a hot plate.

Further, as shown in FIG.
Perform development processing using a 1N TMAH developer solution.
An 8 μm line and space pattern was formed. The thickness of the resist pattern after the development processing is 180 nm. As a result of observing the resist profile using a scanning electron microscope, it was found that there was no wavy shape due to a standing wave in the resist film on any of the organic silicon films, and a good resist profile was obtained.

Thereafter, a reactive ion etching apparatus was used as an etching apparatus, and a flow rate of 20 /
CF ₄ / O ₂ / Ar of 60/80 SCCM, excitation power 8
The organic silicon film 23 was etched under the conditions of 00 W, a degree of vacuum of 40 mTorr, and a substrate temperature of 60 ° C. At this time, the etching rate of the resist and the antireflection film and the etching selectivity of the antireflection film with respect to the resist (= etching rate of the antireflection film / etching rate of the resist)
Is as shown in the table below. The etching rate was measured for the solid film as in Example 1.

[0418]

[Table 23] The etching time was a time for detecting the end point by light emission and performing 50% over-etching with respect to the just time. As a result, all the resist patterns disappear,
The processed shape of the anti-reflection film was a tapered shape as shown in FIG.

Comparative Example 9 In this comparative example, the resist film thickness was increased (R2) to (R2).
The case where the antireflection film of 4) is etched will be described. First, as shown in FIG.
A resist 24 having a thickness of 300 nm was formed on each anti-reflection film by the method described above. Subsequently, after pattern exposure was performed using a reduction optical type stepper using a KrF excimer laser as a light source, the substrate was heated at 110 ° C. for 90 seconds on a hot plate. Further, as shown in FIG. 9D, a developing process was performed using a 0.21 N TMAH developing solution to obtain a 0.18 μm
Was formed. The thickness of the resist pattern after the development processing is 280 nm.

As a result of observing the resist profile using a scanning electron microscope, it was found that there was no wavy shape due to a standing wave in the resist film on any of the antireflection films, and a good resist profile was obtained. Was. However, the focus margin at the optimal exposure dose (19 mJ / cm2) is 0.3 μm, which is an allowable value of 0.6 μm.
Is below. This is considered to be due to the fact that the resolution was deteriorated due to the large thickness of the resist.

Next, the antireflection film was etched in the same manner as in Comparative Example 7. As a result, as shown in FIG. 9E, the anti-reflection film 23 could be etched without the resist pattern 24 being eliminated halfway. Anti-reflection film 2
Table 13 shows the dimensional conversion difference (= YX) generated by the etching of No. 3. The etching condition of the antireflection film of Comparative Example 7 is more suitable for etching a general resin film composed of carbon, hydrogen and oxygen with good anisotropy than the etching conditions of (P1) to (P12). Condition. However, the dimensional conversion difference is larger than that of the organic silicon film according to the present invention. It is considered that this is because the etching selectivity between the resist and the antireflection film is not sufficient, and the resist pattern has receded due to the etching of the antireflection film.

Next, as shown in FIG. 9F, the SiO ₂ film was etched using the resist pattern and the antireflection film pattern as an etching mask. As the etching conditions, (Q1) to (Q6) of Example 13 were used. Dimensional conversion difference generated by etching of SiO ₂ film (=
The results of measuring ZY) are shown in Table 1 above.

From Table 1, it can be seen from the table that the difference in dimensional conversion in the case of etching with (Q1) is compared with that of the embodiment, the organic silicon film according to the present invention is more effective than the conventional antireflection film and SiO ₂ is etched. It can be seen that the dimensional conversion difference is small. This is because the organic silicon film pattern hardly recedes during etching of the SiO ₂ film because the organic silicon film has high resistance as an etching mask material.

Example 21 As shown in FIG. 1A, a 500 nm-thick SiO ₂ film was formed on a silicon wafer. Then, FIG.
As shown in (b), (B3) to (B10) of Example 2
A 100 nm-thick organic silicon film is
It was formed on an iO ₂ film. Next, as shown in FIG. 1C, a resist having a thickness of 200 nm was formed on each organic silicon film by the method (R1) of Example 1. Subsequently, after pattern exposure was performed using an electron beam having an acceleration voltage of 50 keV, the substrate was heated at 110 ° C. for 90 seconds on a hot plate.
At that time, g-line (436nm) of mercury lamp
And pattern exposure was performed while imparting photoconductivity to the organic silicon film.

Further, as shown in FIG.
Perform development processing using a 1N TMAH developer solution.
An 8 μm line and space pattern was formed. The thickness of the resist pattern after the development processing is 180 nm. Irradiation of ultraviolet light during pattern exposure caused photoconductivity in the organic silicon film, and a resist pattern free from displacement due to charge-up on any of the organic silicon films could be obtained. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

After that, as shown in FIG. 1E, the resist pattern was transferred to the organic silicon film in the same manner as in Example 18, and as in Example 20, (B3) to (B10)
When the film was etched under the conditions of (P2) to (P4), the swelling of the organic silicon film did not occur, and the film could be etched with good anisotropy. The results of measuring the dimensional conversion difference (= YX) caused by the etching of the organic silicon film are shown in Table 2 above.

As can be seen from Table 2, the organic silicon film of the present invention has a good etching control ratio with respect to the resist as compared with the dimensional conversion difference when the conventional anti-reflection film is etched in Comparative Example 9, so that the dimensional controllability is good. It can be seen that it has been etched.

Next, as shown in FIG. 1F, the case where the organic silicon film is etched under the condition (P3) will be described.
Using the organic silicon film pattern and the resist pattern as masks, the SiO ₂ film was etched under the conditions (Q2) of Example 13. Table 2 shows the measurement results of the dimensional conversion difference (= ZY) generated by the etching of the SiO ₂ film.

From Table 2, in Comparative Example 9, SiO ₂ was used under the etching conditions (Q2) using the conventional anti-reflection film.
It can be seen that the dimensional conversion difference caused by the etching of the SiO ₂ film is smaller in the case of the present embodiment than in the case of etching the film. Further, the dimensional conversion difference (= Z−X) generated by the etching of the organic silicon film and the etching of the SiO ₂ film is within the allowable range of −9 nm to +9 nm, and the SiO ₂ film can be formed with good dimensional control. Could be processed.

Example 22 As shown in FIG. 1A, a film having a thickness of 5 was formed on a silicon wafer.
A 00 nm SiO ₂ film was formed. Next, FIG.
As shown in (3), the organic silicon films having a thickness of 100 nm were each formed of SiO ₂ by the method of (C1) to (C10) in Example 3.
Formed on the film. Next, in the same manner as in Embodiment 20, FIG.
As shown in (d), 0.18 μm
The line and space resist pattern was formed. The thickness of the resist pattern after the development processing is 180 nm
It is.

As a result of observing the resist profile using a scanning electron microscope, it was found that there was no wavy shape due to a standing wave in the resist film on any of the organic silicon films, and a good resist profile was obtained. Was.
There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

Next, as shown in FIG.
The resist pattern was transferred to the organic silicon film using the etching conditions (P6) to (P8) described in Example 2.
0, the films (C3) to (C10) were changed from (P6) to (P6).
When the etching was performed under the condition of 8), the swelling of the organic silicon film did not occur, and the etching was performed with good anisotropy. Table 3 shows the measurement results of the dimensional conversion difference (= YX) caused by the etching of the organic silicon film.

From Table 3, it can be seen that the organic silicon film of the present invention has an etching selectivity with respect to the resist, and thus has better dimensional controllability than the dimensional conversion difference when the conventional antireflection film is etched in Comparative Example 9. It can be seen that it has been etched.

Next, as shown in FIG. 1F, the case where the organic silicon film is etched under the condition (P7) will be described.
Using the organic silicon film and the resist pattern as a mask, the SiO ₂ film was etched under the conditions (Q3) of Example 13. In Comparative Example 9, the conventional antireflection film was replaced with (Q
Compared with the case where the etching was performed under the etching condition of 3), the dimensional conversion difference caused by the etching of the SiO ₂ film was smaller in the case of the present embodiment.

When the dimensional conversion difference (= Z−X) generated by the etching of the organic silicon film and the etching of the SiO ₂ film was calculated, it was within the allowable range of −9 nm to +9 nm, and the SiO ₂ film had good dimensional controllability. _Two films could be processed.

Example 23 As shown in FIG. 1A, a film having a thickness of 5 was formed on a silicon wafer.
A 00 nm SiO2 film was formed. Next, FIG.
As shown in (1), the organic silicon films having a thickness of 100 nm were formed by SiO ₂ by the methods (D1) to (D10) in Example 4.
Formed on the film. Next, in the same manner as in Embodiment 20, FIG.
As shown in (d), 0.18 μm
The line and space resist pattern was formed. The thickness of the resist pattern after the development processing is 180 nm
It is.

As a result of observing the resist profile using a scanning electron microscope, it was found that there was no wavy shape due to a standing wave in the resist film on any of the organic silicon films, and a good resist profile was obtained. Was.
There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

Next, the etching conditions (P5) of Example 3
When the resist pattern was transferred to the organic silicon film using (P8) to (P8), (D3) to
When the film of (D10) was etched under the conditions of (P6) to (P8), the swelling of the organic silicon film did not occur, and the etching could be performed with good anisotropy. Table 4 shows the results of measuring the dimensional conversion difference (= YX) caused by the etching of the organic silicon film.

From Table 4, it can be seen that the organic silicon film of the present invention has a good etching dimensional controllability since the etching selectivity with the resist can be obtained as compared with the dimensional conversion difference when the conventional antireflection film is etched in Comparative Example 9. It can be seen that it has been etched.

Next, when etching was performed under the condition (P6), the resist pattern on the organic silicon film was removed using oxygen plasma. Further, the SiO ₂ film was etched under the etching conditions (Q4) of Example 13 using the organic silicon film as an etching mask. Example 20
Similarly to Comparative Example 9, the conventional anti-reflection film was replaced with (Q
Compared with the case of etching under the etching condition of 4), the dimensional conversion difference caused by the etching of the SiO ₂ film was smaller in the case of the present embodiment.

When the dimensional conversion difference caused by the etching of the organic silicon film and the etching of the SiO 2 film was calculated, it was within the allowable range of −9 nm to +9 nm, and the SiO ₂ film could be processed with good dimensional control. did it.

Example 24 As shown in FIG. 1A, a film having a thickness of 5 was formed on a silicon wafer.
It was formed on a 00 nm SiO ₂ film. Then, FIG.
As shown in (b), (E1) to (E10) of Example 5
A 100 nm-thick organic silicon film is
It was formed on an iO ₂ film. Next, in the same manner as in Example 20, as shown in FIG.
An 18 μm line and space resist pattern was formed. The thickness of the resist pattern after the development process is 18
0 nm.

As a result of observing the resist profile using a scanning electron microscope, it was found that there was no wavy shape due to a standing wave in the resist film on any of the organic silicon films, and a good resist profile was obtained. Was.
There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

Next, as shown in FIG.
The resist pattern was transferred to the organic silicon film under the etching conditions (P9) to (P12). as a result,
When the films (E3) to (E10) were etched under the conditions of (P10) to (P12), the swelling of the organic silicon film did not occur, and the film could be etched with good anisotropy. Dimensional conversion difference (= Y) caused by etching of organic silicon film
-X) is shown in Table 5 above.

As can be seen from the above Table 5, since the etching selectivity with the resist can be obtained in the organic silicon film of the present invention as compared with the dimensional conversion difference when the conventional antireflection film is etched in Comparative Example 9, the dimensional controllability is improved. It turns out that it is etched well.

Next, as shown in FIG. 1 (f), when the organic silicon film was etched under the condition (P12), the condition (Q3) of the thirteenth embodiment was used using the organic silicon film and the resist pattern as a mask. Was used to etch the SiO ₂ film. In Comparative Example 9, as compared with the case where etching was performed under the etching condition (Q2) using the conventional antireflection film, the dimensional conversion difference caused by the etching of the SiO ₂ film was smaller in the case of this example. Was. When the dimensional conversion difference caused by the etching of the organic silicon film and the etching of the SiO ₂ film was calculated, an allowable range of -9 n
within the range of m to +9 nm, with good dimensional controllability.
The iO ₂ film could be processed.

Example 25 This example shows a case where an organic silicon film containing an organic silicon compound having a structure other than the general formula 12 was used.

As shown in FIG. 1A, a 500 nm-thick SiO ₂ film was formed on a silicon wafer. Next, as shown in FIG.
An organic silicon film having a thickness of 100 nm was formed on the SiO ₂ film by the method (F10). Next, in the same manner as in Example 20, as shown in FIG. 1C, a 0.30 μm line and space resist pattern was formed on the organic silicon film. The thickness of the resist pattern after the development processing is 180 nm.

As a result of observing the resist profile using a scanning electron microscope, it was found that there was no wavy shape due to standing waves in the resist film on any of the organic silicon films, and a good resist profile was obtained. Was.
There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

Next, a magnetron-type reactive ion etching apparatus was used as the etching apparatus, and (P
Etching was performed under the conditions 1) to (P4). The etching time was set such that the end point due to light emission was detected and 50% over-etching with respect to the just time was performed. When the organic silicon films of (F1) and (F2) are etched, the processed organic silicon film pattern swells under any of the conditions of (P1) to (P4), indicating that the anisotropic etching cannot be performed. Was. (F3) ~
In the organic silicon film of (F10), the organic silicon film pattern swells even under the condition of (P1). These are considered to be due to the sponge-like transformation of the organic silicon film due to the etching.

(F3) to (F10) are replaced with (P2) to (P
When etching was performed under the condition 4), the organic silicon film pattern could be etched without being sponge-likely altered. The dimension of the resist pattern before etching is defined by X in FIG. 1D, and the dimension of the organic silicon film pattern after etching is defined by Y in FIG. 1E, and the dimensional conversion difference (= Y-X) is shown in Table 6 above.

As can be seen from Table 6, the organic silicon film pattern after the etching is large. The product of etching the organic silicon film adheres to the side wall of the resist pattern and the organic silicon film pattern. This is considered to be caused by the fatness of the organic silicon film pattern.

Next, as shown in FIG. 1F, when the organic silicon film was etched under the condition (P2), the SiO ₂ film was etched using the organic silicon film and the resist pattern as a mask. As the etching apparatus, a magnetron-type reactive plasma etching apparatus was used, and etching was performed under the conditions of (Q6) in Example 13.

Etching of Organic Silicon Film and SiO
Dimensional conversion difference caused by etching of _two films (= ZX)
When the organic silicon film was etched under any of the conditions (P1) to (P4), the dimensional change was within the allowable range of −15 nm to +15 nm, and the resist pattern was faithfully applied to the SiO ₂ film. Could be transcribed.

Example 26 This example also shows a case where an organic silicon film containing an organic silicon compound having a structure other than the general formula [12] is used.

As shown in FIG. 1A, a 500 nm thick SiO ₂ film was formed on a silicon wafer. next,
As shown in FIG. 1B, (G1) to (G1)
An organic silicon film having a thickness of 100 nm was formed on the SiO ₂ film by the method of 0). Next, as shown in FIG. 1C, a 0.35 μm line and space resist pattern was formed on the organic silicon film in the same manner as in Example 18. The thickness of the resist pattern after the development processing is 180 nm.

As a result of observing the resist profile using a scanning electron microscope, it was found that there was no wavy shape due to a standing wave in the resist film on any of the organic silicon films, and a good resist profile was obtained. Was.
There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

Next, the resist pattern was transferred to the organic silicon film. That is, a magnetron-type reactive ion etching apparatus was used as an etching apparatus, and (P
Etching was performed under the conditions of 5) to (P8). The etching time was set such that the end point due to light emission was detected and 50% over-etching with respect to the just time was performed. When the organic silicon films of (G1) and (G2) were etched, the processed organic silicon film pattern swelled under any of the conditions (P5) to (P8), indicating that the anisotropic etching could not be performed with good anisotropy. .

In the organic silicon films (G3) to (G10), the organic silicon film pattern swells even under the condition (P5). These are considered to be due to the sponge-like transformation of the organic silicon film by etching, as can be seen from Example 7. When (G3) to (G10) were etched under the conditions of (P6) to (P8), the etching could be performed without the sponge-like transformation of the organic silicon film pattern. The dimension of the resist pattern before etching is defined by X in FIG. 1D, and the dimension of the organic silicon film pattern after etching is defined by Y in FIG. 1E, and the dimensional conversion difference (=
Y-X) is shown in Table 7 above. The size of the organic silicon film pattern after etching is large, which is thought to be caused by the product of etching the organic silicon film adhering to the resist pattern and the side wall of the organic silicon film, and the resist pattern becoming thicker. Can be

Next, as shown in FIG. 1 (f), (P7)
In the case where etching was performed, the SiO ₂ film was etched under the conditions of (Q1) in Example 13 using the resist pattern and the organic silicon film pattern as etching masks. A magnetron-type reactive plasma etching apparatus to an etching apparatus, as compared with the case of etching under the etching condition of the conventional anti-reflection film of Comparative Example 9 (Q1), the SiO ₂ film toward the case of the present embodiment The difference in dimensional conversion caused by the etching was small. The dimensional conversion difference (= ZX) caused by the etching of the organic silicon film and the etching of the SiO ₂ film was measured. As a result, even when the organic silicon film is etched under any of the conditions (P6) to (P8), the dimensional change difference is within an allowable range of -1.
It was within 5 nm to +15 nm, and the resist pattern could be faithfully transferred to the SiO ₂ film.

In Examples 20 to 25, the compounds represented by the general formula [1]
When the organic silicon film containing the organic silicon compound shown in 2] was etched, the resist pattern was not thickened. When an organic silicon compound having a structure represented by the general formula 12 is etched using a gas containing at least one of chlorine, bromine, and fluorine atoms, thickening of the resist pattern is suppressed because a volatilized product is a resist pattern and It is considered that it is difficult to adhere to the side wall of the organic silicon film. Accordingly, in the present invention, it is preferable to use an organosilicon film containing an organosilicon compound represented by the general formula 12, but when the pattern size is relatively large and the thickness of the resist pattern is not a problem, the formula is not necessarily represented by the general formula 12. It is not limited to the structure.

Example 27 A solution material of an organosilicon film was prepared by dissolving 8 g of polysilane having a weight average molecular weight of 8000 represented by the above formula [14] in 92 g of anisole. 5000 angstrom thick Si film formed by sputtering on a silicon substrate
A solution material of an organic silicon film is applied on the O ₂ film by a spin coating method, and then baked at 150 ° C. for 90 seconds to crosslink polysilane, and to have a glass transition temperature of 125.
The organic silicon film of ° C was obtained. The thickness of the organic silicon film after baking is 3000 Å.

Next, the chemically amplified positive resist formed in R19 of Example 1 was applied and baked at 98 ° C. for 120 seconds, and the resist film thickness after baking was 5000 Å. Exposure (exposure amount: 18 mJ / cm ² ) using a reduction optical type stepper using a KrF excimer laser as a light source, and baking at 98 ° C. for 120 seconds, followed by 0.21 N TMA.
H developing solution for 90 seconds, 0.25 μm
A line and space pattern was formed. When the dimensions of the resist pattern were measured by changing the thickness of the resist, no dimensional change was observed due to the standing wave generated in the resist film, and it was found that the reflected light to the resist was sufficiently suppressed. . There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

Next, the organic silicon film was etched using the resist pattern as a mask. Using a magnetron type RIE apparatus as the etching apparatus, HBr was flowed as a source gas at a flow rate of 200 SCCM, and the etching was performed under the conditions of an excitation power of 0.4 kW. We were able to. The dimensional conversion difference after the end of the etching of the organic silicon film is shown in FIG.
When defined by (X), the dimensional conversion difference generated at this time is −0.0.
005 μm, which was within the allowable range.

Further, the SiO ₂ film was etched using the etched organic silicon film and the resist pattern remaining after the etching on the organic silicon film as a mask. As the etching device, a magnetron type RIE device was used. Table 14 below shows the etching conditions when etching was performed at the highest selectivity for each gas system together with the selectivity. The selectivity in the table was defined as (etching rate of SiO ₂ film) / (etching rate of organic silicon film).

[0466]

[Table 24] From Table 14 above, C ₄ F ₁₀ was used as the source gas at a flow rate of 20.
When etching was performed under the condition of excitation power of 0.7 kW while flowing with SCCM, the selectivity was 4 and it was found that the selectivity was significantly increased.

Example 28 This example shows a case where the etching of the SiO ₂ film was performed under the etching conditions which can obtain the highest selectivity obtained in Example 27. Since the selectivity is 4 under these etching conditions, the thickness of the organic silicon film serving as a mask can be made smaller than in the above-described embodiment. The solution material of the organic silicon film was applied on the SiO ₂ film, and baked at 150 ° C. for 90 seconds. At this time, the thickness of the organic silicon film is 1
500 angstroms.

Next, a resist pattern was formed on the organic silicon film. When the dimensions of the resist pattern were measured while changing the thickness of the resist, no dimensional change was observed due to the standing wave generated in the resist film, and it was found that the reflected light to the resist was sufficiently suppressed. . There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

Next, the organic silicon film was etched under the same etching conditions as in Example 25. Since the thickness of the organic silicon film could be reduced, the dimensional conversion difference after etching of the organic silicon film could be suppressed to 0.002 μm or less. Then, using the organic silicon film as an etching mask, the SiO
_{When the two} films were etched, they could be etched with desired processing dimensions.

Comparative Example 10 A solution material for an antireflection film prepared by dissolving 10 g of polysulfone having a weight average molecular weight of 8000 in 90 g of cyclohexanone was applied on a SiO ₂ film by a spin coating method, and baked at 220 ° C. for 90 seconds. went. The thickness of the antireflection film thus obtained was 1000 Å
It is.

Next, a resist pattern was formed in the same manner as in Example 27, and the antireflection film was etched.
A magnetron type RIE apparatus was used as the etching apparatus, and CF ₄ and O ₂ were used as source gases at a flow rate of 180 SCC.
When etching was carried out under the conditions of M and 20 SCCM and excitation power of 1.2 kW, the antireflection film could be etched without the resist pattern being removed halfway.

Further, the SiO ₂ film was etched using the etched anti-reflection film as a mask. As the etching apparatus, a magnetron type RIE apparatus was used, and (CF ₄ , H ₂ ), (CHF ₃ ), (CHF ₃ , O
₂ ), (CHF ₃ , CO ₂ ), (C ₂ F ₆ ), (C ₃ F
₈ ) Etching was performed in each of the source gas systems (C ₄ F ₁₀ ) while changing etching conditions such as flow rate and excitation power. As a result, in any case, the antireflection film was not removed during the etching, and the etching could not be performed at a desired size.

Example 29 As shown in FIG. 1A, a 500 nm-thick SiN film was formed on a silicon wafer 1 by LPCVD. Next, on this SiN film 2, 8 g of polysilane having a weight average molecular weight of 1500 represented by the above formula [17-1] and a compound of the formula [3-8]
1.8 g of the crosslinking agent shown in [2], and 0.2 g of the compound shown in the formula [4-25] as a radical generator, 90 g of anisole
Is applied and baked at 180 ° C. for 10 minutes in a nitrogen atmosphere (oxygen concentration: 50 ppm or less) to crosslink polysilane and to have a glass transition temperature of 1
An organic silicon film at 83 ° C. was obtained. The thickness of the organic silicon film is 250 nm (FIG. 1B).

The exposure wavelength of the organic silicon film is 248n.
When the complex refractive index at m was measured by spectroscopic ellipsometry, n
= 2.03 and k = 0.42. Subsequently, a positive chemically amplified resist (trade name: TDU) is formed on the organic silicon film.
R-P007, manufactured by Tokyo Ohka Kogyo Co., Ltd.), and baked at 98 ° C. for 120 seconds (FIG. 1C). At this time, the thickness of the resist is 250 nm.

Next, pattern exposure (exposure amount: 30 mJ / cm ² ) was performed using a reduction optical type stepper using a KrF excimer laser beam as a light source, baking was performed at 98 ° C. for 120 seconds, and then 0.21 standard. Was developed with a TMAH developing solution of No. 1 to form a resist pattern of 0.18 μm line and space (FIG. 1D). The thickness of this resist pattern is 230 nm.

When the profile of the resist pattern thus obtained was observed by a cross-sectional SEM, no wavy shape due to a standing wave was found on the side wall. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

Using the resist pattern formed as described above as a mask, the organic silicon film was etched using a magnetron type RIE apparatus (FIG. 1).
(E)). HB with a flow rate of 20 SCCM as a source gas
r, using a mixed gas with Cl _{2 at} a flow rate of 180 SCCM,
When the organic silicon film was etched under the conditions of an excitation power of 300 W and a degree of vacuum of 30 mTorr, the organic silicon film could be etched without removing the resist pattern halfway.

The processed shape of the organic silicon film was vertically etched with good anisotropy, and the organic silicon film could be etched without deviation from the resist pattern dimension before etching. After the etching, the remaining resist film thickness is 100 nm. When the etching rate of the resist film and the organic silicon film was measured with the solid film,
25 nm / min for resist film and 95 for organic silicon film
nm / min, indicating that the etching rate of the organic silicon film was 3.8 times faster than that of the resist film.

Further, using the patterned organic silicon film and the resist pattern remaining on the organic silicon film as an etching mask, the SiN film was etched by a magnetron-type reactive ion etching apparatus (FIG. 1 (f)). ). 30 SCCM flow rate as source gas
C ₄ F ₈ , Ar flow at 160 SCCM, 140 S flow
Using CO of CCM, excitation power 350W, degree of vacuum 30m
When the etching was performed under the Torr etching conditions, the organic silicon film was not removed during the etching,
The SiN film could be etched.

At this time, the shape of the SiN film was vertically anisotropically etched with good anisotropy, and the organic silicon film could be etched without deviation from the resist pattern dimensions before etching. In this etching condition, Example 1
When the etching rates of the resist, the organic silicon film and the SiN film were measured with the solid film in the same manner as in Example 5, the resist film was 45 nm / min, and the organic silicon film was 17 nm / min.
min, the SiN film is 230 nm / min
The etching rate of the film is 13.5 than that of the organic silicon film.
It can be seen that the organic silicon film is used as an etching mask when etching SiN, which is more dry-resistant than the resist film, 5.1 times faster than the resist film. Therefore, it is considered that the SiN film could be etched without deviation from the resist pattern dimension before etching and with good vertical anisotropy.

Example 30 As shown in FIG. 1A, a 500 nm-thick SiO ₂ film 2 was formed on a silicon wafer 1 by LPCVD.
Next, a solution material prepared by dissolving 10 g of polyphenyl having a weight-average molecular weight of 8900 in 90 g of xylene was applied on the SiO ₂ film 2 and baked at 160 ° C. for 120 seconds to evaporate the solvent. The thickness of the organic silicon film 3 thus obtained is 250 nm, the complex refractive index at a wavelength of 248 m is n = 1.92, k = 0.48, and the glass transition temperature is 98 ° C. (FIG. 1 (b)).

Next, a positive chemically amplified resist (trade name: TDUR-P007, manufactured by Tokyo Ohka Kogyo Co., Ltd.) 4 was applied on the organic silicon film 3 and baked at 98 ° C. for 120 seconds (FIG. 1 ( c)). At this time, the thickness of the resist 4 is 150 nm. Then, for this resist 4, K
Pattern exposure is performed using a reduction optical stepper using rF excimer laser light as a light source (exposure amount: 30 mJ / c).
m ² ), after baking at 98 ° C. for 120 seconds,
Developing with 0.21 TMAH developing solution
As shown in (d), a 0.18 μm line and space resist pattern 4 was formed.

The thickness of this resist pattern 4 is 130 n.
m. When the profile of the resist pattern 4 was observed by a cross-sectional SEM, no wavy shape due to a standing wave was found on the side wall. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

The resist pattern 5 formed as described above
Is used as an etching mask, and a magnetron type RI is used.
The organic silicon film 3 was etched by the E apparatus. When the organic silicon film 3 was etched using Cl ₂ at a flow rate of 200 SCCM as a source gas and under the etching conditions of an excitation power of 200 W and a degree of vacuum of 25 mTorr, the resist pattern 4 was not removed during the etching. Was able to be etched.

The processed shape of the organic silicon film 3 was vertically etched with good anisotropy, and the organic silicon film 3 could be etched without deviation from the resist pattern dimension before etching. After the etching, the remaining resist film thickness is 80 nm. When the etching rates of the resist film and the organic silicon film were measured with the solid film, the etching rate of the resist film was 23 nm / min, the organic silicon film was 210 nm / min, and the etching rate of the organic silicon film was 9.1 times faster than the resist film. I understood.

Further, the resist pattern was peeled off and the SiO ₂ film was sequentially etched by a magnetron type RIE apparatus (FIG. 2C). The stripping of the resist pattern was performed under the conditions of an excitation power of 200 W and a degree of vacuum of 30 mTorr using an O ₂ gas at a flow rate of 20 SCCM as a source gas.

Next, the etching conditions were changed in the same chamber to etch the SiO ₂ film. That is,
CHF _{3 at} a flow rate of 30 SCCM and a flow rate of 1 as a source gas
When etching was performed under the etching conditions of 280 W of excitation power and 15 mTorr of vacuum using CO of 00 SCCM and Ar of a flow rate of 100 SCCM, the SiO ₂ film could be etched without the organic silicon film being removed halfway. Was. At this time, the shape of the SiO ₂ film was vertically etched with good anisotropy, and the organic silicon film could be etched without shifting from the resist pattern dimensions before the etching.

[0488] Under these etching conditions, when the etching rates of the resist film, the organic silicon film and the SiO ₂ film were measured using the solid film, the resist film was 56 nm / min, the organic silicon film was 20 nm / min, and the SiO ₂ film was 368 nm.
It was found that the etching rate of the SiO ₂ film was 18.4 times faster than that of the organic silicon film at nm / min, and that the organic silicon film was used as an etching mask of the SiO ₂ film having a higher dry etching resistance than the resist.

[0489] Therefore, the resist pattern before etching does not deviate from the dimension of the resist pattern and has good vertical anisotropy.
It is considered that the O ₂ film could be etched.

Example 31 In Example 29, after processing the SiO ₂ film, the resist and the organic silicon film as an etching mask were sequentially peeled off using a downflow etching apparatus. When O ₂ gas at a flow rate of 20 SCCM was used as a source gas and the etching was performed under the etching conditions of an excitation power of 200 W and a vacuum degree of 8 mTorr, the resist could be completely removed.

The infrared absorption spectrum of the organic silicon film after the resist was stripped was measured.
An absorption due to the Si—O—Si bond was observed at 00 cm ⁻¹ . This means that polysilane was glassed by exposure to oxygen plasma.

Next, hydrofluoric acid and pure water were added in a weight ratio of 1: 500.
When the solution was infiltrated into a diluted hydrofluoric acid solution mixed for 90 seconds, the vitrified organic silicon film could be selectively removed from the silicon oxide film.

Example 32 In Example 29, after processing the SiO ₂ film, the resist and the organic silicon film as an etching mask were sequentially peeled off using a downflow etching apparatus. Using O ₂ at a flow rate of 20 SCCM as a source gas,
When the resist was etched under the etching conditions of an excitation power of 200 W and a degree of vacuum of 8 mTorr, the resist could be completely removed. The polysilane was glassized by exposure to oxygen plasma, but the glassy polysilane was etched under the etching conditions of source gas CF ₄ = 30 SCCM, O ₂ = 40 SCCM, excitation power of 800 W, and vacuum degree of 35 mTorr. It was possible to selectively peel off without removing the SiO ₂ film.

Example 33 As shown in FIG. 8A, a 500 nm thick SiO ₂ film 22 was formed on a silicon wafer 21 by LPCVD. Then, an organic silicon compound having a weight average molecular weight 14000 represented by the formula [1-99] on the SiO ₂ film 2 (n / m
= 1/4) A solution material prepared by dissolving 10 g in 90 g of anisole was applied and baked at 160 ° C for 120 seconds to evaporate the solvent. The organic silicon film 3 thus obtained has a thickness of 150 nm and a glass transition temperature of 132 ° C. The complex refractive index at a wavelength of 248 m is n = 2.01, and k = 0.38 (FIG. 1).
(B)). Next, a positive chemically amplified resist (trade name: TDUR-P007, manufactured by Tokyo Ohka Kogyo Co., Ltd.) 4 was applied on the organic silicon film 23, and baked at 98 ° C. for 120 seconds (FIG. 1C). . At this time, the thickness of the resist 4 is 150 nm. Then, for this resist 4, K
Pattern exposure is performed using a reduction optical stepper using rF excimer laser light as a light source (exposure amount: 30 mJ / c).
m ² ), after baking at 98 ° C. for 120 seconds,
Developing with 0.21 TMAH developing solution
As shown in (d), a 0.18 μm line and space resist pattern 24 was formed.

The resist pattern 4 has a thickness of 130 n.
m. When the profile of the resist pattern 4 was observed by a cross-sectional SEM, no wavy shape due to a standing wave was found on the side wall. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

The resist pattern 4 formed as described above
Is used as an etching mask, and a magnetron type RI is used.
The organic silicon film 3 was etched by the E apparatus. As a source gas, a mixed gas of Cl _{2 at} a flow rate of 200 SCCM and SF _{6 at} a flow rate of 10 SCCM was used, and an excitation power of 2 was used.
When the organic silicon film 3 was etched under the etching conditions of 00 W and a degree of vacuum of 25 mTorr, the organic silicon film 3 could be etched without the resist pattern 5 being removed in the middle.

The processed shape of the organic silicon film 3 was vertically etched with good anisotropy, and the organic silicon film 3 could be etched without shifting from the resist pattern dimension before etching. After the etching, the remaining resist film thickness is 80 nm. When the etching rates of the resist film and the organic silicon film were measured with the solid film, the etching rate of the resist film was 48 nm / min, the organic silicon film was 210 nm / min, and the etching rate of the organic silicon film was 4.4 times faster than the resist film. I understood.

Further, the resist pattern was peeled off and the SiO ₂ film was etched sequentially by a magnetron type RIE apparatus (FIG. 2C). The stripping of the resist pattern was performed under the conditions of an excitation power of 200 W and a degree of vacuum of 30 mTorr using an O ₂ gas at a flow rate of 20 SCCM as a source gas.

Next, the etching of the SiO ₂ film was performed in the same chamber under different etching conditions. That is,
CHF _{3 at} a flow rate of 30 SCCM and a flow rate of 1 as a source gas
Using CO of 00 SCCM and O ₂ of flow rate 100 SCM,
When etching was performed under the etching conditions of an excitation power of 280 W and a degree of vacuum of 15 mTorr, the SiO ₂ film could be etched without the organic silicon film being cut off halfway. At this time, the shape of the SiO ₂ film was vertically etched with good anisotropy, and the organic silicon film could be etched without shifting from the resist pattern dimensions before the etching.

Under these etching conditions, a resist film, an organic silicon film and a SiO
_When the etching rate of the _two films was measured, the resist film was 54 nm / min, and the organic silicon film was 20 nm / mi.
n, the etching rate of the SiO ₂ film is 18.4 times faster than that of the organic silicon film when the SiO ₂ film is 368 nm / min,
It was found that the organic silicon film was used as an etching mask for the SiO ₂ film having a higher dry etching resistance than the resist.

[0501] Therefore, the resist pattern before etching does not deviate from the resist pattern size and has good vertical anisotropy.
It is considered that the O ₂ film could be etched.

Example 34 As shown in FIG. 1A, a 500 nm-thick SiN film 2 was formed on a silicon wafer 1 by LPCVD. Next, on the SiN film 2, an organosilicon compound having a weight average molecular weight of 12800 represented by the above formula [1-95] (n / m =
1/1) A solution material prepared by dissolving 10 g in 90 g of anisole is applied, baked at 160 ° C. for 120 seconds, and the solvent is vaporized to form an organic silicon film as shown in FIG. 3 was formed. At this time, the thickness of the organic silicon film 3 is 250 nm, and the glass transition temperature is 138 ° C. The complex refractive index at a wavelength of 248 m is n = 2.01, k = 0.35.

Next, a positive chemically amplified resist (trade name: TDUR-P007, manufactured by Tokyo Ohka Kogyo Co., Ltd.) 4 was applied on the organic silicon film 3 and baked at 98 ° C. for 120 seconds (FIG. 1). (C)). At this time, the thickness of the resist 4 is 150 nm.

Next, the resist 4 was subjected to pattern exposure (exposure amount: 30 mJ / cm ² ) using a reduction optical stepper using KrF excimer laser light as a light source.
After baking at 8 ° C. for 120 seconds, development processing was performed with a 0.21 N TMAH developer to form a resist pattern 4 of 0.18 μmL / S as shown in FIG. 1D.

The thickness of the resist pattern is 130 nm. When the profile of the resist pattern 4 was observed with a cross-sectional SEM, no wavy shape due to a standing wave was found on the side wall. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

Using the resist pattern formed as described above as a mask, the polysilane film was etched by a magnetron type RIE apparatus (FIG. 1E). Using Cl ₂ at a flow rate of 200 SCCM as a source gas and etching the organic silicon film under the etching conditions of an excitation power of 200 W and a degree of vacuum of 25 mTorr, the organic silicon film is etched without the resist pattern being removed in the middle. I was able to.

[0507] Observation of the processed shape of the polysilane film shows that the etching was performed vertically and anisotropically with good anisotropy, and that the organic silicon film could be etched without deviation from the resist pattern dimensions before etching. After the etching, the remaining resist film thickness is 80 nm. When the etching rates of the resist film and the organic silicon film were measured with the solid film, the resist film was found to be 52 nm / mi.
n, the organic silicon film is 195 nm / min, and the etching rate of the polysilane film is 3.75 times higher than that of the resist film.
It turned out to be twice as fast.

Further, the resist pattern was peeled off and the SiN film was sequentially etched by a magnetron type RIE apparatus (FIG. 2 (f)). The resist pattern was peeled off using O ₂ at a flow rate of 30 SCCM as a source gas.
The test was performed under the conditions of an excitation power of 200 W and a degree of vacuum of 30 mTorr.

Next, the etching conditions were changed in the same chamber to etch the SiN film. That is,
C ₄ H _{8 at} a flow rate of 30 SCCM and a flow rate of 1 as a source gas
When etching was performed under the etching conditions of 280 W of excitation power and 15 mTorr of vacuum using CO of 00 SCCM and O ₂ at a flow rate of 3 SCCM, the SiN film could be etched without the organic silicon film being removed halfway. Was. At this time, the shape of the SiN film was vertically etched with good anisotropy, and the organic silicon film could be etched without shifting from the resist pattern dimensions before the etching.

[0510] Under these etching conditions, when the etching rates of the resist film, the organic silicon film and the SiN film were measured for the solid film, the resist film was 62 nm / min, the organic silicon film was 42 nm / min, and the SiN film was 368 nm.
/ Min, the etching rate of the SiN film was 10.1 times faster than that of the organic silicon film, and it was found that the organic silicon film was used as an etching mask of SiN which was more resistant to etching than the resist. Therefore, it is considered that the SiN film could be etched without deviation from the resist pattern dimension before etching and with good vertical anisotropy.

Example 35 A TEOS oxide film having a thickness of 600 nm was formed on a silicon wafer by a plasma CVD method. Next, a weight average molecular weight of 12,500 represented by the above formula [13] is formed on the TEOS oxide film.
13 g of polysilane (n / m = 4/1) from Anisole 8
A solution material dissolved in 7 g was applied and baked at 160 ° C. for 180 seconds. The thickness of the organic silicon film thus obtained was 400 nm and the glass transition temperature was 1
39 ° C. The complex refractive index at a wavelength of 248 nm is n =
2.03, k = 0.32.

A positive chemically amplified resist (trade name: APEX-E, manufactured by Shipley Co.) was applied on the organic silicon film, and baked at 98 ° C. for 120 seconds. At this time, the thickness of the resist is 250 nm. Then, an upper antireflection film (trade name: Aquatar (Aq) is formed on the resist film.
uatar) (manufactured by Hoechst) to a thickness of 42 nm.

Next, pattern exposure was performed (exposure amount: 28 mJ / cm ² ) using a reduction optical type stepper using a KrF excimer laser beam as a light source, baking was performed at 98 ° C. for 120 seconds, and then 0.21 standard. Was developed using a TMAH developer solution of No. 1, and a resist pattern of 0.25 μmL / S was formed. Since the upper antireflection film is water-soluble, it is removed from the resist film during the development process.

When the profile of the resist pattern thus obtained was observed by a cross-sectional SEM, no wavy shape due to a standing wave was found on the side wall.

[0515] A resist pattern is formed as described above.
As a result of processing the TEOS oxide film under the no etching condition as in Example 29, the TEOS oxide film could be etched without deviating from the resist pattern dimensions before etching.

Example 36 A spin-on glass (trade name: R) was placed on a silicon wafer.
7, Hitachi Chemical Co., Ltd.) by spin coating method,
After baking sequentially at 80 ° C. for 1 minute, at 150 ° C. for 1 minute, and at 200 ° C. for 1 minute, 4 times while performing nitrogen purging.
Baking was performed at 00 ° C. for 30 minutes to form a spin-on-glass film. The film thickness after the baking treatment is 500 nm.

Next, a solution material prepared by dissolving 10 g of polysilane (n / m = 4/1) having an average molecular weight of 12,500 represented by the above formula [13] in 90 g of anisole was applied on a spin-on glass, and the solution was heated at 180 ° C. Baking was performed for 60 seconds to form an organic silicon film. At this time, the thickness of the organic silicon film was 300 nm, and the glass transition temperature was 1
39 ° C.

[0518] The ratio of O / Si in the thickness direction of the organic silicon film was examined by XPS spectroscopy.
0 was obtained. FIG. 10 shows that although the surface is oxidized, the reflected light of exposure light from the organic silicon film to the resist can be suppressed, and a resist pattern with high dimensional control can be obtained. As described above, the reflection coefficient may be suppressed by increasing the extinction coefficient of the silicon organic film in the thickness direction from the surface toward the insulating film.

Next, a positive chemically amplified resist (trade name: APEX-E, manufactured by Shipley Co.) is formed on the organic silicon film.
Was applied and baked at 98 ° C. for 120 seconds to form a resist film. At this time, the thickness of the resist film is 10
0 nm. Then, KrF
Perform pattern exposure using a reduction optical type stepper using excimer laser light as a light source (exposure amount: 28 mJ / c
m ² ), after baking at 98 ° C. for 120 seconds,
Develop with a 0.21 normal TMAH developing solution.
A resist pattern of 25 μmL / S was formed.

When the profile of the resist pattern thus obtained was observed by a cross-sectional SEM, no wavy shape due to a standing wave was found on the side wall. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

[0521] A resist pattern is formed as described above.
As a result of processing the spin-on-glass in the same manner as in Example 29, the spin-on-glass could be etched without deviating from the resist pattern dimensions before the etching.

Example 37 A BPSG film having a thickness of 500 nm was formed on a silicon wafer by a plasma CVD method. Next, a solution prepared by dissolving 10 g of polysilane (n / m = 4/1) having a weight average molecular weight of 9000 represented by the above formula [14] and 5 g of poly (phenylsilane) having a molecular weight of 2,000 in 85 g of anisole on the BPSG film. After applying the material, baking was performed at 160 ° C. for 180 seconds. At this time, the thickness of the silicon organic film is 15
At 0 nm, the glass transition temperature is 152 ° C. Wavelength 24
The complex refractive index at 8 nm is n = 2.20 and k = 0.39. Then, add 10 g of polysulfone to Anisole 90
g, and applied to the silicon organic film, and baked at 220 ° C. for 180 seconds to form a lower layer film for improving the resist profile. The thickness of the lower layer film is 30 nm.

Next, a negative chemically amplified resist (trade name: TDUR-N908, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is formed on the lower film.
And baked at 98 ° C. for 120 seconds. The thickness of the resist film thus obtained is 300 nm. Thereafter, the resist film was subjected to pattern exposure (exposure amount: 38 mJ / cm ² ) using a reduction optical type stepper using KrF excimer laser light as a light source, and baked at 98 ° C. for 120 seconds, followed by 0.21 The resist was developed with a specified TMAH developer to form a resist pattern of 0.18 μmL / S. When the profile of this resist pattern was observed by a cross-sectional SEM, no wavy shape due to a standing wave was found on the side wall. Further, on the lower layer film, as shown in FIG. 1D, a resist pattern having a good shape without footing or erosion was obtained.

[0524] A resist pattern is formed as described above.
As a result of processing the BPSG film in the same manner as in Example 29, the BPSG film could be etched without deviating from the resist pattern dimensions before etching. As in this embodiment, a lower layer film may be formed on the organic silicon film to improve the resist shape.

Example 38 Fluorine-doped S having a thickness of 500 nm was formed on a silicon wafer.
An iO ₂ film was formed by a low pressure CVD method. Next, polysilane 1 having a molecular weight of 4000 represented by the above formula [1-84]
A solution material prepared by dissolving 0 g in 90 g of anisole was applied on the SiO ₂ film, and then baked at 160 ° C. for 60 seconds to form an organic silicon film. At this time, the thickness of the organic silicon film is 180 nm, and the glass transition temperature is 141 ° C.

A resist solution prepared by dissolving 10 g of polymethyl methacrylate in 90 g of ethyl lactate was applied to the organic silicon film, and baked at 98 ° C. for 120 seconds to form a resist film. At this time, the thickness of the resist is 200 nm. And for the resist film,
Pattern exposure was performed using a reduction optical type stepper using ArF excimer laser light as a light source (800 mJ / cm).
² ) After baking at 98 ° C for 120 seconds,
Develop with a 0.21 normal TMAH developing solution.
A resist pattern of 18 μmL / S was formed.

When the profile of the resist pattern thus obtained was observed by a cross-sectional SEM, no wavy shape due to a standing wave was observed on the side wall. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

[0528] A resist pattern is formed as described above.
As a result of processing the SiO ₂ film in the same manner as in Example 29, the SiO ₂ film could be etched without deviating from the resist pattern dimensions before etching.

Example 39 First, the polysilane used in this example was synthesized as follows. That is, 60 ml of diethyl ether and zirconocene dichloride dried at −20 ° C. in an argon atmosphere.
34 g was stirred, 1.5 M methyl ether was added little by little, and the mixture was stirred for 70 minutes. Then at 0 ° C. for 30
After stirring for minutes, diethyl ether was removed and the resulting white solid was sublimated to prepare zirconocene methyl.

Next, this zirconocene dimethyl was added to phenylsilane at a molar ratio of 50: 1, and the phenylsilane was polymerized at room temperature for 5 hours. Then, the obtained polymer was dissolved in toluene and poured into methanol with stirring to reprecipitate the polymer. Further, after reprecipitating the polymer twice with methanol in the same manner, 80-90
The polymer was dried at reduced pressure under reduced pressure to obtain a polymer represented by the formula [16-1] having a weight average molecular weight of about 2.000.

In the same manner as in Example 17, a SiO ₂ film was formed on a silicon wafer. Then, the SiO ₂ film, polysilane 8g obtained by the above method, wherein [6-
A solution in which 2 g of the crosslinking agent shown in [9] was dissolved in 90 g of anisole was applied and baked at 150 ° C. for 60 seconds to crosslink polysilane to form an organic silicon film having a thickness of 250 nm. The glass transition temperature of the crosslinked organic silicon film is 158 ° C.

Next, a resist pattern was formed on the organic silicon film in the same procedure as in Example 20.

When the profile of the obtained resist pattern was observed with a cross-sectional SEM, no wavy shape due to a standing wave was found on the side wall. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

When the organic silicon film and the SiO ₂ film were etched, as in Example 29, S
The iO ₂ film could be processed.

Example 40 An average molecular weight of 12 prepared on a quartz substrate in Example 38
A solution material prepared by dissolving 10 g of polysilane of 000 and 12 g of a crosslinking agent represented by the formula [5-24] in 90 g of anisole was applied and baked at 160 ° C. for 100 seconds. The thickness of the organic silicon film thus obtained is 300
nm and the glass transition temperature is 132 ° C.

A chemically amplified positive resist (trade name: APEX, manufactured by Shipley Co., Ltd.) was applied on the organic silicon film.
Baking was performed at 8 ° C. for 120 seconds. The thickness of the resist film thus obtained is 200 nm. Next, pattern exposure is performed with an electron beam drawing apparatus (1 μC / c
m ² ), and baked at 98 ° C. for 120 seconds. Then, a development process is performed with a 0.21 TMAH developer,
A resist pattern of 0.9 μmL / S was formed. When the profile of the resist pattern was observed by a cross-sectional SEM, no wavy shape due to a standing wave was found on the side wall.

[0537] A resist pattern is formed as described above.
A groove of 0.4 m was formed on a quartz substrate in the same manner as in Example 31. Thus, the method of the present invention can also be used for processing a quartz substrate.

Example 41 Poly (phenylsilene) 10 having a weight average molecular weight of 8000
g was dissolved in 90 g of xylene to prepare a solution material for the organic silicon film. S to be processed on silicon wafer
An iO ₂ film was formed, an organic silicon film solution material was applied on the SiO ₂ film by a spin coating method, baked at 160 ° C. for 300 seconds, and the solvent was dried. At this time, the thickness of the organic silicon film is 250 nm, and the glass transition temperature is 132 ° C. Λ measured by spectroscopic ellipsometry
= 193 nm, the complex refractive index is n = 2.03, k =
0.48.

Next, polymethyl methacrylate 1
A resist solution prepared by dissolving 0 g in 90 g of ethyl lactate was applied and baked at 110 ° C. for 90 seconds. The resist film thickness after baking is 100 nm.
Next, exposure was performed with a reduction optical stepper using ArF excimer laser light as a light source (exposure amount: 500 mJ / cm ² ).
A development process was performed for 90 seconds using a 0.21 N TMAH developer to form a 0.18 μm line and space pattern. The resist pattern did not show any tailing or erosion, and a good resist profile was obtained. The thickness of the resist was changed in the range of 50 nm to 150 nm, and the dimension of the resist pattern was measured at each resist thickness. As a result, it was found that the dimensional variation caused by the standing wave generated in the resist film was negligible. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

Next, using the formed resist pattern as a mask, using Cl ₂ at a flow rate of 300 SCCM as a source gas, and applying a pumping power of
When the organic silicon film was etched in the same manner as in Example 12 except that W was used, the resist pattern was not completely removed even after the etching of the organic silicon film was completed, and the organic silicon film was well controlled. Could be etched.

Example 42 Fluorine-doped S having a thickness of 500 nm was formed on a silicon wafer.
An iO ₂ film was formed by a low pressure CVD method. Next, the weight average molecular weight represented by the formula [1-95] is 12. . . A solution material prepared by dissolving 10 g of an organosilicon compound (n / m = 1/4) in 90 g of anisole is applied on a SiO ₂ film, and then baked at 180 ° C. for 100 seconds in a nitrogen atmosphere to obtain an organic silicon compound. A film was formed. At this time, the thickness of the organic silicon film is 200 nm, and the glass transition temperature is ° C. The complex refractive index at a wavelength of 193 nm is n = 2.
10, k = 0.57.

Next, a resist solution prepared by dissolving 10 g of polymethyl methacrylate in 90 g of ethyl lactate was applied on the organic silicon film, and baked at 98 ° C. for 120 seconds to form a resist film. At this time, the thickness of the resist film is 200 nm. Then, pattern exposure is performed on the resist film using a reduction optical type stepper using ArF excimer laser light as a light source (800 m).
(J / cm ² ), baked at 98 ° C. for 120 seconds, and then developed with a 0.21 N TMAH developer to form a 0.18 μmL / S resist pattern.

When the profile of the resist pattern thus obtained was observed by a cross-sectional SEM, no wavy shape due to a standing wave was observed on the side wall. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

[0544] A resist pattern is formed as described above.
As a result of processing the SiO ₂ film in the same manner as in Example 29, it was possible to etch the SiO ₂ film without deviating from the resist pattern dimensions before the etching.

Example 43 Fluorine-doped Si having a thickness of 500 nm was formed on a silicon wafer.
An O ₂ film was formed by a low pressure CVD method. Then, the average molecular weight of 1 doped with AsF ₅ represented by the above formula [17-7] is 1
A solution material prepared by dissolving 10 g of 2000 polysilane (n / m = 1/4) in 90 g of anisole was applied on the SiO ₂ film, and then baked at 180 ° C. for 100 seconds in a nitrogen atmosphere. The organic silicon film thus obtained has a thickness of 300 nm and a glass transition temperature of ° C.

Then, the organic silicon film was exposed to an atmosphere containing AsF ₅ , and the organic silicon film was doped with AsF ₅ to have conductivity.

A resist solution prepared by dissolving 10 g of polymethyl methacrylate in 90 g of ethyl lactate was applied on the organic silicon film, and baked at 98 ° C. for 120 seconds. The thickness of the resist film thus obtained is 200 n
m. Next, the resist film is subjected to pattern exposure using an electron beam lithography system (10 μm C / c
m ² ), development processing was performed with a 0.21 N TMAH developer to form a 0.18 μmL / S resist pattern. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

As described above, a resist pattern was formed and SiO ₂ was processed in the same manner as in Example 29.
The SiO ₂ film could be etched without shifting from the resist pattern dimensions before etching. Also,
The conductivity of the organic silicon film obtained in this example is
The resist pattern was 5 × 10 ⁻⁶ S / cm, and there was no displacement due to charge-up, and a resist pattern could be formed.

Example 44 Fluorine-doped Si having a thickness of 500 nm was formed on a silicon wafer.
An O ₂ film was formed by a low pressure CVD method. Then, a solution material prepared by dissolving 10 g of polysilane having a weight average molecular weight of 12000 represented by the above formula [17-3] in 90 g of anisole is applied on a SiO ₂ film, and then the solution material is treated in a nitrogen atmosphere.
Baking was performed at 0 ° C. for 100 seconds. The thickness of the organic silicon film thus obtained is 200 nm, and the glass transition temperature is 136 ° C.

A chemically amplified positive resist (APEX, manufactured by Shipley Co.) was applied on the organic silicon film and baked at 98 ° C. for 120 seconds. The thickness of the resist film thus obtained is 200 nm. Next, the resist film was subjected to pattern exposure (45 mJ / cm ² ) using an X-ray stepper using emitted light as a light source,
Baking was performed at 120 ° C. for 120 seconds. And 0.21
Develop with a specified TMAH developer and apply 0.18 μm
An L / S resist pattern was formed. There was no footing or erosion in the shape of the resist pattern, and a good resist profile was obtained.

The resist pattern is formed as described above.
As a result of processing the SiO ₂ film in the same manner as in Example 29, the SiO ₂ film could be etched without deviating from the resist pattern dimensions before etching.

Example 45 A 300 nm thick SiO ₂ film was formed on a silicon wafer by L
It was formed by the PCVD method. Next, as shown in FIG. 1A, a film thickness of 300 n was formed on the silicon wafer by sputtering.
m of amorphous silicon film was formed. And FIG.
As shown in (b), the organic silicon films 3 were formed on amorphous silicon by the methods (B3) to (B10) in Example 2. The thickness of the organic silicon film is 100 nm.

Next, in the same manner as in Embodiment 21, FIG.
As shown in (c), a resist 4 was formed on the organic silicon film. Further, as shown in FIG. 11A, a development process was performed using a 0.21 N
m and a line and space pattern were formed. The thickness of the resist pattern 5 after the development processing is 250 nm.

When the resist pattern was observed, there was no displacement due to charge-up. In addition, no tailing or erosion was observed in the shape of the resist pattern, and a good resist profile was obtained.

Next, as shown in FIG. 11B, the organic silicon film and the amorphous silicon film were collectively etched using the resist pattern as an etching mask. A TCP type etching apparatus is used as an etching apparatus, and a source gas Cl2 = 10 SCCM, an excitation power of 100 W, a degree of vacuum of 12 mTorr, and a substrate temperature of 30 ° C.
When etching was performed under the conditions described above, the organic silicon film and the amorphous silicon could be etched without the resist pattern being scraped off in the middle.
The m line and space pattern 7 could be formed on the amorphous silicon film.

Example 46 A 300 nm thick SiO ₂ film was formed on a silicon wafer by L
It was formed by the PCVD method. Next, as shown in FIG. 1A, a 300 nm-thick tungsten film was sequentially formed on the SiO ₂ film by a sputtering method to form a wiring film. Then, as shown in FIG. 1B, (C3) to (C1) of Example 3
An organic silicon film was formed on each tungsten by the method of 0). The thickness of the organic silicon film is 100 nm.

Next, as shown in FIG.
(R) was applied onto each organic silicon film, and heated on a hot plate at 110 ° C. for 90 seconds to form a resist. Resist thickness is 300nm
It is. Subsequently, after pattern exposure was performed using a reduction optical type stepper using a KrF excimer laser as a light source, the substrate was heated at 110 ° C. for 90 seconds on a hot plate.

Further, as shown in FIG.
Perform development processing using a 21N TMAH developer,
A 0.18 μm line and space pattern was formed. The thickness of the resist pattern after development processing is 250 nm
It is. As a result of observing the resist profile using a scanning electron microscope, it was found that there was no wavy shape due to a standing wave in the resist film on any of the organic silicon films, and a good resist profile was obtained. Next, as shown in FIG. 11B, the organic silicon film and the tungsten film were collectively etched using the resist pattern as an etching mask. A TCP type etching apparatus is used as an etching apparatus, and a source gas C
l2 = 100 SCCM, TCP power / bias power = 500/250 W, degree of vacuum 12 mTorr, substrate temperature 30 ° C. When etching was performed, the organic silicon film and the tungsten film were etched without the resist pattern being cut off in the middle. 0.18
A wiring pattern of a μm line and space pattern could be formed.

As in Embodiments 45 and 46, the film to be processed is made of a silicon-based material such as amorphous silicon, polysilicon, or a silicon substrate, a wiring film alone, a laminated structure of a wiring film and a barrier metal, or a film of a barrier metal and TiN or TiW. In the case of such a laminated structure with an anti-reflection film, the steps can be shortened because the etching can be performed collectively under the same etching conditions as the organic silicon film.

The following Examples 47 to 51 relate to the third embodiment.

Example 47 An 800 nm-thick SiN film was formed on a silicon wafer by LPCVD (see FIG. 1A). Next, SiN
An organic silicon film having a thickness of 100 nm was formed on the film (see FIG. 1B). The following (H1) ~
The films formed by the method (H6) were used.

(H1): 9 g of a polysilane having a weight average molecular weight of 1,000 represented by the formula [1-1], 0.9 g of a crosslinking agent represented by the formula [3-1], and 0.1 g of a radical generator benzoin were added to 90 g of anisole. The solution prepared by dissolution was applied on a base substrate by a spin coating method, and then heated at 180 ° C. for 10 minutes in a nitrogen atmosphere (oxygen concentration: 50 ppm or less). The glass transition temperature of the obtained organic silicon film is 68 ° C.
It is.

(H2): Polysilane having a weight average molecular weight of 12,000 represented by the formula [1-53] (n / m = 1/4) 1
A solution prepared by dissolving 0 g in 90 g of anisole was applied by a spin coating method, and then heated at 160 ° C. for 1 minute. The glass transition temperature of the obtained organic silicon film is 123.
° C.

(H3): Polysilane having a weight average molecular weight of 18,000 represented by the formula [1-13] (n / m = 1/4) 1
A solution prepared by dissolving 0 g in 90 g of anisole was applied by a spin coating method, and then heated at 160 ° C. for 1 minute. The glass transition temperature of the obtained organic silicon film is 148.
° C.

(H4): Polysilane having a weight average molecular weight of 15,000 represented by the formula [1-82] (n / m = 1/4)
9.99 g, 0.01 g of fullerene and 90 g of anisole
Was applied by a spin coating method, and then heated at 160 ° C. for 1 minute. The glass transition temperature of the obtained organic silicon film is 123 ° C.

(H5): Polysilane having a weight average molecular weight of 18,000 represented by the formula [1-50] (n / m = 1/1) 1
A solution prepared by dissolving 0 g in 90 g of anisole was applied by a spin coating method, and then heated at 160 ° C. for 1 minute. The glass transition temperature of the obtained organic silicon film is 118
° C.

(H6): Polysilane represented by the formula [1-51] was formed on an underlying substrate by a CVD method. The glass transition temperature of the obtained organic silicon film is 52 ° C.

Table 15 shows the n and k values at a wavelength of 248 nm, which is the exposure wavelength measured by spectroscopic ellipsometry. It can be seen that each of them has a value necessary to function as an antireflection film. Next, a polyvinylphenol resin 5 having a weight average molecular weight of 20,000 was formed on each organic silicon film.
g, 4.97 g of an inhibitor resin in which 50% of hydroxyl groups of polyvinyl phenol having a weight average molecular weight of 27,000 are substituted with a tertiary butoxycarbonyl group, and 0.03 g of sulfonimide as an acid generator are dissolved in 90 g of ethyl lactate. The prepared resist solution is applied by a spin coating method, and prebaked at 110 ° C. for 90 seconds to form a film having a thickness of 20 μm.
A 0 nm resist was formed (see FIG. 1C). And
After pattern exposure was performed using a reduction optical stepper (NA = 0.5, σ = 0.5) using a KrF excimer laser as a light source, post-exposure bake was performed at 110 ° C. for 90 seconds. Then, TMA of 0.21 regulation
A 0.18 μm line and space pattern was formed by performing a development process using an H developer (see FIG. 1D).
On the organic silicon film (H1), the resist pattern dimensions were measured while changing the thickness of the resist. Table 15 shows the results of measuring the amount of dimensional change due to the change in the resist film thickness for each organic silicon film. The magnitude of this dimensional variation is
Defined in Example 17.

From Table 15, it can be seen that a resist pattern having good dimensional controllability was obtained because the reflected light from the SiN film was suppressed within the allowable range of 9 nm or less in any of the organic silicon films.

Next, the organic silicon film was etched using the resist pattern as an etching mask (FIG. 1).
(E)). A parallel plate type RIE apparatus was used as an etching apparatus, and C was used as a source gas at a flow rate of 200 SCCM.
l ₂ , vacuum degree 75 mTorr, excitation power 200
The etching was performed under the etching conditions of W and the substrate temperature of 60 ° C., and the etching time was set to be 50% over-etching with respect to the end point detected by light emission from plasma.

When the processed shape was observed with a scanning electron microscope, it was found that the organic silicon film could be etched with good anisotropy. Table 15 below shows the result of defining the dimension conversion difference by the difference (= Y−X) between the dimension X of the resist pattern before the etching and the dimension Y after the etching of the organic silicon film. From Table 15, it can be seen that almost -2 nm to +2 nm.
It can be seen that the organic silicon film has been processed with good dimensional controllability.

Next, using the parallel plate type RIE apparatus used for etching the organic silicon film, O ₂ at a flow rate of 300 SCCM was used as a source gas, and the degree of vacuum was 12 mTorr.
Oxygen plasma was generated under the conditions of r and excitation power of 75 W to oxidize the organic silicon film (see FIG. 3A). The infrared absorption spectrum of the organic silicon film was measured before and after the oxidation treatment.
An absorption peak due to a siloxane bond near 000 to 1100 cm ^-1 was growing. This is considered to be due to the fact that the bond between silicon and silicon contained in the main chain in the organosilicon compound was broken by oxygen plasma and combined with oxygen radicals to form a siloxane bond. The resist pattern was not ashed by the irradiation of the oxygen plasma. Dimension W of organic silicon film after oxidation treatment
Table 15 shows the results of measuring the dimensional variation (= W−Y) due to the oxidation treatment. From the table, it can be seen that there is hardly any dimensional change due to the oxidation treatment. The dimensional conversion difference caused by the etching of the organic silicon film and the dimensional variation caused by the oxidation treatment are within the allowable range of -9 nm to +9 nm in any of the organic silicon films, and the mask material is formed with good dimensional control. I was able to.

Next, the SiN film was etched using the oxidized organic silicon film as an etching mask (see FIG. 3B). A parallel plate type RIE device was used as the etching device, and the flow rate was 50 SCC as a source gas.
M CF ₄ and N ₂ at a flow rate of 100 SCCM, a degree of vacuum of 45 mTorr, an excitation power of 200 W, and a substrate temperature of 60
Etching was performed under the etching condition of ° C. The etching time is 5 times with respect to the end point detected by the emission from the plasma.
It was set so that over-etching would be 0%.

When the processed shape was observed with a scanning electron microscope, it was found that the organic silicon film could be etched with good anisotropy. Table 15 shows the result of calculating the etching selectivity between the oxidized organic silicon film and the SiN film (= etch rate of SiN film / etch rate of oxidized organic silicon film) by stopping the etching of the SiN film halfway. Shown in The etch rate of SiN is 25
0 nm / min. From the table, it was found that the selectivity was 10 or more in each case, indicating that the SiN film had sufficient resistance as a mask material.

Comparative Example 11 In Example 47, after etching the organic silicon film,
When the SiN film was etched without performing the oxidation treatment, the resist pattern and the organic silicon film were not removed during the etching of the SiN film, and the SiN film could not be etched.

Comparative Example 12 In Example 47, an SiO ₂ film was used as a hard mask instead of the oxidized organic silicon film. That is,
An SiO ₂ film 33 was formed on a SiN film 32 formed on a silicon wafer 31 by LPCVD (FIG. 12).
(A), 12 (b)). And 10g of polysulfone
Is dissolved in 90 g of cyclohexanone,
After coating by spin coating on the iO ₂ film, 220
Heating was performed at 90 ° C. for 90 seconds to form an antireflection film 34 (FIG. 12C). The thickness of the antireflection film 34 after the heat treatment is 90 nm. The n and k values at a wavelength of 248 nm, which is the exposure wavelength measured by the spectral ellipsometer, are as follows: n = 1.72, k
= 0.23.

Next, a resist 35 is formed on the antireflection film 34 in the same manner as in the embodiment 47 (FIG. 12D).
A 0.18 μm line and space pattern was formed (FIG. 12E). Then, using the resist pattern 35 as an etching mask, the anti-reflection film 34 and the SiO 2
_{The two} films 33 were collectively etched (FIG. 12F).
A parallel plate type RIE apparatus was used as an etching apparatus, and C ₄ F _{8 at} a flow rate of 30 SCCM and a flow rate of 100 were used as a source gas.
Using SCCM CO, flow rate of 100 SCCM Ar, vacuum degree 45 mTorr, excitation power 200 W, substrate temperature 60
The etching was performed under the condition of ° C., and the etching time was set so as to be 50% over-etched with respect to the end point detected by the emission from the plasma.

The resist pattern dimension X before etching
And the difference between the dimension Y of the SiO ₂ film after etching (= Y−
X) defined the dimensional conversion difference. Dimension conversion difference is +12 nm
It can be seen that it exceeds the allowable range of -9 nm to +9 nm. This is considered to be caused by the interposition of the antireflection film between the resist and the SiO ₂ film.

In the method according to the present invention, the organic silicon film acts as an antireflection film at the time of pattern exposure, so that it is not necessary to intervene between the resist and the hard mask. To that extent, the resist pattern can be faithfully transferred to the organic silicon film.

Next, the resist pattern 35 and the antireflection film 34 were removed by oxygen plasma, and the SiN film 32 was etched using the SiO ₂ film pattern 33 as an etching mask (FIG. 12 (g)). The etching conditions are the same as in Example 47. It stopped halfway etching of SiO ₂ film, etching selectivity of the SiO ₂ film and the SiN film (= SiN film etching rate / SiO
As a result of calculating (etching rate of the _two films), it was found to be 10.6. From these results, it can be seen that the oxidized organic silicon film according to the present invention has the same etching resistance as the SiO ₂ film even in the plasma suitable for etching the SiN film. Comparative Example 13 This is an example in which the silicon film is directly irradiated with ultraviolet light to pattern the organic silicon film.

[0580] Si formed on the silicon wafer 41
An organic silicon film 43 having a thickness of 100 nm is formed on the N film 42.
Was formed in the same manner as in Example 47 (FIG. 13A, FIG.
2B). Next, pattern exposure is performed using an exposure apparatus using an ArF excimer laser as a light source, and the organic silicon film 4 is exposed.
The exposed portion 44 of No. 3 was oxidized (FIG. 13C).

Next, the unexposed portion of the organic silicon film 43 that has not been oxidized is etched using the oxidized portion 44 of the exposed portion as an etching mask to form a 0.18 μm line and space pattern 43. Was formed (FIG. 13D). A parallel plate type RIE device was used as the etching device, and the flow rate was 200 SCC
M Cl ₂ , vacuum degree 75 mTorr, excitation power 2
Etching was performed under the etching conditions of 00 W and a substrate temperature of 60 ° C., and the etching time was set to be 50% over-etching with respect to the end point detected by light emission from plasma. When the processed shape was observed with a scanning electron microscope, the organic silicon film could be etched with good anisotropy.

Next, in the same manner as in Example 47, the organic silicon film was irradiated with oxygen plasma to oxidize the organic silicon film (FIG. 13E). Table 16 shows the results of measuring the dimensional variation (= W−Y) of the organic silicon film due to the oxidation treatment. It can be seen that the dimensions are thick in any of the organic silicon films.

From this comparative example, it can be seen that, when the organic silicon film is etched using the resist pattern as an etching mask, an organic silicon film pattern which is hardly thickened by oxidation is obtained. Probably, when the organic silicon film is etched using the resist pattern as an etching mask, the product generated during the etching adheres to the side wall of the organic silicon film and suppresses the thickening due to oxidation. Embodiment 48 This embodiment is an example in which the SH treatment is performed for the oxidation treatment.

In the same manner as in Example 47, organic silicon films (H1) to (H6) were formed on the SiN film, and a resist pattern was formed on the organic silicon film. Then, the organic silicon film was etched under the same conditions as in Example 47 using the resist pattern as an etching mask.

Next, the organic silicon film was oxidized by permeating the wafer into a solution in which sulfuric acid and aqueous hydrogen peroxide were mixed at a weight ratio of 1: 2. As a result of measuring the infrared absorption spectrum of the organic silicon film, it was confirmed that a siloxane bond was generated by the oxidation treatment as in Example 47.
Also, as a result of measuring the amount of dimensional change of the organic silicon film pattern due to the oxidation treatment, it was confirmed that the dimensions were hardly changed by the oxidation treatment as in Example 47.

Next, using the oxidized organic silicon film as an etching mask, S
When the iN film was etched, the SiN film could be etched with good anisotropy.

Embodiment 49 This embodiment is an example in which ultraviolet light is irradiated as a method for the oxidation treatment.

In the same manner as in Example 47, organic silicon films (H1) to (H6) were formed on the SiN film, and a resist pattern was formed on the organic silicon film. Then, the organic silicon film was etched under the same conditions as in Example 47 using the resist pattern as an etching mask.

Next, the organic silicon film was oxidized by irradiating it with a high-pressure mercury lamp at an exposure amount of 1 W / cm ² (FIG. 12).
(F)). As a result of measuring an infrared absorption spectrum, as shown in Example 47, it was confirmed that a siloxane bond was generated by the oxidation treatment. Further, as a result of measuring the amount of dimensional change of the organic silicon film pattern due to the oxidation treatment, it was confirmed that there was almost no change as in Example 47.

Next, the SiN film was etched in the same manner as in Example 47 using the resist pattern and the oxidized organic silicon film as an etching mask.
The SiN film could be etched with good anisotropy (FIG. 12 (g)).

Embodiment 50 This embodiment is an example in which a wiring layer composed of a laminate of a barrier metal and a metal film is used as a film to be processed.

[0593] A 300 nm thick S
An iO ₂ film was formed by the LPCVD method. And SiO ₂
50 nm thick W film, 300 nm thick AlSi on the film
A W film having a thickness of 50 nm is formed by a sputtering method,
A wiring layer was formed. Then, similarly to the embodiment 47,
Organic silicon films (H1) to (H6) were formed on the SiN film, and a resist pattern was formed on the organic silicon film. Then, the organic silicon film was etched under the same conditions as in Example 47 using the resist pattern as an etching mask.

Next, in the same manner as in Example 47, the organic silicon film was oxidized. Further, the wiring layer was etched using the oxidized organic silicon film as an etching mask. An ICP type RIE apparatus was used as an etching apparatus, Cl _{2 at} a flow rate of 90 SCCM and BCl ₃ at a flow rate of 10 SCCM were used as source gases, and the degree of vacuum was 12 mTorr.
r, ICP power 500W, bias power 250W,
Etching was performed under the condition of a substrate temperature of 30 ° C., and the etching time was set so as to be 50% over etching with respect to the end point due to light emission from plasma.

When the processed shape was observed with a scanning electron microscope, the organic silicon film could be etched with good anisotropy. Table 16 shows the results of calculating the etching selectivity between the oxidized organic silicon film and the AlSi film (= the etching rate of the AlSi film / the etching rate of the oxidized organic silicon film) by stopping the etching of the AlSi film halfway. Show. From Table 16, it can be seen that the selectivity is 10 or more in each case, and a value sufficient to act as a mask material for etching the AlSi film is obtained.

Comparative Example 14 In Example 50, after etching the organic silicon film,
When the AlSi film was etched without performing the oxidation treatment, the resist pattern and the organic silicon film were not removed during the etching of the AlSi film, and the AlSi film could not be etched.

Comparative Example 15 By the same method as in Comparative Example 12, the etching selectivity of the SiO ₂ film and the AlSi film under the etching condition of the wiring layer of Example 50 (= etching rate of AlSi film / organic silicon film subjected to oxidation treatment) As a result, the selectivity was found to be 13.0. From this result, it can be seen that the oxidized organic silicon film according to the present invention has the same level of etching resistance as the SiO ₂ film even in plasma suitable for etching the wiring layer.

Embodiment 51 This embodiment shows a case where silicon is processed by the method according to the present invention.

The (H) of Example 47 was placed on a silicon wafer.
An organic silicon film having a thickness of 500 nm was formed by the methods 1) to (H6). Next, the resist solution prepared in Example 47 was formed on the organic silicon film, and heated at 110 ° C. for 90 seconds. Resist thickness after heating is 300n
m. Subsequently, a reduction optical stepper using a KrF excimer laser as a light source (NA = 0.5, σ = 0.5)
After performing pattern exposure using, a post-exposure bake was performed at 110 ° C. for 90 seconds. And
The contact hole pattern having a diameter of 0.18 μm was formed by performing development processing using a 0.21 N TMAH developer.

Next, the organic silicon film was etched under the same conditions as in Example 47 using the resist pattern as an etching mask, and the organic silicon film was oxidized in the same manner as in Example 47.

After that, silicon was etched using the oxidized organic silicon film as an etching mask. Using a magnetron-type RIE apparatus as an etching apparatus, using Cl ₂ at a flow rate of 200 SCCM as a source gas, performing etching under the conditions of a vacuum degree of 12 mTorr, an ICP power of 500 W, a bias power of 250 W, and a substrate temperature of 30 ° C., and a trench of 2000 nm in depth Was formed.

When the processed shape was observed with a scanning electron microscope, the organic silicon film could be etched with good anisotropy. Table 1 shows the results of calculating the etching selectivity between the oxidized organic silicon film and silicon (= etching rate of silicon / etching rate of oxidized organic silicon film) by stopping the etching of silicon halfway.
FIG. From Table 17, it can be seen that all have a selectivity of 6 or more, and have sufficient resistance as a mask material for etching silicon.

Comparative Example 16 In Example 51, after etching the organic silicon film,
When the silicon was etched without performing the oxidation treatment, the resist pattern and the organic silicon film were not removed during the etching of the silicon, and a trench structure having a desired depth could not be obtained. .

Comparative Example 17 In the same manner as in Comparative Example 12, the etching selectivity between the SiO ₂ film and silicon under the etching conditions for the wiring layer in Example 51 (= etching rate of silicon / etching of oxidized organic silicon film) Rate), the result was SiO
It can be seen that the film has the same etching resistance as the _two films.

[0605]

[Table 25]

[0606]

[Table 26]

[0607]

[Table 27] The following Examples 52 to 59 relate to peeling of the organic silicon film.

Example 52 First, as a first step, a silicon organic film was formed by the following methods (J1), (J2) and (J3).

(J1): A solution prepared by dissolving 10 g of an organic silicon compound having a weight average molecular weight of 12,000 represented by the formula [1-84] in 90 g of anisole on a SiO ₂ film having a thickness of 500 nm on a silicon substrate. The material was applied by a spin coating method. Then, using a hot plate,
The solvent was vaporized and dried by heating at 60 ° C. for 90 seconds to form an organic silicon film having a thickness of 0.1 μm.

(J2): As shown in FIG. 14A, an SiO ₂ film 52 having a thickness of 300 nm was formed on a silicon substrate 51 by a sputtering method. Then, on the SiO ₂ film 52, Ti
N / Ti / 0.5% Cu-Al / Ti / TiN (Film thickness 400A / 50A / 2300A / 100A /
200A) was formed. Next, FIG.
As shown in FIG. 4 (b), a solution material prepared by dissolving 10 g of an organosilicon compound having a weight average molecular weight of 12,000 represented by the formula [1-66] in 90 g of anisole was spin-coated on the metal wiring layer 53. It was applied by a method.
Next, the solvent was vaporized and dried at 160 ° C. for 90 seconds using a hot plate to form an organic silicon film 54 having a thickness of 0.1 μm.

(J3): A 390 nm thick polysilicon film was formed on a 500 nm thick SiO ₂ film on a silicon substrate. An organic silicon compound 1 having a weight average molecular weight of 12,000 represented by the formula [1-84] is formed on the polysilicon film.
A solution material prepared by dissolving 0 g in 90 g of anisole was applied by a spin coating method. Next, the solvent was vaporized and dried by heating at 160 ° C. for 90 seconds using a hot plate to form an organic silicon film having a thickness of 0.1 μm.

The glass transition temperature of the organic silicon film formed in (J1) to (J3) is 132 ° C.

FIGS. 14 (a) and 14 (b) B show the case of the above embodiment (J2), that is, the case where there is an organic silicon film on the metal wiring layer. The case of J3) is the same except that an organic silicon film is directly provided on SiO ₂ .

Next, as a second step, a chemically amplified resist APEX-E is formed on the organic silicon film 54.
(Shipley) is spin-coated to a thickness of 1 micron,
Baking at 100 ° C. for 90 seconds on a hot plate (FIG. 1)
4 (c)). Thereafter, the resist 55 is exposed using a KrF excimer stepper, and is exposed on a hot plate for 100 hours.
After baking at 90 ° C for 90 seconds,
The development was performed for 2 seconds to form the resist pattern 55 (FIG. 14D).

Next, as a third step, using a magnetron type reactive ion etching apparatus, a flow rate of 100 sc
cm Cl ₂ , excitation power 100 W, vacuum degree 20 mTorr
r, at a substrate temperature of 50 ° C., the organic silicon film 53
Is etched to form the organic silicon film pattern 5
3 was formed.

Thereafter, as a fourth step, the film to be processed was etched and a pattern was formed. First, regarding (J1), the SiO ₂ film was etched using a magnetron-type reactive ion etching apparatus under the conditions of O ₂ / CF ₄ = 100/20 sccm, excitation power of 500 W, vacuum degree of 10 mTorr, and substrate temperature of 30 ° C. And the above SiO
_Two film patterns were formed. About (J2), IC
Using a P-type reactive ion etching system, Inductive
Power / Bias Power = 400 / 180W, Cl2 / BCl3 / N2 = 50/60 / 5SCCM,
The metal wiring layer 53 was etched at a pressure of 12 mTorr (FIG. 11E). About (J3), HBr = 100S using a magnetron type reactive ion etching apparatus.
The polysilicon layer was etched under the conditions of CCM and a pressure of 30 mTorr.

Next, as a fifth step, the following method is used.
The chemically amplified resists (J1) to (J3) were separated from the organic silicon film (FIG. 1F). A down-flow plasma apparatus was used for peeling, and O ₂ + CF ₄ was used for gas.
The substrate temperature and gas flow rate were changed as shown in Table 18 below. Plasma excitation power is 200 W, pressure is 0.1 Torr
r.

[0618]

[Table 28] Table 19 below shows the results of investigations as to whether or not the resist and the organic silicon film could be stripped without residues. In the table, ○ indicates that there is no residue, and X indicates that there is a residue. When the ratio of CF ₄ is 0, a residue remains at any substrate temperature. When the ratio of CF ₄ was set to 0.2%, when the substrate temperature was 80 ° C. and 160 ° C., good peelability was exhibited. CF
_When the ratio of ₄ was 0.5% or more, the peelability was good at any substrate temperature. Further, after peeling, a cross-sectional SEM observation was performed to examine whether or not there was a mixing layer of the base and the organic silicon film. In Table 20, all of those having no residue showed no mixing layer.

[0619]

[Table 29]

[0620]

[Table 30] In Table 19, when the organic silicon film was peeled off, the film to be processed ((J1) was SiO _{2 as} a base and (J2) was a metal wiring film as a base) when the organic silicon film was peeled. , (J3), the polysilicon film is shown in Table 20 above. From Table 20 above, it can be seen that in most cases, the shaving amount is 1 nm or less (measurable), and the base is hardly damaged.

Next, the following experiment was performed as a comparative example. First, as the first step, the following (K1), (K2),
And (K3), a silicon organic film was formed.

(K1): An organic silicon film was formed on a 500 nm-thick SiO ₂ film on a silicon substrate in the same manner as in (J1).

(K2): In the same manner as in (J2), a TiN / Ti / 0.5% Cu— film was formed on a SiO ₂ film having a thickness of 300 nm on a silicon substrate.
A metal wiring layer made of Al / Ti / TiN was formed, and a 0.1-micron organic silicon film was formed on the metal wiring layer.

(K3): A polysilicon film was formed on a 500-nm-thick SiO ₂ film on a silicon substrate in the same manner as in (J3), and an organic silicon film was formed on the polysilicon layer.

As a second step, for (K1) to (K3), a resist pattern was formed on the organic silicon film in the same manner as in (J1) to (J3).

As a third step, CF ₄ = 200 scc using a magnetron type reactive ion etching apparatus.
The organic silicon film was etched under the conditions of m, excitation power of 100 W, degree of vacuum of 20 mTorr, and substrate temperature of 50 ° C. to form a pattern of the organic silicon film.

As a fourth step, a film to be processed was etched and a pattern was formed. The method is the same as (J1) for (K1), (J2) for (K2), and (J3) for (K3).

[0628] Table 20 shows the results obtained by examining whether the resist and the organic silicon film could be peeled off without residue.
In this example, since the etching gas at the time of etching the organic silicon film was only CF ₄ , it can be seen that a residue remained at any substrate temperature.

Next, as a second comparative example, a case where patterning is performed by directly irradiating an organic silicon film with ultraviolet light will be described. First, a silicon organic film was formed by the following methods (L1), (L2), and (L3).

(L1): An organic silicon film 63 is formed on the SiO ₂ 62 film on the silicon substrate 61 in the same manner as in (J1).
Was formed (FIGS. 15A and 15B).

(L2): SiO _{2 in the same} manner as (J2)
An organic silicon film was formed on the wiring layer on the film.

(L3): SiO _{2 in the same} manner as (J3)
An organic silicon film was formed on the polysilicon film on the film.

Next, (L1), (L2) and (L3)
The organic silicon film 63 was irradiated with ArF excimer laser to perform pattern exposure to oxidize the exposed portion 63a (FIG. 15C). Next, using a magnetron-type reactive ion etching apparatus, the unexposed portion is etched,
A 0.18 μm pattern was formed. Etching condition is C
l ₂ = 200 SCCM, excitation power 100 W, degree of vacuum 20
The test was performed under the conditions of mTorr and a substrate temperature of 50 ° C.

Then, the exposed and oxidized portion 63a
Was used as an etching mask to etch the SiO ₂ film, the wiring layer, and the polysilicon film, respectively. The etching method is the same as in the fourth step of the embodiment 52. FIG. 15D shows a case where the SiO ₂ film is etched.

Further, the organic silicon film was peeled off in the same manner as in the fifth step of Example 52 (FIG. 15E). The peeling method is the same as in the fifth step of Example 52. Table 20 above shows the results of examination as to whether the resist and the organic silicon film could be peeled off without residue. In this example, since the organic silicon film was not etched using the resist pattern as an etching mask, a residue remained at any substrate temperature. From this experiment, it can be seen that peeling is easier when the organic silicon film is etched using the resist pattern as an etching mask.

In Example 52, a magnetron type etching apparatus was used, and instead of Cl 2, HBr was used.
That is, when etching was performed under the conditions of HBr = 100 SCCM, excitation power of 150 W, vacuum degree of 20 mTorr, and substrate temperature of 60 ° C., the same result as that of Example 5247 was obtained.

Embodiment 53 First, as a first step, (J1) to (J1) of Embodiment 52
3) A silicon organic film was formed in the same manner as in (K1) to (K3). Next, in the second, third, and fourth steps,
In the same manner as in Example 52, an SiO ₂ film, a metal wiring layer,
Alternatively, a polysilicon film was processed.

Next, as a fifth step, the chemically amplified resist and the organic silicon films (J1) to (J3) were separated by the following method. For separation, a down-flow plasma apparatus is used, and gas is O ₂ + SF ₆ or O ₂ + NF.
₃ was used. The O ₂ flow rate was fixed at 500 SCCM, and the substrate temperature and the flow rates of SF ₆ and NF ₃ were changed as shown in Table 21 below. The plasma excitation power is 200 W and the pressure is 0.
1 Torr.

[0639]

[Table 31] Table 22 below shows the results of an investigation as to whether or not the resist and the organic silicon film could be peeled off without residue. After the peeling, a cross-sectional SEM observation was performed to examine whether or not there was a mixing layer of the base and the organic silicon film. As a result, no mixing layer was observed in any of Table 22 having no residue.

[0640]

[Table 32] As described above, when the organic silicon film was peeled off, the film to be processed ((J1) was SiO _{2 as} a base, (J2) was a metal wiring film as a base,
Table 23 below shows the shaved amount of the underlying polysilicon film in the case of (AJ). From Table 23 below, it can be seen that in most cases, the shaved amount is 1 nm or less (measurable) and hardly damages the base.

[0641]

[Table 33] Example 54 First, as a first step, (J1) to (J1) of Example 52 were used.
3) A silicon organic film was formed in the same manner as in (K1) to (K3). Next, in the second, third, and fourth steps,
In the same manner as in Example 52, an SiO ₂ film, a metal wiring layer,
Alternatively, a polysilicon film was processed.

Next, as a fifth step, the chemically amplified resist and the organic silicon films (J1) to (J3) were separated by the following method. First, processing was performed for 1 minute at a substrate temperature of 80 ° C., a plasma excitation power of 200 W, and a pressure of 0.1 Torr by an O ₂ gas using a downflow plasma apparatus.
Next, it was immersed in a solvent containing HF or NH ₄ F at room temperature. Table 2 below shows the ratio of HF or NH ₄ F in the solvent.
It is shown in FIG. In addition, Table 25 below shows the results obtained by examining whether the resist and the organic silicon film could be peeled off without residue.

[0643]

[Table 34] The following can be seen from Table 25 above. First, (J1) ~
For (J3), with the only by peeling O ₂ plasma, as shown in Example 52, whereas what leaves a residue in the substrate temperature, if the ratio of CF ₄ and 0.2%, When the substrate temperature was 30 ° C. or 160 ° C., good peelability was exhibited. When the ratio of CF ₄ was 0.5% or more, the releasability was good at any substrate temperature.

Next, in the cases of (K1) to (K3), since CF ₄ was used as the etching gas for the organic silicon film, the separation did not proceed smoothly, and residues were generated after the separation. Further, after peeling, a cross-sectional SEM observation was performed to examine whether there was a mixing layer of the underlayer and the organic silicon film. In Table 26, no mixing layer was found for any of the samples having no residue.

In the above example, when the organic silicon film was peeled off, the film to be processed ((J1) was SiO _{2 as} the base, and (J2) was the base) when the organic silicon film was peeled off. Table 26 below shows the shaved amounts of the metal wiring film and the underlying polysilicon film in the case of (A3). From Table 26, it can be seen that in most cases, the shaving amount is 1 nm or less (measurable), and the base is hardly damaged.

[0646]

[Table 35] Example 55 First, as a first step, (J1) to (J1) of Example 52 were used.
3) A silicon organic film was formed in the same manner as in (K1) to (K3). Next, in the second, third, and fourth steps,
In the same manner as in Example 52, an SiO ₂ film, a metal wiring layer,
Alternatively, a polysilicon film was processed.

Next, as a fifth step, the following method is used.
The resists (J1) to (J3) and the organic silicon film were peeled off. First, it is immersed in a solution containing sulfuric acid and hydrogen peroxide solution for 10 minutes at room temperature, and then HF or NH ₄ F
Was immersed in a solvent containing The mixing ratio of the solution is shown in Table 27 below.
Shown in Table 28 below shows the results of investigations as to whether or not the resist and the organic silicon film could be peeled off without residue.

[0648]

[Table 36] Then, in the case of (K1) ~ (K3), the release by using CF ₄ as the etching gas of the organic silicon film does not proceed smoothly, it had occurred residue after peeling. Further, after peeling, a cross-sectional SEM observation was performed to determine whether there was a mixing layer between the base and the organic silicon film.
No mixing layer was observed for all of the samples having no residue in No. 6.

In the above example, when the organic silicon film was peeled off, the film to be processed ((J1) was SiO _{2 as} the base, and (J2) was the base) when the organic silicon film was peeled off. (Metal wiring film, polysilicon film in case of (J3))
Is shown in Table 29 below. From Table 30, it can be seen that in most cases, the shaving amount is 1 nm or less (measurable), and the base is hardly damaged.

[0650]

[Table 37] Example 56 In this example, the peeling method described in Example 52 was used.
The case where the structure and the peeling property of the material are examined will be described.

First, on the SiO ₂ film formed on the silicon substrate by the method of (J1) of Example 52, the following (S1)
An organic silicon film was formed by the methods (1) to (S12).

(S1): A weight average molecular weight 3,000 organosilicon compound represented by the formula [1-95] (n / m = 1 /
4) A solution material was prepared by dissolving 10 g in 90 g of anisole, applied on a base substrate by a spin coating method, and baked at 160 ° C. for 90 seconds.

(S2): an organosilicon compound having a weight average molecular weight of 6,000 represented by the formula [1-95] (n / m = 1 /
4) Same as (S1) except that 10 g was used.

(S3): Same as (S1), except that the weight average molecular weight shown in the formula [1-95] was 40,000. n / m = 1/4 (S4): weight average molecular weight 1,0 shown in the formula [1-47]
Same as (S1) except that 10 g of the organosilicon compound of No. 00 was used.

(S5): Same as (S1) except that 10 g of an organosilicon compound having a weight average molecular weight of 4,000 represented by the formula [1-47] was used.

(S6): Same as (S1) except that 10 g of an organosilicon compound having a weight average molecular weight of 12,000 represented by the formula [1-47] was used.

(S7): Same as (S1) except that 10 g of an organosilicon compound having a weight average molecular weight of 3,000 represented by the formula [1-1] was used.

(S8): 10 g of an organosilicon compound having a weight average molecular weight of 3,000 represented by the formula [1-1] and a compound of the formula [3-
61], and a solution prepared by dissolving 1 g of a crosslinking agent and 0.1 g of a silyl peroxide as a radical generator in 88.9 g of anisole was formed on a base substrate by a spin coating method.
After being applied on the base substrate by spin coating, 90 °
Baking for seconds. (S9): weight average molecular weight of 3,000 represented by the formula [1-2]
A solution material is prepared by dissolving 10 g of an organic silicon compound of No. 0 in 90 g of anisole, and is applied on a base substrate by a spin coating method.
b) at 100 ° C. for 90 seconds.

(S10): Same as (S1) except that 10 g of an organosilicon compound having a weight average molecular weight of 12,000 represented by the formula [1-17] was used.

(S11): Same as (S1) except that 10 g of an organosilicon compound having a weight average molecular weight of 8,000 represented by the formula [1-29] was used.

(S12): Same as (S1) except that 10 g of an organosilicon compound having a weight average molecular weight of 8,000 represented by the formula [1-22] was used.

Table 31 below shows the results of measurement of the glass transition temperatures of the organic silicon films (S1) to (S12).

Next, the silicon film was etched, and then the SiO 2 film was etched. Table 30 below shows the result of investigation as to whether or not the resist and the organic silicon film could be peeled off without residue in the same manner as in Example 2.
Table 31 below shows the result of measuring the amount of shaving of the SiO2 film after the completion of the peeling.

From this example, it can be seen that when the glass transition temperature is about O ° C. or higher, and when the organic silicon film is made of an organic silicon compound having a structure represented by the general formula (1), the releasability is good. Similar results were obtained when the film to be processed was a wiring layer and polysilicon.

[0665]

[Table 38]

[0666]

[Table 39]

[0667]

[Table 40]

[0668]

[Table 41] Example 57 Except for using the peeling method described in Example 53,
In the same manner as in Example 56, the structure of the material and the peeling characteristics were examined. The results are shown in Tables 32 and 33 below.

From Tables 32 and 33 below, when the glass transition temperature is approximately O ° C. or higher, and when the organic silicon film contains an organic silicon compound having a structure represented by the general formula 12, the peelability is good. You can see that. Also,
Similar results were obtained when the film to be processed was a wiring layer or polysilicon.

[0670]

[Table 42]

[0671]

[Table 43]

[0672]

[Table 44] Example 58 Except for using the peeling method described in Example 54,
In the same manner as in Example 56, the structure of the material and the peeling characteristics were examined. The results are shown in Tables 35 and 36 below.

From Tables 35 and 36 below, when the glass transition temperature is approximately O ° C. or higher, and when the organic silicon film contains an organic silicon compound having a structure represented by the general formula 12, the peelability is good. You can see that. Also,
Similar results were obtained when the film to be processed was a wiring layer or polysilicon.

[0674]

[Table 45]

[0675]

[Table 46] Example 59 Except for using the peeling method described in Example 54,
In the same manner as in Example 56, the structure of the material and the peeling characteristics were examined. The results are shown in Tables 37 and 38 below.

From Tables 37 and 38 below, when the glass transition temperature is approximately O ° C. or higher, and when the organic silicon film contains an organic silicon compound having a structure represented by the general formula 12, the peelability is good. You can see that. Also,
Similar results were obtained when the film to be processed was a wiring layer or polysilicon.

[0677]

[Table 47]

[0678]

[Table 48]

[0679]

[Table 49]

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a pattern formation method according to one embodiment of the present invention in the order of steps;

FIG. 2 is a cross-sectional view showing a step of etching a film to be processed using only an organic silicon film pattern as a mask;

FIG. 3 is a sectional view showing a pattern forming method according to another embodiment of the present invention in the order of steps;

FIG. 4 is an electron micrograph showing the state of the organic silicon film after etching;

FIG. 5 is a graph showing the result of calculating the light intensity reflectance at the interface between the resist and the polysilane film;

FIG. 6 is a graph showing a relationship between a resist film thickness and a resist pattern dimension;

FIG. 7 is a graph showing the relationship between the thickness of a SiO ₂ film and the dimensions of a resist pattern;

FIG. 8 is a view showing a processed shape of a carbon film obtained according to a comparative example;

FIG. 9 is a sectional view showing a pattern forming method according to a comparative example in the order of steps;

FIG. 10 is a graph showing the ratio of O / Si in the thickness direction of the polysilane film in one embodiment of the present invention;

FIG. 11 is a sectional view showing a pattern forming step according to another embodiment of the present invention;

FIG. 12 is a sectional view showing a pattern forming method according to another comparative example in the order of steps;

FIG. 13 is a sectional view showing a pattern forming method according to still another comparative example in the order of steps;

FIG. 14 is a sectional view showing a pattern forming step according to still another embodiment of the present invention;

FIG. 15 is a cross-sectional view showing a pattern forming step in still another embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Film to be processed 3 ... Organic silicon film 4 ... Resist 5 ... Resist pattern 6 ... Organic silicon film pattern 7 ... Film pattern to be processed

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/26 511 G03F 7/26 511 H01L 21/027 H01L 21/30 564D 21/3213 574 21/88 C (72) Inventor Hideto Matsuyama 8 Shinsugita-cho, Isogo-ku, Yokohama-shi, Kanagawa Prefecture Inside the Toshiba Yokohama office (72) Inventor Yoshihiko Nakano 1 Toshiba-cho, Komukai-Toshiba-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Inside the R & D center (72 ) Inventor Sawako Fujioka 1 Toshiba R & D Center, Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa Prefecture (72) Inventor Rikako Kawada 1 Ritsuko Toshiba-cho, Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa Inside the center (72) Inventor Shuji Hayase 1 Toshiba R & D Center, Komukai Toshiba-cho, Saiyuki-ku, Kawasaki-shi, Kanagawa (72) Inventor Narita Masataka Yokohama, Kanagawa Prefecture Isogo-ku, Shinsugita-cho, address 8 Co., Ltd. Toshiba Yokohama workplace (72) inventor Eiji Shiobara Yokohama, Kanagawa Prefecture Isogo-ku, Shinsugita-cho, address 8 Co., Ltd. Toshiba Yokohama workplace

Claims (20)

[Claims] A step of forming an organic silicon film on a film to be processed containing an organic silicon compound having a bond between silicon and silicon in a main chain and having a glass transition temperature of 0 ° C. or more; Forming a resist pattern thereon; and etching the organic silicon film using an etching gas containing at least one atom selected from the group consisting of chlorine, bromine, and iodine, thereby forming the resist pattern by etching. Transferring to an organic silicon film. 2. The pattern forming method according to claim 1, further comprising a step of etching the film to be processed using the resist pattern and the organic silicon film as an etching mask. 3. The pattern forming method according to claim 1, further comprising: a step of removing the resist pattern; and a step of etching a film to be processed using the organic silicon film as an etching mask. 4. The organic silicon film is formed by forming a coating film with a solution material containing an organic silicon compound having a bond between silicon and silicon in a main chain, and heating the coating film. 2. The pattern forming method according to claim 1, wherein: 5. The method according to claim 1, wherein the organic silicon film is formed by forming a coating film with a solution material containing an organic silicon compound having a bond between silicon and silicon in a main chain, and crosslinking the organic silicon compound. Claim 1.
4. The pattern forming method according to 1. 6. The pattern forming method according to claim 5, wherein the crosslinking is performed by heating the coating film. 7. The method of claim 1, wherein the crosslinking heats the coating, irradiates the coating with an energy beam, and irradiates the coating with an energy beam while heating the coating. The pattern forming method according to claim 5, wherein the method is performed by a method selected from the group consisting of: 8. The method according to claim 1, wherein the organic silicon compound is represented by the following general formula. Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 3 or less carbon atoms, and R ⁶ is a hydrogen atom or a carbon atom having 1 to 3 carbon atoms. 20 represents a substituted or unsubstituted aliphatic hydrocarbon group or aromatic hydrocarbon group.) 9. The pattern forming method according to claim 1, wherein the film to be processed is one type selected from the group consisting of a metal wiring layer and a silicon-based material film. 10. The pattern forming method according to claim 1, wherein the film to be processed is a silicon-based insulating film. 11. The pattern forming method according to claim 1, wherein the etching of the silicon-based insulating film is performed using an etching gas containing a fluorine-based gas. 12. The semiconductor device according to claim 10, wherein the silicon-based insulating film is one type selected from the group consisting of a silicon oxide film, a silicon nitride film, a silicon oxynitride film, and a spin-on-glass film. Pattern formation method. 13. The pattern forming method according to claim 1, wherein the organic silicon film contains a conductive substance or a substance that becomes conductive when irradiated with light. 14. The pattern forming method according to claim 1, wherein the organic silicon film is etched using an etching gas containing at least one selected from the group consisting of Cl ₂ and HBr. 15. A step of forming an organic silicon film having a glass transition temperature of 0 ° C. or higher on a film to be processed, containing an organic silicon compound having a bond between silicon and silicon in a main chain; Forming a resist pattern on the organic silicon film using an etching gas containing at least one kind of atom selected from the group consisting of chlorine, bromine, and iodine; A pattern forming method, comprising: a step of performing an oxidation treatment; and a step of etching the film to be processed using a pattern including the oxidized organic silicon film as an etching mask. 16. The method according to claim 15, wherein the oxidation treatment is performed by one selected from the group consisting of energy beam irradiation, plasma irradiation, and immersion in a solution containing an oxidizing agent. Pattern formation method. 17. The film to be processed is selected from the group consisting of silicon nitride, a silicon-based material, and a metal wiring layer.
The pattern forming method according to claim 15, wherein the pattern is a seed. Law. 18. A step of forming an organosilicon film having a glass transition temperature of 0 ° C. or higher on a film to be processed, containing an organosilicon compound having a bond between silicon and silicon in a main chain; Forming a resist pattern on the organic silicon film using an etching gas containing at least one atom selected from the group consisting of chlorine, bromine, and iodine; Etching the film to be processed using: a pattern containing the organic silicon film, a gas containing at least one atom selected from the group consisting of chlorine, bromine, and fluorine; and a gas containing oxygen atoms. Stripping using a mixed gas. A method for forming a pattern, comprising: 19. A step of forming an organosilicon film having a glass transition temperature of 0 ° C. or more on a film to be processed, the organosilicon compound having a bond between silicon and silicon in a main chain thereof; Forming a resist pattern on the organic silicon film using an etching gas containing at least one atom selected from the group consisting of chlorine, bromine, and iodine; Etching the film to be processed, and treating the pattern including the organic silicon film with at least one solution selected from the group consisting of a solution containing an amine-based solvent and a solution containing a fluorine atom. A pattern forming method, comprising the steps of: 20. The pattern forming method according to claim 18, wherein the organic silicon compound has a structure represented by the following general formula in a main chain. Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 3 or less carbon atoms, and R ⁶ is a hydrogen atom or a carbon atom having 1 to 3 carbon atoms. 20 represents a substituted or unsubstituted aliphatic hydrocarbon group or aromatic hydrocarbon group.)