JP3486123B2 - Pattern transfer composition and pattern transfer method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern transfer composition for forming a pattern transfer film necessary for finely processing an insulating film or a conductive film formed on a semiconductor substrate in a semiconductor device manufacturing process. The present invention relates to a pattern transfer method.

[0002]

2. Description of the Related Art In the manufacture of semiconductor devices, there are many steps for processing an insulating film such as a silicon oxide film or a silicon nitride film formed on a semiconductor substrate. Usually, the processing of these insulating films is performed as follows. That is, a resist film is formed on the insulating film, exposed and developed to form a resist pattern, and then the insulating film is processed by dry etching using the resist pattern as an etching mask. At this time, in order to secure a desired resolution, exposure dose margin, or focus margin at the time of exposure, it is necessary to reduce the film thickness of the resist. But,
If the resist is too thin, the resist pattern is not etched during dry etching of the insulating film, and the insulating film cannot be processed any further.
In order to solve this problem, a method is used in which a pattern transfer material is applied on the insulating film, a resist is applied, the resist pattern is transferred to the pattern transfer material, and then the insulating film is dry-etched.

Conventionally, the following materials have been known as pattern transfer materials. Examples include I) silicon-based materials such as polysilicon and amorphous silicon, II) carbon, III) novolac resin, and resin materials such as polyhydroxystyrene. However, there are problems with any pattern transfer material.

For example, when the silicon-based material of I) is used, a strong standing wave is generated in the resist film because the silicon-based material exhibits strong reflection during exposure. Therefore, there is a problem that the side wall of the developed resist pattern has a wavy shape as shown in FIG. In FIG. 2, a silicon oxide film 2 is formed on a silicon substrate 1, a pattern transfer material layer 3 is formed thereon, and a resist 4 is formed.
Pattern is formed.

On the other hand, since the carbon of II) and the resin material of III) function as an antireflection film, the above problems can be avoided. However, there is a problem that the etching selectivity between the resist and these pattern transfer materials is small. Therefore, there is a problem that the resist pattern disappears during the etching of the pattern transfer material, or the pattern of the pattern transfer material has a tapered shape as shown in FIG. Also in FIG. 3, the same parts as those in FIG. 2 are denoted by the same reference numerals.

Further, since the materials I) and II) are formed by the CVD method or the sputtering method, the process is complicated as compared with the case where the film is formed by the coating method, and the cost is increased. III)
When the resin material and the silicon-containing resist are combined, the etching selection ratio between the resist and the pattern transfer material becomes sufficiently large. However, the silicon-containing resist has a problem that the resolution resolution, the exposure dose margin, or the focus margin is lower than that of a normal resist.

As described above, conventionally, the film can be formed by the coating method, the reflected light can be suppressed at the time of exposure, the etching selection ratio with respect to the resist is large, and the dry etching resistance is excellent when the film to be processed is processed. No pattern transfer material was known.

[0008]

An object of the present invention is to form a film by a coating method, to suppress reflected light at the time of exposure, to have a large etching selection ratio with respect to a resist, and to dry a film to be processed. An object of the present invention is to provide a pattern transfer composition capable of forming a pattern transfer film having excellent etching resistance.

[0009]

The pattern transfer composition of the present invention is a pattern transfer composition containing at least the following components (a), (b) and (c). (B) a repeating unit represented by the following a) or b) of at least one polysilane a) the following general formula (1), below
Polysilane containing a copolymer containing a bonding unit represented by the general formula (3)

[Chemical 6] (However, R is a substituted or unsubstituted aliphatic hydrocarbon group having 6 or less carbon atoms, R1 and R2 are substituted or unsubstituted hydrocarbon groups having 20 or less carbon atoms, and a is 0.1 or more. 0.
It is 9 or less, and b is 0 or more and 0.7 or less. )

[Chemical 7] b) A polysilane containing a copolymer having a repeating unit represented by the following general formula (2), a bonding unit represented by the following general formula (3), and two or more carbon-carbon multiple bonds in the molecule.

[Chemical 8] (However, R3, R4, and R5 may be the same or different and each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 20 or less carbon atoms. A'is 0.1 or more and 0.
It is 8 or less. )

[Chemical 9] (B) Acid generator (c) Organic solvent Further, a repeating unit represented by the general formula (1) ,
The copolymer containing the bonding unit represented by the general formula (3) preferably further contains a repeating unit represented by the following general formula (4) .

[Chemical 10] (However, Ar is a substituted or unsubstituted aromatic hydrocarbon group having 20 or less carbon atoms. A ″ is 0.1 or more and 0.9 or less.) Further, the present invention processes the pattern transfer composition. A step of applying the film on the film, a step of heating the film to be processed in an atmosphere having an oxygen concentration of 0.1% or less to form a pattern transfer film on the film to be processed, and a resist pattern formed on the pattern transfer film. A pattern transfer method, comprising: a step, a step of etching a pattern transfer film using the resist pattern as an etching mask, and a step of etching a film to be processed using the etched pattern transfer film as an etching mask. .

(A) At least one of the following polysilanes a) or b) a) Polysilane containing a copolymer containing a repeating unit represented by the following general formula (1).

[Chemical 6] (However, R is a substituted or unsubstituted aliphatic hydrocarbon group having 6 or less carbon atoms, R1 and R2 are substituted or unsubstituted hydrocarbon groups having 20 or less carbon atoms, and a is 0.1 or more. 0.
It is 9 or less, and b is 0 or more and 0.7 or less. B) Polysilane containing a copolymer containing a repeating unit represented by the following general formula (2) and a bonding unit represented by the general formula (3).

[Chemical 7] (However, R3, R4, and R5 may be the same or different and each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 20 or less carbon atoms. A'is 0.
It is 1 or more and 0.8 or less. )

[Chemical 8] (B) Acid generator (c) Organic solvent Further, the copolymer containing the repeating unit represented by the general formula (1) has a repeating unit represented by the following general formula (4) and the following general formula (4): It is desirable to further include a binding unit represented by 3).

[Chemical 9] (However, Ar is a substituted or unsubstituted directional hydrocarbon group having 20 or less carbon atoms. A ″ is 0.1 or more and 0.9 or less.)

[Chemical 10] Further, according to the present invention, a step of applying the pattern transfer composition onto a film to be processed and the film to be processed having an oxygen concentration of 0.
A step of forming a pattern transfer film on the film to be processed by heating in an atmosphere of 1% or less; a step of forming a resist pattern on the pattern transfer film; and a step of etching the pattern transfer film using the resist pattern as an etching mask. And a step of etching the film to be processed using the etched pattern transfer film as an etching mask.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The pattern transfer composition of the present invention contains (a) at least one of the above polysilanes a) or b) as a main component. The above-mentioned polysilane a) has a Si—H bond at a cross-linking reaction point, and is cross-linked by adding a cross-linking agent and heating. The polysilane b) has a crosslinkable bond (carbon-carbon multiple bond) and is crosslinked by heating.

The (b) acid generator has a function of preventing the deterioration of the resist pattern shape due to the mixture of the resist and the pattern transfer composition at the interface with the resist layer.

The organic solvent (c) has a function of dissolving the components of the composition.

In the pattern transfer composition of the present invention, it is desirable to add the following components (d) and (e). (D) Radical generator (e) Antioxidant (d) The radical generator acts as a crosslinking initiator for polysilane. The radical generator functions to assist the self-polymerization of polysilane and the reaction between the cross-linking agent and polysilane. In particular, the polysilane of b) is apt to undergo a crosslinking reaction due to the presence of the radical generator.

The antioxidant as the component (e) has the function of increasing the storage stability.

Further, in the pattern transfer composition of the present invention, it is desirable to add any one of the following (f) or (g). (F) A compound having two or more carbon-carbon multiple bonds in the molecule (g) A compound (f) component having a Si-H bond in the molecule is a crosslinking agent. In particular, when polysilane a) is used and there is no crosslinkable bond (carbon-carbon multiple bond) in polysilane a), it is desirable to add it. In this case, (f) component is polysilane of Si-
An addition reaction occurs with the H bond to crosslink the polysilane.

The component (g) is preferably added when a polysilane a) or a polysilane b) having a crosslinkable bond (carbon-carbon multiple bond) is used. In this case, the component (g) acts as a crosslinking agent.

In particular, in the case of a combination in which the pattern transfer composition is dissolved in the resist composition forming the resist layer, in order to efficiently insolubilize the resist by cross-linking polysilane after applying the pattern transfer composition ( ) Or (g) component is preferably added.

The above components (a) to (g) will be described in more detail below. <About component (a)> Polysilane of a) Among the polysilanes of component (a) used in the present invention, a) is represented by the repeating unit represented by the general formula (1) and the general formula (3).
And a copolymer containing a bond unit .

In the general formula (1), R is a substituted or unsubstituted aliphatic hydrocarbon having 6 or less carbon atoms. Examples of the aliphatic hydrocarbon that can be introduced as R include a methyl group,
Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group,
Examples thereof include cyclohexyl group, 3,3,3-trifluoropropyl group, and 3-methoxypropyl group, but are not particularly limited.

R1 and R2 are substituted or unsubstituted hydrocarbon groups having 20 or less carbon atoms and may be the same or different. The substituted or unsubstituted hydrocarbon group that can be introduced as R1 and R2 is a methyl group, an ethyl group, a phenyl group, a benzyl group, a phenethyl group, a butyl group, an isobutyl group, a cyclohexyl group, 3,3,3-trifluoropropyl. Examples thereof include groups, but are not particularly limited.

A in the general formula (1) is 0.1 or more and 0.
It is 9 or less. When a is less than 0.1, not only the polymer becomes liquid but also easily oxidized, while 0.
If it exceeds 9, insolubilization may occur. In addition, a is more preferably 0.2 to 0.6. Further, b is 0 or more and 0.7 or less. When b is 0.7 or more, Tg becomes low and heat resistance becomes poor. Note that b is more preferably 0.1 to 0.5
Is.

Specific examples of the repeating unit represented by the general formula (1) are shown below.

[Chemical formula 11]

In the present invention, the copolymer containing the repeating unit represented by the general formula (1) has a molecular weight of 500 to 100,
000 is preferable, and 1000 to 50,000 is preferable.
Is more preferable. If it is less than 500, the polymer becomes liquid, while if it exceeds 100,000, it may become insoluble.

In the present invention, it is represented by the general formula (3).
Heat resistance and resist
The etching selection ratio of can be improved. Also,
The repeating unit represented by the general formula (1) and the general formula (3)
The copolymer containing the bonding unit represented by is preferably further containing a repeating unit represented by the following general formula (4).

[Chemical formula 12] (However, Ar is a substituted or unsubstituted aromatic hydrocarbon group having 20 or less carbon atoms. A ″ is 0.1 or more and 0.9 or less.)

Further, by introducing the repeating unit of the general formula (4), both stability against oxidation and the effect of Si--H bond can be achieved. In the repeating unit represented by the general formula (4), Ar is a substituted or unsubstituted aromatic hydrocarbon group having 20 or less carbon atoms, and as Ar, for example, phenyl group, naphthyl group, anthranyl group, toluyl group,
A methicylene group etc. are mentioned.

Specific examples of the polysilane containing the repeating unit of the general formula (4) and the bonding unit represented by the general formula (3) are shown below.

[Chemical 14] The bond unit of the general formula (3) is preferably contained in the copolymer in an amount of 0.1 mol% or more and 80 mol% or less. This is because if it is too large, it may become insoluble, and if it is too small, the effect of improving the etching selectivity decreases.

The repeating unit of the general formula (4) is preferably contained in the copolymer in an amount of 0.1 mol% or more. This is because if the amount is too small, the effect of stabilizing the oxidation is reduced.

Polysilane of b) In the polysilane of the component (a) used in the present invention, b) is a repeating unit represented by the general formula (2), a bonding unit represented by the general formula (3), and a carbon atom. -Including copolymers containing more than one carbon multiple bond in the molecule.

In the general formula (2), R3, R4 and R5 may be the same or different and each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having a prime number of 20 or less. Examples of R3, R4, and R5 are hydrogen atom, vinyl group, allyl group, benzyl group, paravinylphenyl group,
Phenyl group, phenethyl group, methyl group, perfluoropropyl group, perfluorobutyl group, sec-butyl group,
Examples thereof include an isopropyl group, an ethyl group, and a t-butyl group, but are not particularly limited.

In the general formula (2), a'is 0.1 or more and 0.8 or less. If a'is less than 0.1, it may be insolubilized, while if it exceeds 0.8, Tg may be lowered and heat resistance may be deteriorated.

Further, a is more preferably 0.2 to 0.5.

The repeating unit represented by the general formula (2) is
In the polysilane which is the copolymer according to the present invention, it is desirable that the polysilane be contained in a molar ratio of 0.1 or more, with 1 being the polysilane. If it is too small, it may become insoluble in the solvent.

The bond unit represented by the general formula (3) is 0.1.
It is desirable that the content is from mol% to 80 mol%. If it is too large, it will not dissolve in the solvent, and if it is too small, the effect will be poor.

In the present invention, the molecular weight of the copolymer containing the repeating unit represented by the general formula (2), the bonding unit represented by the general formula (3) and two or more carbon-carbon multiple bonds in the molecule is: It is preferably 500 to 100,000, and more preferably 1,000 to 30,000.
If it is less than 500, it becomes liquid, while if it exceeds 100,000, it may become insoluble.

A repeating unit represented by the general formula (2),
Specific examples of the copolymer containing the bonding unit represented by the general formula (3) and two or more carbon-carbon multiple bonds in the molecule are shown below.

[Chemical 15] <About the component (b)> It is necessary that the acid generator of the component (b) generates an acid during exposure and does not decompose at the temperature applied when the polysilane in the pattern transfer composition is crosslinked and does not hinder the crosslinking. Is. The temperature to add is 100
Although the temperature is higher than or equal to 0 ° C, it is carried out at 150 ° C to 250 ° C in order to shorten the crosslinking time in terms of the process. Examples of compounds that can be sufficiently used under these conditions include triarylsulfonium salts, iodonium salts, and N-hydroxyimide sulfonates. In particular, since polysilane has low solubility in a polar solvent, N- which is not an ionic compound
Hydroxyimide sulfonates are preferred. A specific example will be given.

[Chemical 16] The addition amount of the component (b) is 0.05 to 30 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of polysilane.

If it is less than 0.05 parts by weight, the effect of improving the pattern shape of the resist is not observed, and if it exceeds 30 parts by weight, the coating properties and the properties of the film after forming the pattern transfer film are deteriorated. <About component (c)> Any solvent may be used as the solvent for component (c) as long as it can dissolve all of the components uniformly. Specific examples thereof include ether solvents such as ansole, tetrahydrofuran and diethoxyethane, aromatic hydrocarbons such as toluene, xylene, methicylene, cumene and ethylbenzene, and mixed solvents such as solvent naphtha. <About component (d)> Examples of the radical generator of component (d) include azo compounds (for example, azobisisobutyronitrile), peroxides, alkylaryl ketones, silyl peroxides, organic halides, and the like. The radical generator decomposes an O—O bond or a C—C bond in the molecule by light irradiation or heating to generate a radical. Examples of the radical generator include benzoyl peroxide, ditertiary butyl peroxide, benzoin, benzoin alkyl ether, benzoin alkylaryl thioether, benzoyl aryl ether, benzyl alkyl aryl thioether, benzyl aralkyl ethanol, phenylglyoxal alkyl acetal, benzoyl oxime, Examples include triphenyl-t-butylsilyl peroxide, and the compounds shown below.

[Chemical 17] (D) The amount of radical generator added is 1 weight of polysilane.
When the amount is 00 parts by weight, the amount is preferably 1 part by weight or more and 100 parts by weight or less, and particularly preferably 5 to 50 parts by weight. <About component (e)> On the other hand, a) containing Si-H bond
In the case where the polysilane or other compound containing a Si—H bond is included, it tends to be easily oxidized. Therefore, an antioxidant may be added to the pattern transfer composition in order to increase storage stability.

As the antioxidant, for example, those listed below can be used. 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 4,
4'-butylidene-bis (6-t-butyl-m-cresol), 2,2'-methylene-bis (4-methyl-6-
t-butylphenol), 4,4'-thiobis (6-t
-Butyl-m-cresol) and the like.

The amount of addition is 0.01 to 20 parts by weight of antioxidant with respect to 100 parts by weight of polysilane. It is preferably 0.1 to 6 parts by weight. When the amount of the antioxidant exceeds 20 parts by weight, the crosslinking reaction between the polysilane and the crosslinking agent does not occur, and when it is less than 0.01 part by weight, the effect of improving the storage stability cannot be obtained. <About component (f)> When polysilane a) is used and there is no crosslinkable bond (carbon-carbon multiple bond) in polysilane a), the carbon-carbon multiple bond of component (f) is incorporated into the molecule. You may add the compound which has two or more.
Examples of the component (f) include organic substances having a carbon-carbon multiple bond. The organic compound having a multiple bond is a compound having a double bond or a triple bond, more specifically, a compound having a vinyl group, an acryl group, an aryl group, an imide group, an acetylenyl group, a derivative thereof, or the like.
The organic group having such a multiple bond may be any of a monomer, an oligomer and a polymer. The organic substance having multiple bonds may be self-polymerized.

The amount of component (f) added is 5 to 200 parts by weight per 100 parts by weight of polysilane. If it is less than 5 parts by weight, the effect of crosslinking is not observed, and if it is 200 or more, the selectivity with respect to the resist may decrease. More preferably 20-
It is 100 parts by weight.

However, in the case of a polysilane or oligosilane cross-linking agent having two or more multiple bonds, the above-mentioned addition amount is not limited.

Specific examples of the compound (f) having two or more carbon-carbon multiple bonds in the molecule are shown below.

[Chemical 18]

[Chemical 19]

[Chemical 20]

[Chemical 21] <About (to) component> In the case of using polysilane a) having a bond (carbon-carbon multiple bond) capable of cross-linking to polysilane itself, or using polysilane b), Si-of (to) component It is desirable to add a compound containing an H bond in the molecule.

The amount of component (g) added is 5 to 200 parts by weight per 100 parts by weight of polysilane. If it is less than 10 parts by weight, the effect of crosslinking is not observed, and if it is 200 parts by weight or more, the selectivity with respect to the resist may decrease. It is more preferably 10 to 50 parts by weight.

Specific examples of compounds containing a Si--H bond in the molecule are shown below.

[Chemical formula 22] In order to use the pattern transfer composition according to the present invention as a pattern transfer film, the oxygen concentration is 0.1% (100%).
It is desirable to perform heating in an atmosphere of 0 ppm) or less.
The concentration is more preferably 200 ppm or less. The polysilane in the pattern transfer composition according to the present invention contains Si—H bonds, Si (Si) 4 bonds, R—
Si (Si) ₃ bonds and the like are included. Polysilanes having these bonds are very susceptible to oxidation at high temperatures in air. Therefore, by heating in an atmosphere having an oxygen concentration in the above range to carry out a crosslinking reaction, the oxidation reaction is suppressed and the properties of polysilane are not deteriorated.
It is possible to form a pattern transfer film that does not dissolve in the resist solvent.

Next, with reference to FIGS. 1A to 1D, a process of processing a silicon type insulating film using a pattern transfer film formed of the pattern transfer composition according to the present invention will be described. An insulating film such as TaO ₂ or RuO ₂ , AlSi, AlSiCu, or Ti salicide,
Processing of a conductive film such as Co salicide or Cu can be performed in the same process.

As shown in FIG. 1A, the silicon substrate 1
A silicon-based insulating film 12, a pattern transfer film 13 and a resist film 14 are formed on the substrate 1. The thickness of the insulating film is preferably 10 μm or less, more preferably 0.5 to 2 μm. When the film thickness of the insulating film exceeds 10 μm, the aspect ratio becomes high and the macro loading effect such as etching stop occurs remarkably. The thickness of the pattern transfer film is preferably about 20 to 500 nm. The film thickness of the pattern transfer film 13 is determined so as to satisfy the following two conditions. Calculate the reflectance at the interface between the resist and the pattern transfer film, taking into account the multiple reflection of the exposure light,
The film thickness is such that the reflectance is as small as possible. The pattern transfer film thickness retention dependency of the reflectance at the interface between the resist and the pattern transfer film is calculated using the complex refractive index of the resist, the pattern transfer film and the insulating film at the exposure wavelength. The specific calculation method is PH Be
rning, Physics of Thin Film, Vol.1, pp.69-121 (196
3); AE Bell & FW Spong, IEEE Journalof Quant
um Electronics, Vol. QE-14, pp.487-495 (1978); K. Oh
ta & H. Isida, Applied Optics, Vol.29, pp.1952-1958
(1990). (2) The resist pattern is used as a mask for etching, and the etched pattern transfer film is used as a mask for etching the insulating film.

The pattern transfer film is applied with the pattern transfer composition and then heated in an atmosphere gas having an oxygen concentration of 0.1% or less to vaporize the solvent.
It is formed by a crosslinking reaction. If necessary, the pattern transfer film has an adhesion improver for improving the adhesion to the base; a dye or polymer (for example, polysulfone) that absorbs ultraviolet rays to prevent reflected light from the insulating film into the resist film. , Polybenzimidazole); a surfactant or the like for improving the wettability with the base may be added. In this case, the compounding amount of the additive is adjusted so that the silicon content in the pattern transfer film containing the additive formed by baking is in the range of 1 to 50% by weight. If the silicon content is less than 1% by weight, the exposure light cannot be sufficiently absorbed, and furthermore, a sufficient etching rate ratio cannot be obtained when the pattern transfer film is etched using the resist pattern as a mask. On the other hand, the silicon content is 50% by weight
A coating film having a thickness of more than 10 is poor in coatability and is likely to have pinholes in the coating film. The resist film is formed by applying a resist solution on the pattern transfer film and then baking. The thinner the resist film is, the more the exposure dose margin, the focus margin, or the resolution at the time of exposure can be improved. Therefore, the film pressure of the resist film is preferably as thin as possible within the range in which the pattern transfer film can be etched with good dimension controllability, and is preferably 500 nm or less.

The resist is not particularly limited as long as it is a composition that can be patterned by exposure to ultraviolet light, electron beam or the like. In addition, a positive or negative resist can be selected and used according to the purpose. As the positive resist, for example, a resist composed of naphthoquinonediazide and a novolac resin (IX-770, manufactured by Japan Synthetic Rubber Co., Ltd.), a chemically amplified resist composed of a polyvinylphenol resin protected by t-BOC and an onium salt (APEX-
E, manufactured by Shipley) and the like. As the negative resist, for example, a chemically amplified resist (XP containing a phenolphenol, a melamine resin and a photoacid generator) is used.
-89131, manufactured by Shipley Co., Ltd., a resist (RD-20) composed of polyvinylphenol and a bisazide compound.
0D, manufactured by Hitachi Chemical Co., Ltd.) and the like. In order to prevent the dimensional controllability of the resist pattern from deteriorating due to standing waves generated in the resist film, a dye such as coumarin or glutamine that absorbs ultraviolet rays is added to the resist to reduce the transparency of the resist. Good.

In order to more surely prevent exposure light reflection from the underlayer to the resist film and to make the resist profile after development a good shape, the distance between the pattern transfer film and the resist film is about 10 to 150 nm. You may form a thin film of a film thickness. Examples of the material of the thin film formed for this purpose and the film forming method thereof include the following.

For example, a silicon nitride film, a silicon oxide film, a silicon oxynitride film, a silicon carbide film or a carbon film is formed by the sputtering method or the CVD method. Further, a solution of a polymer such as polysulfone, polyamide, novolac resin, or polyhydroxystyrene in an organic solvent such as ethyl lactate or cyclohexanone is spin-coated to form a film. In the latter case, a dye such as coumarin or curcumin may be added.

Further, by forming an upper antireflection film on the resist film to reduce the light reflection at the interface between the resist film and air, it is possible to suppress the generation of standing waves in the resist film. Good. As such an upper antireflection film, for example, Aquata. r and the like.

Next, as shown in FIG. 1B, a resist pattern is formed by irradiating the resist with ultraviolet light as exposure light through a mask having a desired pattern and then developing the resist. A mercury lamp, XeF (wavelength = 351 nm), Xe is used as a light source for irradiating ultraviolet light.
C1 (wavelength = 308 nm), KrF (wavelength = 248n)
m), KrCl (wavelength = 222 nm), ArF (wavelength =
193 nm), F ₂ (wavelength = 151 nm) and other excimer lasers. The polysilane of the present invention is Si-
Since it has Si and has high absorptivity to ultraviolet rays having a wavelength of 150 to 360 nm, it can absorb exposure light and suppress light reflected into the resist film. As a result, no wavy shape due to standing waves is observed in the resist profile after development.
In addition, even if the resist film thickness and the insulating film thickness vary,
It is possible to suppress the variation amount of the resist pattern dimension.
As the resist developing solution, an organic alkaline aqueous solution such as tetramethylammonium hydroxide, sodium hydroxide,
An inorganic alkaline aqueous solution such as potassium hydroxide or an organic solvent such as xylene or acetone is used.

Then, as shown in FIG.
Pattern transfer film (e.g.
Etching the Cheunda mask). Etching method and
For example, reactive plasma etching, magneto
Ron reactive plasma etching, electron beam plasma etching
Etching, TCP plasma etching, ICP plasma
Etching or ECR plasma etching are listed.
You can CF as source gas_Four, CF_ThreeCl, C
F_TwoC1_Two, CF_ThreeBr, CC1_Four, C_TwoF₅Cl_Two,
CF_Four+ H_Two, (CF_Four, C_TwoF₆, CHF_Three, SiF
_Four, CF_ThreeBr) + (Cl_Two, Br_Two), Cl_Two(+ H
_Two), SiCl_Four, Br_Two, I_Two, Cl _Two+ Ar, SF
_Four(+ N_Two), HBr, HI, HCl, Cl_Two+ He
It is preferable to use any combination selected from the group
Good Using these source gases, resist and
It is important to increase the etching rate ratio of the turn transfer film.
The pattern transfer film with good dimensional controllability.
Can be used. The reason for this is considered as follows.

That is, the etchant is unlikely to cause a chemical reaction with the atoms constituting the resist and is unlikely to generate a volatile product, whereas the etchant causes a chemical reaction with silicon contained in the pattern transfer film to have a high vapor pressure. This is to produce a product that is easily volatilized. Particularly, if the source gas containing Cl ₂ or HBr is used, the pattern transfer film can be etched at a high speed ratio. As a result, even if the film thickness of the resist is thinned, the resist is not scraped off, and the resist pattern recedes and the dimensional controllability of the pattern of the pattern transfer film does not deteriorate.

Finally, as shown in FIG. 1D, the insulating film is etched by using the resist pattern and the pattern transfer film film pattern as a mask. Examples of the etching method include reactive plasma etching, magnetron reactive plasma etching, electron beam plasma etching, TCP plasma etching, ICP plasma etching, and ECR plasma etching. As the source gas, a fluorine-based gas such as CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , CF ₄ + (H ₂ , C
₂ F ₂ ), C ₄ F ₈ , CHF ₃ + CO, C ₄ F ₈ + CO
Are preferred. When these source gases are used, the silicon-based insulating film can be etched at a high rate ratio. At this time, when the polymer film is remarkably deposited on the surface of the resist pattern or the pattern transfer film pattern and the etching shape is deteriorated, it is preferable to add argon or oxygen to the source gas so that the polymer film can be removed. .

Here, after the step of FIG. 1C, a method of removing the resist pattern remaining on the pattern transfer film pattern and etching the insulating film using only the pattern transfer film pattern as a mask is adopted. You can also

[0057]

EXAMPLES (Synthesis Example 1) Copper tetrachloride (1) 0.50 g, 15- in a mixed solvent of anhydrous toluene 136 mL and anhydrous heptane in an argon gas atmosphere in a four flask equipped with a dropping funnel and a reflux condenser. Crown-5-ether 1
3.26g (0.0602mo1) and metallic sodium 2
7.6 g (1.20 ml) was added and heated to the solvent reflux temperature to prepare sodium dispersion. Next, while maintaining the solvent reflux temperature, 29.27 g (0.250 ml) of methyldichlorosilane and 47.78 g (0.250 mol) of methylphenyldichlorosilane dissolved in a mixed solvent of 34 mL of anhydrous toluene and 6 mL of anhydrous heptane were added from a dropping funnel.
Was added dropwise over about 30 minutes, and the mixture was further reacted at the solvent reflux temperature for 2 hours. Then, 0.8 g (0.10 mol) of trimethylchlorosilane dissolved in 20 mL of anhydrous toluene was added, the mixture was reacted for 2 hours, and then cooled to room temperature. .

500 ml of toluene was added, the precipitate was pressure filtered under nitrogen and the filtrate was concentrated. 500 mL of ethanol was added to the solution to precipitate the polymer. After the polymer was filtered, it was dissolved in toluene, the solution was washed with ion-exchanged water, and dried with anhydrous magnesium sulfate.
After removing the desiccant, the solvent was removed under reduced pressure, and 100 mL of toluene was added and dissolved, and then ethanol 1000 m was added.
1), and the precipitate was filtered and dried in vacuum to obtain 11.2 g (27.3%) of pale-yellow solid polysilane (PS-1).

According to ¹ H-NMR (CDCl ₃ ), the substituent ratio is Ph / Me / H = 0.3 / 1.0 / 0.2 (R in formula 1, R1 = Me, R2 = Ph, a = 0.28, b
= 0.3), the weight average molecular weight is 450 by GPC analysis.
It was 0.

[Chemical formula 23] (Synthesis example 2) In a four flask equipped with a dropping funnel and a reflux condenser, anhydrous toluene 136 m under an argon gas atmosphere.
Copper (I) chloride in a mixed solvent of L and anhydrous heptane (24 mL)
0.50 g, 15-crown-5-ether 13.26
g (0.0602 mol) and metallic sodium 27.6 g
(1.20 mol), and heated to the solvent reflux temperature,
Sodium dispersion was prepared. Next, while maintaining the solvent reflux temperature, 29.27 g (0.250 mol) of methyldiglorosilane and 63.30 g (0.250 mol) of diphenyldichlorosilane dissolved in a mixed solvent of 34 mL of anhydrous toluene and 6 mL of anhydrous heptane were added from a dropping funnel. About 30
The mixture was added dropwise over a period of 2 minutes, and the mixture was further reacted at the solvent remote flow temperature for 2 hours. Then, 0.8 g (0.10 mol) of trimethylchlorosilane dissolved in 20 mL of anhydrous toluene was added, and the mixture was reacted for 2 hours and then cooled to room temperature.

500 ml of toluene was added, the precipitate was pressure filtered under nitrogen and the filtrate was concentrated. 500 mL of ethanol was added to the solution to precipitate the polymer. After the polymer was filtered, it was dissolved in toluene, the solution was washed with ion-exchanged water, and dried with anhydrous magnesium sulfate.
After removing the desiccant, the solvent was removed under reduced pressure, and 100 mL of toluene was added and dissolved, and then 1000 m of ethanol was added.
1), and the precipitate was filtered and vacuum dried to obtain 13.2 g (23.3%) of a pale yellow solid polysilane (PS-2).

By 1H-NMR (CDCl3), the substituent ratio is Ph / Me / H = 1.0 / 1.0 / 0.3 (R = Me, R1, R2 = Ph, a = in the chemical formula (1). 0.
3, b = 0.33) and the weight average molecular weight was 5,100 as determined by GPC analysis.

[Chemical formula 13] (Synthesis Example 3) 100 mL of anhydrous dimethoxyethane was added to a four flask equipped with a dropping funnel and a reflux condenser under an argon gas atmosphere.
And 48.62 g (2.00 mol) of magnesium metal were added, and a small amount of iodine was added. Next, a small amount of 84.96 g (0.500 mol) of tetrachlorosilane dissolved in 30 mL of anhydrous dimethoxyethane was added from a dropping funnel to confirm the start of the reaction, and then anhydrous dimethoxyethane 3 was added to the flask.
After adding 70 mL, the solution was gradually added dropwise (about 60 minutes), and further reacted at room temperature for 16 hours. In a four-necked flask equipped with another dropping funnel and a reflux condenser, 100 mL of anhydrous dimethoxyethane and 33.91 g (1.40 mol) of magnesium metal were added under an argon gas atmosphere, and a small amount of iodine was added. Then, from the dropping funnel, 84.28 g of allyl bromide dissolved in 30 mL of anhydrous dimethoxyethane.
After confirming the start of the reaction by adding a small amount of (0.698 mol),
Then, add 370 mL of anhydrous dimethoxyethane to the flask and gradually add dropwise (for about 60 minutes).
The reaction was carried out for 6 hours to prepare an allylmagnesium bromide solution.

Next, this prepared allylmagnesium bromide solution was added to another flask over about 1 hour, and after reacting for about 16 hours, a part of the solution was taken out and hydrolyzed with reion-exchanged water to obtain acidity. Since it is presumed that many Si-C1 bonds remain in the reaction system from the above,
Furthermore, 20 mL of anhydrous dimethoxyethane was added to this reaction system.
76.54 g of dissolved allyl chloride was added dropwise over about 50 minutes, and further reacted at the solvent reflux temperature for 2 hours. At a reaction temperature of 60 to 65 ° C., 54.34 g (0.50 mo) of trimethylchlorosilane dissolved in 20 mL of anhydrous toluene.
l) was added and the mixture was reacted for 1.5 hours and then cooled to room temperature. Toluene (500 ml) was added, the precipitate was pressure-filtered under nitrogen, the filtrate was washed with ion-exchanged water, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was removed under reduced pressure, 50 mL of toluene was added and dissolved, and then dropped into 500 ml of ethanol, the orange precipitate was filtered, and vacuum dried to obtain 8.0 lg of polysilane (PS-3). It was

It was confirmed by 1H-NMR (CDC13) that an allyl group had been introduced. From the GPC analysis, the weight average molecular weight was 3100.

[Chemical formula 14] (Synthesis Example 4) To a four-necked flask equipped with a dropping funnel and a reflux condenser, 100 ml of anhydrous dimethoxyethane and 48.62 g (2.00 ml) of magnesium metal were added under an argon gas atmosphere, and a small amount of iodine was added. Next, from the dropping funnel, tetrachlorosilane 8 dissolved in 30 mL of anhydrous dimethoxyethane was added.
After confirming the start of the reaction by adding a small amount of 4.96 g (0.500 mol 1), anhydrous dimethoxyethane 37 was added to the flask.
After adding 0 mL, the mixture was gradually added dropwise (about 60 minutes), further reacted at room temperature for 20 hours, and then reacted at a solvent reflux temperature for 2 hours. Next, 137.02 g of butyl bromide dissolved in 20 mL of anhydrous dimethoxyethane (1.
00mo1) was added dropwise over about 80 minutes, and further reacted at the solvent reflux temperature for 2 hours. Reaction temperature 40 to 60 ° C
Then, 108.61 g (1.00 mo1) of trimethylchlorosilane dissolved in 20 mL of anhydrous dimethoxyethane was gradually added, and the mixture was reacted for 1 hour and then cooled to room temperature.
Toluene (500 ml) was added, the precipitate was pressure-filtered under nitrogen, the filtrate was washed with ion-exchanged water, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was removed under reduced pressure, 50 mL of toluene was added and dissolved, and then ethanol 5 was added.
The mixture was added dropwise to 00 ml, and the precipitate was filtered and dried in vacuum to obtain 11.7 g of a reddish orange solid polysilane (PS-4). 1
It was confirmed by H-NMR (CDCl3) that a butyl group had been introduced. From GPC analysis, the weight average molecular weight was 4,800.

[Chemical formula 15] (Synthesis example 5) To a four-necked flask equipped with a dropping funnel and a reflux condenser, 100 mL of anhydrous dimethoxyethane and 48.62 g (2.00 mol) of magnesium metal were added under an argon gas atmosphere, and iodine was added in a small amount. Next, from the dropping funnel, tetrachlorosilane 8 dissolved in 30 mL of anhydrous dimethoxyethane was added.
A small amount of 4.96 g (0.500 mol) was added to confirm the start of the reaction, and then anhydrous dimethoxyethane 37 was added to the flask.
Under gradually drops after adding 0mL was (approximately 60 minutes), was further reacted at room temperature for 20 hours, the reaction was carried out for 2 hours at the reflux temperature of the solvent. Next, in this reaction system, 120.9 g of allyl bromide dissolved in 120 mL of anhydrous dimethoxyethane (1.
00mo1) was added dropwise over about 80 minutes, and the reaction was further performed at the solvent reflux temperature for 9 hours. After cooling to room temperature, a 3.0 M solution of ethylmagnesium bromide in diethyl ether 80 was added.
ml was added. After reacting for 11 hours at room temperature, it was reacted for 3 hours at the solvent reflux temperature. There, trimethylchlorosilane 26.1 dissolved in 20 mL of anhydrous dimethoxyethane
1 g (0.200 mol) was gradually added, and the mixture was reacted for 2 hours and then cooled to room temperature. Toluene (500 ml) was added, the precipitate was pressure-filtered under nitrogen, the filtrate was washed with ion-exchanged water, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was removed under reduced pressure, 50 mL of toluene was added and dissolved, and then the solution was added dropwise to 500 mL of ethanol, the precipitate was filtered and vacuum dried, and polysilane (P
S-5) 4.0g was obtained. 1H-NMR (CDCl3)
Thus, it was confirmed that the introduction was carried out with ethyl group / allyl group = 1 / 1.3. Weight average molecular weight of 4 from GPC analysis
It was 800.

[Chemical Formula 16] (Example 1) (Reference example) 1 g of polysilane (PS-1) synthesized in Synthesis example 1, 0.3 g of a cross-linking agent (K1) represented by the following chemical formula, and a toluene solution of 25% BTTB as a radical generator. A pattern transfer composition was prepared by dissolving 8 g of the acid generator NAI-106 in 0.03 g and 9 g of anisole.

[Chemical formula 17] A SiO ₂ film having a film thickness of 500 nm was formed on a silicon wafer, the above-mentioned pattern transfer composition was applied on the SiO ₂ film, and baked to form a pattern transfer film having a film thickness of 250 nm.

The pattern transfer film was crosslinked and insolubilized by heating at 240 ° C. for 1 minute in a nitrogen atmosphere. Then, a positive chemically amplified resist TDUR-P007 is applied on this pattern transfer film, and 89
The resist film having a film thickness of 250 nm was formed by baking at 120 ° C. for 120 seconds. 30mJ / c through a mask using a reduction exposure type stepper using a KrF excimer laser as a light source
It was exposed with an exposure amount of m ² and baked at 98 ° C. for 120 seconds. The exposed resist film was developed with a 0.21N TMAH developer to form a 0.18 μm line-and-space resist pattern. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.
Using the resist pattern as a mask, the HBr flow rate is 50 sc
When the pattern transfer film was etched under the conditions of cm, vacuum degree of 80 mTorr and excitation power of 200 W, a pattern transfer film pattern having vertical sidewalls was formed. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Next, using the pattern transfer film as a mask, the flow rate of C ₄ F _{8 is} 50 sccm, and the flow rate of CO is 10 sc.
cm, Ar flow rate 100 sccm, O ₂ flow rate 3 sccm,
SiO under the conditions of a vacuum degree of 10 Torr and an excitation power of 200 W
_{The two} films were etched. Pattern transfer film etch
The ching resistance was sufficient, and a SiO ₂ film pattern having vertical sidewalls was obtained. Further, the remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution.

Table 1 shows the components of the pattern transfer composition of Example 1.

[Table 1] The components of the pattern transfer compositions of Comparative Examples 1 to 4 and Examples 2 to 16 shown below are also shown in Table 1. (Comparative Example 1) In the same manner as in Example 1, the silicon wafer 1 has a film thickness of 500 n.
m SiO ₂ film was formed. Next, a polysilicon film having a film thickness of 200 nm necessary for etching this SiO ₂ film was formed. Then, a positive type chemically amplified resist (trade name APEX-E, manufactured by Shipley Co., Ltd.) was applied on the polysilicon film, and baking was performed at 98 ° C. for 120 seconds. The film thickness of the resist at this time is 300 nm.

Then, exposure and development were performed in the same manner as in Example 1 to form a resist pattern of 0.18 μm line and space.

The side wall of the obtained resist pattern is shown in FIG.
The wavy shape shown in Fig. 3 was observed, and a good pattern could not be obtained. It is considered that this is because a standing wave was generated in the resist film due to strong light reflection by the polysilicon film. (Comparative Example 2) As in Example 1, a 500 nm thick SiO ₂ film was formed on a silicon wafer. Next, this Si
A film thickness of 20 which is a film thickness necessary for etching the O ₂ film
A 0 nm carbon film was formed. Furthermore, a positive chemically amplified resist (trade name: APEX-E,
(Manufactured by Shipley) was applied and baking was performed at 98 ° C. for 120 seconds. At this time, the film thickness of the resist is 200 nm
Is.

Next, in the same manner as in Example 1, exposure / development processing was performed to form a resist pattern of 0.18 μm line and space. The carbon film has a wavelength of 248
Since the light absorption property in nm is high, a resist pattern having good dimensional controllability and having a good resist profile in which reflection from the underlying film was suppressed was obtained as in Example 1.

Using the resist pattern formed as described above as a mask, a magnetron RIE apparatus was used.
CF ₄ flow rate 80 sccm, O ₂ flow rate 8 sccm, Ar flow rate 20 sccm, vacuum degree 10 mTorr, excitation power 20
The carbon film was etched under the condition of 0 W. As a result, the resist pattern was not removed during the etching of the carbon film, and the SiO ₂ film could not be etched to a desired size. Further, under the above conditions, the etching rates of the single resist film and the carbon film were changed. When measured, the resist film was 185 nm / min, and the carbon film was 65 nm / min.

It was found that the etching rate of the carbon film was only 0.35 times that of the resist film, and the resist film and the carbon film did not have a high selection ratio. For this reason,
It is considered that the resist pattern collapsed and disappeared during the etching of the carbon film. (Comparative Example 3) In the same manner as in Example 1, a 500 nm SiO ₂ film was formed on a silicon wafer. Next, the film thickness 20
A 0 nm carbon film was sequentially formed. Then, on this carbon film, a positive chemically amplified resist (trade name,: A
PEX-E, manufactured by Shipley Co., Ltd., and applied at 98 ° C for 12
Baking was performed for 0 seconds. The thickness of the resist film thus obtained is 700 nm. Then, this resist film was exposed and developed in the same manner as in Example 2 to form a resist pattern of 0.18 μm line and space.

Using the resist pattern formed as described above as a mask, the carbon film was etched under the same conditions as in Comparative Example 2. As a result, the carbon film could be etched, but as shown in FIG. 3, the processed shape was a tapered shape and could not be etched with good anisotropy. It is considered that this is because the etching selectivity between the resist pattern and the carbon film is not high, and the resist pattern recedes during the carbon etching.

Further, since the resist film is as thick as 700 nm, the focus margin at the optimum exposure amount is 0.3.
Narrow as 1.0 μm, which is the required value for device manufacturing 1.0 μm
The focus margin of m could not be obtained. Comparative Example 4 In the same manner as in Example 1, a SiO ₂ film 2 having a film thickness of 500 nm was formed on the silicon wafer 1. Next, a coating solution 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 to form a polysulfone film 3 as an antireflection film.

Next, a positive type chemically amplified resist (trade name: APEX-E, manufactured by Sibbley Co.) was applied on the polysulfone film 3 and baked at 98 ° C. for 120 seconds,
A resist film 4 was formed. The resist film 4 thus obtained has a thickness of 300 nm. Then, exposure and development were performed in the same manner as in Example 2 to form a 0.18 μm line-and-space resist pattern.

Using the resist pattern formed as described above as a mask, the polysulfone film 3 was etched under the same etching conditions as in Comparative Example 2. This state is shown in FIG. The polysulfone film 3 pattern did not show a marked taper shape as the carbon film pattern of Comparative Example 3. This is because the etching rate of the polysulfone film 3 measured with a single film is 200 n.
m / min and faster than the etching rate of the carbon film,
Moreover, the film thickness (115 nm) of the polysulfone film 3 is Comparative Example 3
This is because it is thinner than the thickness (700 nm) of the carbon film.

Next, using the resist pattern 4 and the polysulfone film pattern 3 thus obtained as a mask, the SiO ₂ film 2 was etched under the same etching conditions as in Example 3. This state is shown in FIG.

In this state, compared with the bottom dimension (X) of the polysulfone film 3 before etching, Si after etching
Since the pattern dimension (Y) of the O ₂ film 2 was reduced by 20 nm, it was not possible to perform etching with good dimension controllability that is faithful to the dimension of the resist pattern 4.

Further, the processed shape of the SiO 2 film 2 was also tapered, and it was not possible to etch vertically with good anisotropy. When the etching rate of the single film was measured under these etching conditions, the etching rate of the polysulfone film 3 was 102 nm / min, which was less dry etching resistant than the resist. Therefore, Si
It is considered that the resist pattern 4 and the polysulfone film pattern 3 receded during the etching of the O ₂ film 2, the pattern dimension of the SiO ₂ film 2 was thinned, and the etching shape was tapered. (Example 2) (Reference example) 1 g of polysilane (PS-2) synthesized in Synthesis example 2, 0.3 g of a crosslinking agent K2 represented by the following chemical formula, 0.8 g of a toluene solution of 25% BTTB as a radical generator. the acid generator NAI-106 0.005 g, was dissolved in anisole 9 g, to prepare a pattern transfer composition.

[Chemical formula 18] A SiO ₂ film having a film thickness of 500 nm was formed on a silicon wafer, and the above-mentioned pattern transfer solution was applied onto the SiO ₂ film and baked to form a pattern transfer film having a film thickness of 250 nm. Further under nitrogen atmosphere, 200
The pattern transfer film was crosslinked and insolubilized by heating at 0 ° C. for 3 minutes.

Then, similarly to Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with Cl ₂ gas using the resist pattern as a mask to form a pattern of the pattern transfer film having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Next, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask.
The pattern transfer film had a sufficient etching resistance, and a SiO ₂ pattern having vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Example 3) (Reference Example) 1 g of polysilane (PS-1) synthesized in Synthesis Example 1, 1.0 g of a crosslinking agent (K3) represented by the following chemical formula, and a toluene solution of 25% BTTB as a radical generator. 8g, acid generator NAI-106 0.005g, anisole 9g
To prepare a pattern transfer composition.

[Chemical formula 19] A SiO ₂ film having a film thickness of 500 nm was formed on a silicon wafer, and the above-mentioned pattern transfer solution was applied onto the SiO ₂ film and baked to form a pattern transfer film having a film thickness of 250 nm. Further under a nitrogen atmosphere, 240
The pattern transfer film was crosslinked and insolubilized by heating at 0 ° C. for 1 minute.

Then, as in Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with Cl ₂ using the resist pattern as a mask to form a pattern transfer film pattern having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Then, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask. The pattern transfer film has sufficient etching resistance,
A SiO ₂ pattern with vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Example 4) The polysilane synthesized in Synthesis Example 1 (PS-
1) 1 g, 1.0 g of polysilane (PS-3) synthesized in Synthesis Example 3 as a crosslinking agent, 25% B as a radical generator
0.8g of toluene solution of TTB, acid generator NAI-10
0.005 g of 6 was dissolved in 9 g of anisole to prepare a pattern transfer composition.

A SiO ₂ film having a film thickness of 500 nm is formed on a silicon wafer, and the above-mentioned pattern transfer solution is applied onto the SiO ₂ film and baked to form a film having a film thickness of 250 n.
m pattern transfer film was formed. Further, by heating at 240 ° C. for 1 minute in a nitrogen atmosphere, the pattern transfer film was crosslinked and insolubilized.

Then, similarly to Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with HBr using the resist pattern as a mask to form a pattern of the pattern transfer film having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Then, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask. The pattern transfer film has sufficient etching resistance,
A SiO ₂ pattern with vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Example 5) Polysilane synthesized in Synthesis Example 3 (PS-
3) 1.0 g and 25% BTTB in toluene solution 0.8
g, NAI-106 0.005 g, toluene 9.0 g
To prepare a pattern transfer composition.

A SiO ₂ film having a film thickness of 500 nm is formed on a silicon wafer, and the above-mentioned pattern transfer solution is applied on the SiO ₂ film and baked to form a film having a film thickness of 250 n.
m pattern transfer film was formed. Further, by heating at 240 ° C. for 1 minute in a nitrogen atmosphere, the pattern transfer film was crosslinked and insolubilized.

Then, similarly to Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with Cl ₂ using the resist pattern as a mask to form a pattern of the pattern transfer film having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Next, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask. The pattern transfer film has sufficient etching resistance,
A SiO ₂ pattern with vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Example 6) The polysilane synthesized in Synthesis Example 4 (PS-
4) 1.0 g and 0.005 g of NAI-106 were dissolved in 9.0 g of anisole to prepare a pattern transfer composition.

A 500 nm-thickness SiO ₂ film is formed on a silicon wafer, and the above-mentioned pattern transfer solution is applied onto this SiO ₂ film and baked to form a film having a thickness of 250 n.
m pattern transfer film was formed. Further, by heating at 160 ° C. for 1 minute in a nitrogen atmosphere, the pattern transfer film was crosslinked and made insoluble.

Then, similarly to Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with HBr using the resist pattern as a mask to form a pattern of the pattern transfer film having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Next, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask.
The pattern transfer film had a sufficient etching resistance, and a SiO ₂ pattern having vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Example 7) 1.0 g of polysilane (PS-5) synthesized in Synthesis Example 5 and 1.0 g of a crosslinking agent (K4) represented by the following chemical formula, and a toluene solution of 25% BTTB as a radical generator 0.8
g, 0.03 g of the acid generator NAI-106, cumene 9.
It was dissolved in 0 g to prepare a pattern transfer composition.

[Chemical formula 20] A SiO ₂ film having a film thickness of 500 nm was formed on a silicon wafer, and the above-mentioned pattern transfer solution was applied onto the SiO ₂ film and baked to form a pattern transfer film having a film thickness of 250 nm. Further under a nitrogen atmosphere, 240
The pattern transfer film was crosslinked and insolubilized by heating at 0 ° C. for 1 minute.

Then, similarly to Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with Cl ₂ using the resist pattern as a mask to form a pattern transfer film pattern having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Next, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask.
The pattern transfer film had a sufficient etching resistance, and a SiO ₂ pattern having vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. Example 8 1.0 g of polysilane having the following chemical formula and 1.0 g of polysilane (PS-3) synthesized in Synthesis Example 3, 0.8 g of 25% BTTB toluene solution as a radical generator, and NAI-106 acid generator. Was dissolved in 9.0 g of cumene to prepare a pattern transfer composition.

[Chemical formula 21] A SiO ₂ film having a film thickness of 500 nm was formed on a silicon wafer, and the above-mentioned pattern transfer solution was applied onto the SiO ₂ film and baked to form a pattern transfer film having a film thickness of 250 nm. Further under a nitrogen atmosphere, 240
The pattern transfer film was crosslinked and insolubilized by heating at 0 ° C. for 1 minute.

Then, similarly to Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with HBr using the resist pattern as a mask to form a pattern of the pattern transfer film having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Next, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask.
The pattern transfer film had a sufficient etching resistance, and a SiO ₂ pattern having vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Example 9) 1.0 g of polysilane (PS-3) synthesized in Synthesis Example 3,
0.3 g of a crosslinking agent (K5) represented by the following chemical formula, and a toluene solution of 25% BTTB as a radical generator 0.8
and 0.03 g of the acid generator NAI-106 were dissolved in 9.0 g of anisole to prepare a pattern transfer composition.

[Chemical formula 22] A SiO ₂ film having a film thickness of 500 nm was formed on a silicon wafer, and the above-mentioned pattern transfer solution was applied onto the SiO ₂ film and baked to form a pattern transfer film having a film thickness of 250 nm. Further under a nitrogen atmosphere, 240
The pattern transfer film was crosslinked and insolubilized by heating at 0 ° C. for 1 minute.

Then, similarly to Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with HBr using the resist pattern as a mask to form a pattern of the pattern transfer film having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Next, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask.
The pattern transfer film had a sufficient etching resistance, and a SiO ₂ pattern having vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Example 10) 1.0 g of polysilane (PS-3) synthesized in Synthesis Example 3,
0.3 g of a cross-linking agent (K6) represented by the following chemical formula, 0.8% toluene solution of 25% BTTB as a radical generator
and 0.03 g of the acid generator NAI-106 were dissolved in 9.0 g of anisole to prepare a pattern transfer composition.

[Chemical formula 23] A SiO ₂ film having a film thickness of 500 nm was formed on a silicon wafer, and the above-mentioned pattern transfer solution was applied onto the SiO ₂ film and baked to form a pattern transfer film having a film thickness of 250 nm. Further under a nitrogen atmosphere, 240
The pattern transfer film was crosslinked and insolubilized by heating at 0 ° C. for 1 minute.

Then, as in Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with HBr using the resist pattern as a mask to form a pattern of the pattern transfer film having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Then, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask. The pattern transfer film has sufficient etching resistance,
A SiO ₂ pattern with vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Example 11) 1.0 g of a polymer (PS-31) synthesized using benzyl bromide instead of butyl bromide in the same manner as in Synthesis Example 3, and an acid generator NAI-106.
Was dissolved in cumene to prepare a pattern transfer composition.

A SiO ₂ film having a film thickness of 500 nm is formed on a silicon wafer, and the above-mentioned pattern transfer solution is applied onto the SiO ₂ film and baked to form a film having a film thickness of 250 n.
m pattern transfer film was formed. Further, by heating at 240 ° C. for 1 minute in a nitrogen atmosphere, the pattern transfer film was crosslinked and insolubilized.

Then, similarly to Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with HBr using the resist pattern as a mask to form a pattern of the pattern transfer film having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Then, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask. The pattern transfer film has sufficient etching resistance,
A SiO ₂ pattern with vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Example 12) 1.0 g of a polymer (PS-41) synthesized using chloromethylstyrene instead of allyl bromide (allyl bromide) by the same method as in Synthesis Example 4, and 25% BTTB toluene as a radical generator. Solution 0.8
and 0.01 g of the acid generator NAI-106 were dissolved in toluene to prepare a pattern transfer composition.

A SiO ₂ film having a film thickness of 500 nm is formed on a silicon wafer, and the above-mentioned pattern transfer solution is applied on the SiO ₂ film and baked to give a film thickness of 250 n.
m pattern transfer film was formed. Further, by heating at 240 ° C. for 1 minute in a nitrogen atmosphere, the pattern transfer film was crosslinked and insolubilized.

Then, similarly to Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with HBr using the resist pattern as a mask to form a pattern of the pattern transfer film having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Next, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask.
The pattern transfer film had a sufficient etching resistance, and a SiO ₂ pattern having vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Synthesis Example 6) 100 mL of anhydrous dimethoxyethane and 48.62 g (2.00 mol) of metallic magnesium were added to a four flask equipped with a dropping funnel and a reflux condenser under an argon gas atmosphere, and iodine was added in a small amount. Next, from the dropping funnel, tetrachlorosilane 8 dissolved in 30 mL of anhydrous dimethoxyethane was added.
A small amount of 4.96 g (0.500 mol) was added to confirm the start of the reaction, and then anhydrous dimethoxyethane 37 was added to the flask.
After adding 0 mL, the mixture was gradually added dropwise (about 60 minutes), further reacted at room temperature for 20 hours, and then reacted at a solvent reflux temperature for 2 hours. Next, 137.02 g of butyl bromide dissolved in 20 mL of anhydrous dimethoxyethane (1.
(00 mol) was added dropwise over about 80 minutes, and further reacted at the solvent reflux temperature for 2 hours. After cooling to room temperature, 500 ml of toluene are added, the precipitate is pressure filtered under nitrogen,
The filtrate was treated with dilute hydrochloric acid, further washed with ion-exchanged water, and dried with anhydrous magnesium sulfate. After removing the desiccant, the solvent was removed under reduced pressure, 50 mL of toluene was added to dissolve it, and the mixture was added dropwise to 500 ml of ethanol, and the precipitate was filtered and vacuum dried to obtain a red-orange solid polysilane (P
0.5 g of S-6) was obtained. 1H-NMR (CDC1
From 3), it was confirmed that a butyl group and a Si—H group were introduced. From GPC analysis, weight average molecular weight of 48
It was 00.

[Chemical formula 24] (Synthesis Example 7) 100 mL of anhydrous dimethoxyethane and 48.62 g (2.00 mol) of magnesium metal were added to a four flask equipped with a dropping funnel and a reflux condenser under an argon gas atmosphere, and iodine was added in a small amount. Next, from the dropping funnel, tetrachlorosilane 8 dissolved in 30 mL of anhydrous dimethoxyethane was added.
A small amount of 4.96 g (0.500 mol) was added to confirm the start of the reaction, and then anhydrous dimethoxyethane 37 was added to the flask.
After adding 0 mL, the mixture was gradually added dropwise (about 60 minutes), further reacted at room temperature for 20 hours, and then reacted at a solvent reflux temperature for 2 hours. Next, 137.02 g of allyl bromide dissolved in 20 mL of anhydrous dimethoxyethane (1.
(00 mol) was added dropwise over about 80 minutes, and further reacted at the solvent reflux temperature for 20 hours. After cooling to room temperature, 500 ml of toluene was added, the precipitate was filtered under pressure under nitrogen, the filtrate was treated with dilute hydrochloric acid, further washed with ion-exchanged water, and dried with anhydrous magnesium sulfate. After removing the desiccant, remove the solvent under reduced pressure, and add 50 mL of toluene.
Was added and dissolved, and then dropped into 500 ml of ethanol,
The precipitate was filtered and dried under vacuum to obtain 0.5 g of polysilane (PS-7) as a reddish orange solid. 1H-NMR (CDC
From 13), it was confirmed that an allyl group and a Si—H group were introduced. From GPC analysis, the weight average molecular weight was 3,800.

[Chemical formula 25] (Synthesis Example 8) 100 mL of anhydrous dimethoxyethane and 24.32 g (1.00 mol) of metal magnesium were added to a four flask equipped with a dropping funnel and a reflux condenser under an argon gas atmosphere, and a small amount of iodine was added. Next, from the dropping funnel, tetrachlorosilane 8 dissolved in 30 mL of anhydrous dimethoxyethane was added.
A small amount of 4.96 g (0.500 mol) was added to confirm the start of the reaction, and then anhydrous dimethoxyethane 37 was added to the flask.
After adding 0 mL, the mixture was gradually added dropwise (about 60 minutes), further reacted at room temperature for 20 hours, and then reacted at a solvent reflux temperature for 2 hours. Next, a separately synthesized dimethoxyethane solution of phenylmagnesium bromide (about 2M solution 500
m1) was added dropwise to this reaction system over about 2 hours and further reacted at the solvent reflux temperature for 2 hours. After cooling to room temperature, 1000 ml of toluene was added, the precipitate was pressure-filtered under nitrogen, the filtrate was treated with dilute hydrochloric acid, further washed with ion-exchanged water, and dried with anhydrous magnesium sulfate. After removing the desiccant, the solvent was removed under reduced pressure to remove toluene 5
After adding 0 mL and dissolving, it was dripped in 500 ml of ethanol, the precipitate was filtered, and vacuum dried to obtain 8.5 g of red-orange solid polysilane (PS-8). 1H-NMR (CD
It was confirmed by CI3) that the phenyl group and the Si-H group were introduced. From GPC analysis, the weight average molecule was 13,800.

[Chemical formula 26] (Example 13) 1.0 g of polysilane (PS-6) synthesized in Synthesis Example 6,
0.5 g of a crosslinking agent (K7) represented by the following chemical formula, 0.018 g of an acid generator NAl-106 (manufactured by Midori Kagaku Co., Ltd.), and an antioxidant 2,6-di (t-butyl) -4 -methylphenol. A solution was prepared by dissolving 005 g and 0.20 g of a radical generator BTTB (manufactured by NOF CORPORATION) in 10 g of cumene.

[Chemical formula 27] A SiO ₂ film having a film thickness of 500 nm was formed on a silicon wafer, and the above-mentioned pattern transfer solution was applied onto the SiO ₂ film and baked to form a pattern transfer film having a film thickness of 250 nm. Further under a nitrogen atmosphere, 240
The pattern transfer film was crosslinked and insolubilized by heating at 0 ° C. for 1 minute.

Then, similarly to Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with HBr using the resist pattern as a mask to form a pattern of the pattern transfer film having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Then, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask. The pattern transfer film has sufficient etching resistance,
A SiO ₂ pattern with vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Example 14) The polysilane synthesized in Synthesis Example 6 (PS-
6) 1.0 g, polysilane (PS- synthesized in Synthesis Example 7)
7) 1.0 g, acid generator NA1-106 (made by Midori Kagaku) 0.018 g, antioxidant 2,6- (t-butyl)
A pattern transfer composition solution was prepared by dissolving 0.005 g of -4-methylphenol and 0.20 g of a radical generator BTTB (manufactured by NOF CORPORATION) in 10 g of cumene.

A SiO ₂ film having a film thickness of 500 nm is formed on a silicon wafer, and the above-mentioned pattern transfer solution is applied onto the SiO ₂ film and baked to form a film having a film thickness of 250 n.
m pattern transfer film was formed. Further, by heating at 240 ° C. for 1 minute in a nitrogen atmosphere, the pattern transfer film was crosslinked and insolubilized.

Then, similarly to Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with HBr using the resist pattern as a mask to form a pattern of the pattern transfer film having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Next, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask. The pattern transfer film has sufficient etching resistance,
A SiO ₂ pattern with vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Example 15) The polysilane synthesized in Synthesis Example 8 (PS-
8) 1.0 g, polysilane (PS- synthesized in Synthesis Example 7)
7) 1.0 g, acid generator NA1-106 (manufactured by Midori Kagaku) 0.018 g, antioxidant 2,6-di (t-butyl) -4-methylphenol 0.005 g, radical generator BTTB (Japan (Fat and oil company) 0.20 g of cumene 10
g to prepare a pattern transfer composition solution.

A SiO ₂ film having a film thickness of 500 nm is formed on a silicon wafer, and the above-mentioned pattern transfer solution is applied onto the SiO ₂ film and baked to form a film having a film thickness of 250 n.
m pattern transfer film was formed. Further, by heating at 240 ° C. for 1 minute in a nitrogen atmosphere, the pattern transfer film was crosslinked and insolubilized.

Then, similarly to Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with HBr using the resist pattern as a mask to form a pattern of the pattern transfer film having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Next, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask. The pattern transfer film has sufficient etching resistance,
A SiO ₂ pattern with vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution. (Example 16) 1.0 g of polysilane synthesized in Synthesis Example 7
(PS-7), acid generator NAl-106 (manufactured by Midori Kagaku) 0.018 g, antioxidant 2,6-di (t-butyl) -4-methylphenol 0.005 g, radical generator BTTB (Japan (Fat and oil company) 0.20 g of cumene 10
g to prepare a pattern transfer composition solution.

A SiO ₂ film having a film thickness of 500 nm is formed on a silicon wafer, and the above-mentioned pattern transfer solution is applied on the SiO ₂ film and baked to form a film having a film thickness of 250 n.
m pattern transfer film was formed. Further, by heating at 240 ° C. for 1 minute in a nitrogen atmosphere, the pattern transfer film was crosslinked and insolubilized.

Then, as in Example 1, a resist pattern was formed on the pattern transfer film. As a result of SEM observation of the cross section of the obtained resist pattern, no wavy shape due to standing waves was observed on the sidewall of the resist pattern.

Further, as in Example 1, the pattern transfer film was etched with HBr using the resist pattern as a mask to form a pattern transfer film pattern having vertical sidewalls. It was found that the resist remained on the upper portion and had a sufficient etching rate ratio.

Next, as in Example 1, the SiO ₂ film was etched using the pattern transfer film as a mask. The pattern transfer film has sufficient etching resistance,
A SiO ₂ pattern with vertical sidewalls was obtained. The remaining pattern transfer film could be easily peeled off with an organic alkali aqueous solution or a dilute hydrofluoric acid aqueous solution.

[0132]

According to the present invention, a film can be formed by a coating method, reflected light can be suppressed during exposure, an etching selection ratio with respect to a resist is large, and an insulating film such as a silicon oxide film or a silicon nitride film can be formed. It is possible to provide a pattern transfer composition capable of forming a pattern transfer film which is excellent in dry etching resistance at the time of processing a film to be processed. Thereby, the insulating film can be processed with good dimensional controllability. The present invention exerts a particularly remarkable effect when the resist film thickness is reduced in order to improve the exposure amount margin focus margin or resolution in optical lithography, and its industrial value is great.

[Brief description of drawings]

FIG. 1 is a schematic view showing a process of processing a film to be processed using a pattern transfer film of the present invention.

FIG. 2 is a shape of a resist pattern when a conventional pattern transfer material is used.

FIG. 3 is a pattern shape obtained by etching a conventional pattern transfer material.

FIG. 4 is a pattern shape when the pattern transfer material of Comparative Example 4 is used.

[Explanation of symbols]

1 ... Silicon substrate 2 ... Silicon oxide film 3 ... Pattern transfer material layer 4 ... Resist 11 ... Silicon substrate 12 ... Silicon oxide film 13 ... Pattern transfer material layer 14 ... Resist

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G03F 7/38 501 G03F 7/38 501 7/40 521 7/40 521 H01L 21/027 H01L 21/30 574 (72) Inventor Hideo Ohta 1 Komukai Toshiba-cho, Kochi-ku, Kawasaki-shi, Kanagawa (56) References JP-A-10-209134 (JP, A) JP-A-11-174684 (JP, A) JP 2000-100700 (JP, A) JP 2000-31118 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ⁷ /00-7/42 C08L 83/16 H01L 21/027

Claims (3)

(57) [Claims] 1. At least the following (a), (b) and (c):
A pattern transfer composition comprising a component. (B) a repeating unit represented by the following a) or b) of at least one polysilane a) the following general formula (1), below
Polysilane containing a copolymer containing a bonding unit represented by the general formula (3) : (However, R is a substituted or unsubstituted aliphatic hydrocarbon group having 6 or less carbon atoms, R1 and R2 are substituted or unsubstituted hydrocarbon groups having 20 or less carbon atoms, and a is 0.1 or more. 0.
It is 9 or less, and b is 0 or more and 0.7 or less. ) [Chemical 2] copolycondensates containing two or more in a molecule multiple bonds carbon - and repeating units represented by b) the following general formula (2), a coupling unit represented by the following <br/> general formula (3), carbon Polysilanes containing coalescence (However, R3, R4, and R5 may be the same or different and each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 20 or less carbon atoms. A'is 0.1 or more and 0.
It is 8 or less. ) [Chemical 4] (B) Acid generator (c) Organic solvent 2. A copolymer containing a repeating unit represented by the general formula (1) and a bonding unit represented by the general formula (3) has a repeating unit represented by the following general formula (4). pattern transfer composition according to claim 1, characterized in that it comprises in a the <br/> et al. [Chemical 5] (However, Ar is a substituted or unsubstituted aromatic hydrocarbon group having 20 or less carbon atoms. A ″ is 0.1 or more and 0.9 or less.) 3. A step of applying the pattern transfer composition according to claim 1 or 2 onto a film to be processed, and heating the film to be processed in an atmosphere having an oxygen concentration of 0.1% or less. Forming a pattern transfer film on the processed film, forming a resist pattern on the pattern transfer film, etching the pattern transfer film using the resist pattern as an etching mask, and etching the pattern transfer film. And a step of etching the film to be processed using the film as an etching mask.