JP3387740B2 - Pattern formation 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 forming method for forming a resist pattern on a semiconductor substrate in a semiconductor device manufacturing process, and a surface treatment agent used in the resist pattern forming process.

[0002]

2. Description of the Related Art In recent years, as the density and integration of semiconductor devices have increased, the need for fine processing technology has increased more and more.

As a first measure for enabling fine processing in a lithography process, DUV light using an excimer laser as a light source or short wavelength light such as EB or X-ray is used as exposure light and acid is used as a resist. A technique for forming a resist pattern composed of a chemically amplified resist that utilizes generation is being developed (“Coloring Material”, Vol. 67).
No. 7, pp 446-455 (1994)).

Hereinafter, referring to FIGS . 10 and 11 ,
As a first conventional example, a pattern forming method using a chemically amplified resist will be described.

FIG . 10 shows a process flow of a pattern forming method according to the first conventional example, and FIG. 11 shows a surface state of a semiconductor substrate formed by the pattern forming method according to the first conventional example.

First, hexamethyldisilazane (hereinafter, abbreviated as HMDS) as a surface treatment agent is supplied to the surface of the semiconductor substrate 1 made of silicon to make the surface of the semiconductor substrate 1 hydrophobic so that the semiconductor substrate 1 is made hydrophobic. 1. Adhesion is improved. This treatment is performed by bubbling liquid HMDS with nitrogen gas and then spraying HMDS on the surface of the semiconductor substrate 1 heated to 60 ° C. for 30 seconds, as shown in FIG . In this way, FIG.
As shown in (b), H of the OH group on the surface of the semiconductor substrate 1
Is replaced by Si (CH ₃ ) ₃ (trimethylsilyl group), the surface of the semiconductor substrate 1 becomes hydrophobic, the adhesion of the semiconductor substrate 1 is improved, and NH ₃ (ammonia) is generated.

Next, after a chemically amplified resist is applied to the surface of the semiconductor substrate 1 to form a resist film, the resist film is exposed using a desired mask, and then a post exposure bake (hereinafter, referred to as "exposure bake"). Abbreviated as PEB.)
And development are sequentially performed to form a resist pattern.

As a second measure for enabling fine processing in the lithography process, Japanese Patent Laid-Open No. 58-1881.
As disclosed in Japanese Patent No. 32, a technique for improving the adhesion between a semiconductor substrate and a resist pattern has been proposed.

A pattern forming method using a resist containing, for example, a phenolic resin will be described below as a second conventional example.

First, on the surface of a semiconductor substrate made of silicon, the general formula: R ¹ SiX _3-n R ² _n (where n is 0, 1
Or 2, X is a halogen or an —OR ′ group (R ′ is an alkyl group having 1 to 3 carbon atoms), and R ¹ is CH ₂ ═CH.
-, ZCH ₂ - (Z is halogen) or

[Chemical 2] And R ² is hydrogen or an alkyl group having 1 to 3 carbon atoms. By supplying a surface treatment agent containing a silane compound represented by (4) to make the surface of the semiconductor substrate hydrophobic, the adhesion of the semiconductor substrate is improved.

Next, a resist containing, for example, phenol resin is applied to the surface of the semiconductor substrate to form a resist film, and then the resist film is exposed using a desired mask, and then PEB and development are performed. Are sequentially performed to form a resist pattern.

[0012]

FIG . 12 and FIG. 13 show
1 shows a schematic cross-sectional shape of a resist pattern 2 formed on a semiconductor substrate 1 made of silicon or a semiconductor substrate 5 made of BPSG by a pattern forming method according to a first conventional example. FIGS. 12 and 13 show a positive chemically amplified resist (manufactured by Japan Synthetic Rubber Co., Ltd., KR) on a semiconductor substrate 1 made of silicon or a semiconductor substrate 5 made of BPSG.
F K2G) is applied to a film thickness of 0.7 μm, and then NA:
Exposure by 0.5 KrF excimer laser stepper, then PEB is carried out for 90 seconds at a temperature of 100 ° C., and development is carried out using a 2.38 wt% tetramethylammonium hydroxide aqueous solution of 0.25 μm line. -The cross-sectional shape of the and-space pattern is shown.

According to the first conventional example, as shown in FIG. 12 , the insolubilized layer 3 is formed on the surface of the resist pattern 2, or as shown in FIG. 4 is formed. Despite the use of the same pattern forming method, the insolubilized layer 3 is formed on the surface of the resist pattern 2 or the bottom portion 4 is formed on the bottom of the resist pattern 2 because of the atmosphere at the time of pattern formation. Or, it is considered that the surface condition of the substrate is different.

The insoluble layer 3 is formed on the surface of the resist pattern 2.
If the ridges are formed or the bottom portion 4 is formed on the bottom of the resist pattern 2, the post-process is adversely affected, which causes a decrease in the yield of the semiconductor device, which is a first problem.

Further, the resist pattern formed on the semiconductor substrate by the pattern forming method according to the second conventional example is treated with the above-mentioned surface treatment agent on the surface of the semiconductor substrate. Although the adhesiveness with the resist pattern is improved as compared with the conventional one, there is a second problem that the adhesiveness is not satisfactory when further fine processing is performed in the lithography process. That is, for example, pattern formation of 0.30 μm or less by i-line exposure, 0.25 μm by KrF excimer laser exposure
In the following pattern formation and pattern formation of 0.20 μm or less by ArF excimer laser exposure, pattern peeling may occur.

In view of the above, the first object of the present invention is to prevent the insolubilized layer from being formed on the surface portion of the resist pattern, and to prevent the bottoming portion from being formed on the bottom portion of the resist pattern. A third purpose is to further improve the adhesion between the semiconductor substrate and the resist pattern.

[0017]

Means for Solving the Problems The present inventors have conducted various studies on the cause of the formation of the hardly soluble layer on the surface of the resist pattern, and as a result, have found that the alkali component is responsible. That is, when an alkaline component is present on the surface of the resist pattern, the acid generated by exposure is deactivated to form a surface insolubilized layer, and the surface portion of the resist pattern has a T-top shape. This is
It is reported that the pattern may not be resolved when there are many alkaline components (SAMacDonald et al., Proc.SPIE, vol.1).
466, p.2 (1991)).

In order to investigate the cause of generation of the ammonia component as an alkaline component which adversely affects the chemically amplified resist, impurities in the environment were analyzed in a clean room . As shown in FIG. 14 , it was a decomposition product of HMDS. It was found that there was a positive correlation between the environmental concentrations of trimethylsilanol and ammonia. From this, it is presumed that the alkaline component that adversely affects the pattern shape of the chemically amplified resist is caused by HMDS, which is the surface treatment agent for the semiconductor substrate.

Further, the inventors of the present invention have conducted various studies on the cause of the formation of the bottom portion at the bottom of the resist pattern, and as a result, when there are atoms having unpaired electrons on the surface portion of the semiconductor substrate, they are exposed to light. It was found that the generated acid was deactivated to form a skirt. Examples of the atom having an unpaired electron include a phosphorus atom in a semiconductor substrate made of BPSG, and a nitrogen atom in a semiconductor substrate made of TiN or SiN.

The first invention of the present invention was made on the basis of the former knowledge, and uses a surface treatment agent containing a silane compound represented by the following general formula (8) in place of the conventional HMDS. Therefore, the alkaline component is prevented from being generated on the surface of the semiconductor substrate.

Specifically, the first pattern according to the present invention
The forming method includes a first step of treating the surface of the semiconductor substrate with a surface treating agent containing a silane compound represented by the following general formula (8), and a chemically amplified resist on the surface of the surface treated semiconductor substrate. And a third step of forming a resist film by exposing the resist film to light using a mask having a desired pattern shape and developing the resist film to form a resist pattern. This is the configuration provided.

R ¹ _4-n Si (OR) _n (8) where n is an integer of 1 to 3 and R is 1 to 6 carbon atoms.
A substituted saturated hydrocarbon group or an unsubstituted saturated hydrocarbon group,
A substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or a substituted alkylcarbonyl group having 1 to 6 carbon atoms or an unsubstituted alkylcarbonyl group, and R ¹ is the same or different. There, a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or a carbon number And 3 to 6 alicyclic saturated hydrocarbon groups.

According to the structure of the first pattern forming method , the semiconductor substrate is surface-treated with the surface-treating agent containing the silane compound represented by the general formula (8). Therefore, alkali components are not present on the surface of the semiconductor substrate after the surface treatment. Does not occur.

[0024] In the first pattern formation method, the chemically amplified resist in the second process, it is possible to use those containing an acid generator and a resin that becomes alkali-soluble by the action of an acid.

[0025] In the first pattern formation method, the chemically amplified resist in the second step, using an acid generator, an alkali-soluble resin, those containing a compound or resin becomes alkali-soluble by the action of an acid thing
You can

[0026] In the first pattern formation method, the chemically amplified resist in the second step, an acid generator, an alkali-soluble resin by the action of an acid which contains a compound or resin undergoes a crosslinking reaction Can be used
it can.

The second invention of the present invention was made on the basis of the latter knowledge. Instead of the conventional HMDS, the following general formula (9), (10), (11) or (12) is used. By using the surface treatment agent containing the silane compound shown, a hydrocarbon group layer is formed between the atom having an unpaired electron existing on the surface of the semiconductor substrate and the chemically amplified resist. As a result, the footing shape of the resist pattern can be significantly improved.

Specifically, the second pattern according to the present invention
The formation method is as follows .
A first step of performing a surface treatment with a surface treatment agent containing a silane compound represented by (10), (11) or (12), and a resist by applying a chemically amplified resist to the surface of the surface-treated semiconductor substrate. a second step of forming a film, after exposure using a mask having a desired pattern shape with respect to the resist film, in a configuration and a third step of forming a resist pattern by developing is there.

R ² R ¹ _3-n Si (OR) _n (9) where n is an integer of 1 to 3 and R is 1 to 6 carbon atoms.
A substituted saturated hydrocarbon group or an unsubstituted saturated hydrocarbon group,
A substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or a substituted alkylcarbonyl group having 1 to 6 carbon atoms or an unsubstituted alkylcarbonyl group, and R ¹ is the same or different. There, a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or a carbon number It is an alicyclic saturated hydrocarbon group having 3 to 6 and R ₂ is a substituted saturated hydrocarbon group having 3 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, having 3 to 6 carbon atoms.
It is a C6 substituted unsaturated hydrocarbon group or an unsubstituted unsaturated hydrocarbon group, or a C3-C6 alicyclic saturated hydrocarbon group.

R ² R ¹ _3-n Si (NR ³ ₂ ) _n (10) wherein n is an integer of 1 to ³ and R ³ is the same or different and is a hydrogen atom or It is an unsubstituted saturated hydrocarbon group having 1 to 3 carbon atoms, R ¹ is the same or different and is a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, and carbon number. 1 to 6 substituted unsaturated hydrocarbon group or unsubstituted unsaturated hydrocarbon group, or carbon number 3
To 6 alicyclic saturated hydrocarbon groups, R ² has 3 carbon atoms
~ 6 substituted saturated hydrocarbon group or unsubstituted saturated hydrocarbon group, C3-6 substituted unsaturated hydrocarbon group or unsubstituted unsaturated hydrocarbon group, or C3-6 alicyclic saturated carbon group It is a hydrogen group.

(R ² R ¹ ₂ Si) ₂ NR ³ (11) However, R ³ is a hydrogen atom or an unsubstituted saturated hydrocarbon group having 1 to 3 carbon atoms, and R ¹ is the same or different. And a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsaturated unsaturated hydrocarbon group, or carbon Number 3
To 6 alicyclic saturated hydrocarbon groups, R ² has 3 carbon atoms
~ 6 substituted saturated hydrocarbon group or unsubstituted saturated hydrocarbon group, C3-6 substituted unsaturated hydrocarbon group or unsubstituted unsaturated hydrocarbon group, or C3-6 alicyclic saturated carbon group It is a hydrogen group.

[0032]

[Chemical 3] However, in the formula, m is an integer of 2 to 6, R ³ is a hydrogen atom or an unsubstituted saturated hydrocarbon group having 1 to 3 carbon atoms, and R ^{1 is}
Is a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or 3 carbon atoms. a 6 alicyclic saturated hydrocarbon group, R ² is a substituted saturated hydrocarbon group or a non-substituted saturated hydrocarbon group having 3 to 6 carbon atoms, a substituted 3 to 6 carbon atoms unsaturated hydrocarbon group or non It is a substituted unsaturated hydrocarbon group or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms.

With the structure of the second pattern forming method , the surface of the semiconductor substrate is formed on the surface of the above general formulas (9), (10), (1).
When the surface treatment is performed with the surface treatment agent containing the silane compound represented by 1) or 12), a hydrocarbon group layer is formed between the atoms having unpaired electrons present on the surface of the semiconductor substrate and the chemically amplified resist. Thus, the acid generated from the chemically amplified resist hardly reacts with the unpaired electrons on the surface of the semiconductor substrate, and the bottom shape of the resist pattern is significantly improved.

R ² in the above general formulas (9) to (12), that is, a substituted saturated hydrocarbon group having 3 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated carbon group having 3 to 6 carbon atoms. A hydrogen group or an unsubstituted unsaturated hydrocarbon group, or
When the surface treatment of the semiconductor substrate is performed with the surface treatment agent containing a silane compound having an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, the hydrophobicity of the semiconductor substrate surface is also improved. This is also a factor that makes it difficult for the acid generated from the chemically amplified resist to react with the unpaired electrons on the surface of the semiconductor substrate, thereby significantly improving the bottom shape of the resist pattern.

Further, a substituted saturated hydrocarbon group having 3 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group represented by the above general formula (10), (11) or (12) and a substituted unsaturated group having 3 to 6 carbon atoms. When a semiconductor substrate is surface-treated with a surface-treating agent containing a silane compound having a hydrocarbon group or an unsubstituted unsaturated hydrocarbon group, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, a by-product ( Ammonia, dialkylamine, etc.) needs to be removed to the outside of the system, but the surface treatment capacity for the semiconductor substrate is equivalent to that of the silane compound represented by the above general formula (9). A layer of hydrocarbon radicals is reliably formed between the atoms with the existing unpaired electrons and the chemically amplified resist.

FIG . 9A shows a contact angle which is a measure of hydrophobicity:
FIG. 9B is a diagram illustrating θ, and FIG. 9B is a diagram showing the relationship between the number of x and the contact angle θ in (Chemical Formula 4). Specifically, the surface treatment agent is bubbled with nitrogen gas. It is the result of spraying on the surface of the semiconductor substrate heated to 120 ° C. for 30 seconds after the heating.

[0037]

[Chemical 4]

As is apparent from FIG . 9 (b), when x is 2 or more, that is, when the number of carbon atoms in the hydrocarbon group is 3 or more, the contact angle: θ becomes significantly large, so that the hydrophobicity of the semiconductor substrate surface is reduced. improves.

Based on such knowledge , the silane represented by the above general formula (9), (10), (11) or (12) in which at least one of the hydrocarbon groups substituting on the Si atom has 3 or more carbon atoms. Compounds are preferred.

[0040] In the second pattern formation method, the chemically amplified resist in the second process, it is possible to use those containing an acid generator and a resin that becomes alkali-soluble by the action of an acid.

[0041] In the second pattern formation method, the chemically amplified resist in the second step, using an acid generator, an alkali-soluble resin, those containing a compound or resin becomes alkali-soluble by the action of an acid thing
You can

[0042] In the second pattern formation method, the chemically amplified resist in the second step, an acid generator, an alkali-soluble resin by the action of an acid which contains a compound or resin undergoes a crosslinking reaction Can be used
I can .

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

BEST MODE FOR CARRYING OUT THE INVENTION (First Reference Mode) The first reference mode realizes the above-described first invention.

[0052] A pattern formation method according to a first referential embodiment of the present invention will be described with reference to FIGS.

FIG. 1 shows the process flow of the pattern forming method according to the first reference embodiment, and FIG. 2 shows the surface state of the semiconductor substrate when the surface treatment is performed with the surface treatment agent according to the first reference embodiment. FIG. 3 shows a schematic cross-sectional shape of a pattern formed on a semiconductor substrate surface-treated with the surface-treatment agent according to the first reference embodiment.

First, as shown in FIG. 2A, isopropenoxytrimethylsilane (hereinafter abbreviated as IPTMS) as a surface treatment agent is supplied to the surface of the semiconductor substrate 1 made of silicon (that is, IPTMS). Bubbling IPTMS with nitrogen gas and spraying it on the surface of the semiconductor substrate heated to 60 ° C. for 30 seconds) to make the surface of the semiconductor substrate 1 hydrophobic and improve the adhesion of the semiconductor substrate 1. By doing so, as shown in FIG. 2B, H of the OH group on the surface of the semiconductor substrate 1 is replaced with Si (CH ₃ ) ₃ (trimethylsilyl group), and (CH ₃ ) ₂ CO (acetone) is obtained.
Is generated.

Next, a chemically amplified resist is applied to the surface of the semiconductor substrate 1 and then exposed using a desired mask, and then PEB and development are sequentially performed to form a pattern.

When the pattern is formed as described above,
As shown in FIG. 3, the hardly soluble layer is not formed on the surface portion of the resist pattern 2. That is, FIG. 3 shows the semiconductor substrate 1
A positive chemically amplified resist (KRF K2G, manufactured by Japan Synthetic Rubber Co., Ltd.) was applied on the above to a film thickness of 0.7 μm, and then exposed by a KrF excimer laser stepper with NA: 0.5, and then PEB was applied. The cross-sectional shape of a 0.25 μm line-and-space pattern is shown when the development is carried out at a temperature of 100 ° C. for 90 seconds and the development is performed using a 2.38 wt% tetramethylammonium hydroxide aqueous solution.

As described above, according to the first reference mode,
Since IPTMS is used as the surface treatment agent, the surface of the semiconductor substrate 1 can be made hydrophobic without generating ammonia, so that it is possible to prevent the formation of the hardly soluble layer on the surface portion of the resist pattern and to stabilize the surface. The resist pattern shape can be obtained.

(Second Reference Embodiment) The second reference embodiment also realizes the above-described first invention.

[0059] A pattern formation method according to a second referential embodiment of the present invention will be described with reference to FIGS.

FIG. 4 shows the process flow of the pattern forming method according to the second reference embodiment, and FIG. 5 shows the surface state of the semiconductor substrate when the surface treatment is performed with the surface treatment agent according to the second reference embodiment. FIG. 6 shows a schematic cross-sectional shape of a pattern formed on a semiconductor substrate surface-treated with the surface-treating agent according to the second reference embodiment.

First, as shown in FIG. 5A, acetoxytrimethylsilane (hereinafter abbreviated as ATMS) as a surface treatment agent is applied to the surface of the semiconductor substrate 1 made of silicon.
Is supplied (that is, ATMS is bubbled with nitrogen gas, and 3 is applied to the surface of the semiconductor substrate heated to 60 ° C.).
After spraying for 0 seconds), the surface of the semiconductor substrate 1 is made hydrophobic to improve the adhesion of the semiconductor substrate 1. By doing so, as shown in FIG. 5B, H of the OH group on the surface of the semiconductor substrate 1 is changed to Si (CH ₃ ) ₃ (trimethylsilyl group).
To produce CH ₃ COOH (acetic acid).

Next, a chemically amplified resist is applied to the surface of the semiconductor substrate 1 and then exposed using a desired mask, and then PEB and development are sequentially performed to form a pattern.

When the pattern is formed as described above,
As shown in FIG. 6, the hardly soluble layer is not formed on the surface portion of the resist pattern 2. That is, FIG. 6 shows the semiconductor substrate 1
A positive chemically amplified resist (KRF K2G, manufactured by Japan Synthetic Rubber Co., Ltd.) was applied on the above to a film thickness of 0.7 μm, and then exposed by a KrF excimer laser stepper with NA: 0.5, and then PEB was applied. The cross-sectional shape of a 0.25 μm line-and-space pattern is shown when the development is carried out at a temperature of 100 ° C. for 90 seconds and the development is performed using a 2.38 wt% tetramethylammonium hydroxide aqueous solution.

As described above, according to the second reference mode,
Since ATMS is used as the surface treatment agent, the surface of the semiconductor substrate 1 can be made hydrophobic without generating ammonia, so that it is possible to prevent the formation of the hardly soluble layer on the surface portion of the resist pattern and to stabilize the surface. The resist pattern shape can be obtained.

As the surface treatment agent, in the first reference embodiment, one which produces acetone as a reaction decomposition product,
In the second reference embodiment, a reaction decomposition product that generates acetic acid and a substance that makes the surface of the semiconductor substrate hydrophobic are used as a substance that forms a trimethylsilyl group. Not limited. That is,
A surface treatment agent containing a silane compound represented by the following general formula (15) can be used.

R ¹ _4-n Si (OR) _n (15) where n is an integer of 1 to 3 and R is a carbon number of 1 to 6
A substituted saturated hydrocarbon group or an unsubstituted saturated hydrocarbon group,
A substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or a substituted alkylcarbonyl group having 1 to 6 carbon atoms or an unsubstituted alkylcarbonyl group, and R ¹ is the same or different. There, a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or a carbon number And 3 to 6 alicyclic saturated hydrocarbon groups.

As a first example of the silane compound represented by the general formula (15), a compound represented by the following general formula (16) can be mentioned.

[0068] R ¹ ₃ SiOR ...... (16) where the meaning of R and R ¹ are the above general formula (1
Same as 5).

The silane compound represented by the above general formula (16) has a single hydrolyzable group on the Si atom, and the semiconductor substrate is processed into a monomolecular film so that the in-plane uniformity is high. A film is obtained. Further, the silane compound represented by the general formula (16) is easily affected by the steric hindrance of the R ¹ substituent, and this property is reflected in the reaction rate (processing ability).

Specific examples of the silane compound represented by the above general formula (16) include compounds represented by (formula 5) and (formula 6).

[0071]

[Chemical 5]

[Chemical 6]

As a second example of the silane compound represented by the general formula (15), a compound represented by the following general formula (17) can be given.

R ¹ ₂ Si (OR) ₂ (17) However, the meanings of R and R ¹ are as shown in the general formula (1) above.
Same as 5).

The silane compound represented by the general formula (17) has high hydrolyzable groups when the number of hydrolyzable groups on the Si atom is two and the semiconductor substrate is processed into a laminated film.

Specific examples of the silane compound represented by the above general formula (17) include compounds represented by the chemical formula (7).

[0076]

[Chemical 7]

As a third example of the silane compound represented by the general formula (15), a compound represented by the following general formula (18) can be given.

R ¹ Si (OR) ₃ (18) However, as for the meaning of R and R ¹ , the above general formula (1)
Same as 5).

The silane compound represented by the above general formula (17) has three hydrolyzable groups on the Si atom and is processed into a laminated film on the semiconductor substrate. The reactive silane compound may be hydrolyzed by moisture in the air to form a gel, which may cause particle contamination depending on the treatment method.

Specific examples of the silane compound represented by the above general formula (18) include compounds represented by the chemical formula (8).

[0081]

[Chemical 8]

The first reference using the silane compounds represented by the above (Chemical formula 5), (Chemical formula 6), (Chemical formula 7) and (Chemical formula 8).
When an experiment similar to the mode of consideration was conducted, good results were obtained as shown in (Table 2), (Table 3) and (Table 4).

The silane compound represented by the general formula (16) is particularly stable in terms of material, and the silane compound represented by the general formula (1)
The silane compound represented by 8) is characterized by having a particularly high reactivity.

[0084]

[Table 2]

[Table 3]

[Table 4]

[0085] In the first and second reference embodiment, as chemically amplified resist, 2-component system chemically amplified positive resist (KRF comprising an acid generator and a resin that becomes alkali-soluble by the action of an acid K2G) was used,
Instead of this, a three-component chemically amplified positive resist containing an acid generator, an alkali-soluble resin, and a compound or resin that becomes alkali-soluble by the action of an acid may be used. As a two-component chemically amplified positive resist,
For example, TDUR-DP007 manufactured by Tokyo Ohka Co., Ltd. may be mentioned. As a three-component chemically amplified positive resist,
Examples include DX561 and DX981 manufactured by Hoechst.

Further, as the chemically amplified resist, a three-component chemically amplified negative resist containing an acid generator, an alkali-soluble resin, and a compound or resin that causes a crosslinking reaction by the action of acid may be used. Examples of the three-component chemically amplified negative resist include X-ray manufactured by Shipley Co., Ltd.
P-8843, SAL-601, etc. are mentioned. Even in such a chemically amplified negative resist, when an alkaline component is generated during the surface treatment, film depletion of the pattern occurs due to deactivation of the acid, which causes deterioration of the shape of the resist pattern,
According to the method of the present invention, it is possible to prevent deactivation of acid, so that it is possible to form a good pattern.

Since the chemically amplified resist is affected by the alkaline component regardless of its constitution or constituent components, the first and second reference embodiments are effective for all chemically amplified resists.

Hereinafter, examples of the constituent components of the above chemically amplified resist will be given, but the constituent components are not limited to the following.

<Two-component chemically amplified positive resist> Resin that becomes alkali-soluble by the action of acid: poly (t-
Butoxycarbonyloxystyrene-co-hydroxystyrene) Poly (t-butoxycarbonylmethyloxystyrene-co-
Hydroxystyrene) Poly (tetrahydropyranyloxystyrene-co-hydroxystyrene) Acid generator: onium salt, nitrobenzyl sulfonic acid ester compound <3-component chemically amplified positive resist> Alkali-soluble resin: polyvinylphenol , Polymethacrylic acid ○ Resin or compound that becomes alkali-soluble by the action of acid ... Poly (t-butoxycarbonyloxystyrene-co-hydroxystyrene) Poly (t-butoxycarbonylmethyloxystyrene-co-
Hydroxystyrene) Poly (tetrahydropyranyloxystyrene-co-hydroxystyrene)

[Chemical 9] ○ Acid generator …… Onium salt, nitrobenzyl sulfonate compound <Three-component chemically amplified negative resist> ○ Alkali-soluble resin …… Polyvinylphenol, polymethacrylic acid ○ Compound or resin that causes cross-linking reaction by the action of acid ......
Melamine compound, melamine resin-acid generator ... Onium salt, nitrobenzyl sulfonate compound (Third Embodiment) The third embodiment realizes the above-described second invention.

The pattern forming method according to the third embodiment of the present invention will be described below with reference to FIGS. 7 and 8.

FIG. 7 shows the surface condition of the semiconductor substrate when the surface treatment with the surface treatment agent of the third embodiment is performed, and FIG. 8 shows the surface treatment with the surface treatment agent according to the third embodiment. The schematic cross-sectional shape of the pattern formed on the semiconductor substrate is shown.

First, as shown in FIG. 7A, BPSG
Isopropenoxy-n-hexyldimethylsilane (hereinafter, referred to as I
Abbreviated as PHDMS. ) Is supplied (ie, IPH
Bubbling DMS with nitrogen gas and spraying on the surface of the semiconductor substrate heated to 120 ° C. for 30 seconds) to form a hydrocarbon-based layer on the surface of the semiconductor substrate 5.
The hydrophobicity of the surface of the semiconductor substrate 5 is improved. This also improves the adhesion of the semiconductor substrate 5. As shown in FIG. 7B, H of the OH group on the surface of the semiconductor substrate 5 is Si (C
H ₃ ) ₂ (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) is substituted to produce (CH ₃ ) ₂ CO (acetone).

Next, a chemically amplified resist is applied to the surface of the semiconductor substrate 5 to form a resist film, and then the resist film is exposed using a desired mask, and then PE is applied.
Pattern formation is performed by sequentially performing B and development.

When the pattern is formed as described above,
As shown in FIG. 8, the bottom portion is not formed on the surface portion of the resist pattern 6. That is, FIG. 8 shows the semiconductor substrate 5
A positive chemically amplified resist (KRF K2G, manufactured by Japan Synthetic Rubber Co., Ltd.) was applied on the above to a film thickness of 0.7 μm, and then exposed by a KrF excimer laser stepper with NA: 0.5, and then PEB was applied. The cross-sectional shape of a 0.25 μm line-and-space pattern is shown when the development is carried out at a temperature of 100 ° C. for 90 seconds and the development is performed using a 2.38 wt% tetramethylammonium hydroxide aqueous solution.

As described above, according to the third embodiment,
Since IPHDMS is used as the surface treatment agent, a hydrocarbon group layer can be formed on the surface of the semiconductor substrate 5 and the hydrophobicity of the surface of the semiconductor substrate 5 can be improved. It is possible to prevent the formation of the pulling portion and obtain a stable resist pattern shape.

In the third embodiment, since the surface treatment agent which does not generate ammonia is used as the reaction decomposition product, the effect of preventing the formation of the hardly soluble layer on the surface portion of the resist pattern 6 can be obtained. To be On the other hand, when a resist pattern made of a chemically amplified resist is formed after the surface treatment using a surface treatment agent that generates ammonia as a reaction decomposition product, a poorly soluble layer is formed on the surface portion of the resist pattern 6. However, it is possible to prevent the bottom portion from being formed at the base of the resist pattern 6.

As the surface treatment agent capable of forming a hydrocarbon group layer on the surface of the semiconductor substrate and rendering the surface of the semiconductor substrate hydrophobic, it is preferable to use one containing a silane compound represented by the following general formula (19). it can.

R ² R ¹ _3-n Si (OR) _n (19) where n is an integer of 1 to 3 and R is a carbon number of 1 to 6
A substituted saturated hydrocarbon group or an unsubstituted saturated hydrocarbon group,
A substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or a substituted alkylcarbonyl group having 1 to 6 carbon atoms or an unsubstituted alkylcarbonyl group, and R ¹ is the same or different. There, a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or a carbon number It is an alicyclic saturated hydrocarbon group having 3 to 6 and R ₂ is a substituted saturated hydrocarbon group having 3 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, having 3 to 6 carbon atoms.
It is a C6 substituted unsaturated hydrocarbon group or an unsubstituted unsaturated hydrocarbon group, or a C3-C6 alicyclic saturated hydrocarbon group.

Examples of the silane compound represented by the above general formula (19) include those represented by the following general formula (20), (21) or (22).

R ² R ¹ ₂ SiOR (20) R ² R ¹ Si (OR) ₂ (21) R ² Si (OR) ₃ (22) (where R is 1 to 1 carbon atoms) 6-substituted saturated hydrocarbon group or unsubstituted saturated hydrocarbon group, C 1-6 substituted unsaturated hydrocarbon group or unsubstituted unsaturated hydrocarbon group, or C 1-6 substituted alkylcarbonyl group or non- A substituted alkylcarbonyl group, R ¹ is the same or different and is a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated carbon group having 1 to 6 carbon atoms A hydrogen group or an unsubstituted unsaturated hydrocarbon group, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, R ²
Is a substituted saturated hydrocarbon group having 3 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 3 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or 3 to 6 carbon atoms.
Is an alicyclic saturated hydrocarbon group. ) Further, as the surface treatment agent capable of forming a hydrocarbon group layer on the surface of the semiconductor substrate and rendering the surface of the semiconductor substrate hydrophobic, it is preferable to use one containing a silane compound represented by the following general formula (23). it can.

R ² R ¹ _3-n Si (NR ³ ₂ ) _n (23) wherein n is an integer of 1 to ³ and R ³ is the same or different and is a hydrogen atom or It is an unsubstituted saturated hydrocarbon group having 1 to 3 carbon atoms, R ¹ is the same or different and is a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, and carbon number. 1 to 6 substituted unsaturated hydrocarbon group or unsubstituted unsaturated hydrocarbon group, or carbon number 3
To 6 alicyclic saturated hydrocarbon groups, R ₂ has 3 carbon atoms
~ 6 substituted saturated hydrocarbon group or unsubstituted saturated hydrocarbon group, C3-6 substituted unsaturated hydrocarbon group or unsubstituted unsaturated hydrocarbon group, or C3-6 alicyclic saturated carbon group It is a hydrogen group.

As a first example of the silane compound represented by the general formula (23), a silane compound represented by the following general formula (24) can be used.

R ² R ¹ ₂ SiNR ³ ₂ (24) However, the meanings of R ¹ , R ² and R ³ are the same as in the general formula (23).

The silane compound represented by the general formula (24) has a single hydrolyzable group on the Si atom, the semiconductor substrate is processed into a monomolecular film, and the in-plane uniformity is high. A film is obtained. Further, the silane compound represented by the general formula (24) is easily affected by the steric hindrance of the R ¹ or R ² substituent, and this property is reflected in the reaction rate (processing ability).

As a second example of the silane compound represented by the general formula (23), a silane compound represented by the following general formula (25) can be used.

R ² R ¹ Si (NR ³ ₂ ) ₂ (25) However, the meanings of R ¹ , R ² and R ³ are the same as in the general formula (23).

The silane compound represented by the general formula (25) has two hydrolyzable groups on the Si atom, is processed into a laminated film on the semiconductor substrate, and has a high processing ability.

As a third example of the silane compound represented by the general formula (23), a silane compound represented by the following general formula (26) can be used.

R ² Si (NR ³ ₂ ) ₃ (26) However, regarding the meaning of R ² and R ³ , the above general formula (2
Same as 3).

The silane compound represented by the general formula (23) has three hydrolyzable groups on the Si atom and is processed into a laminated film on the semiconductor substrate. The reactive silane compound may be hydrolyzed by moisture in the air to form a gel, which may cause particle contamination depending on the treatment method.

Further, as the surface treatment agent capable of forming a hydrocarbon group layer on the surface of the semiconductor substrate and rendering the surface of the semiconductor substrate hydrophobic, one containing a silane compound represented by the following general formula (27) is used. be able to.

[0112] _{^{(R 2 R 1 2 Si)}} 2 NR 3 ...... (27) where, R ³ is a hydrogen atom or a non-substituted saturated hydrocarbon group having 1 to 3 carbon atoms, R ¹ is same or different And a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsaturated unsaturated hydrocarbon group, or carbon Number 3
To 6 alicyclic saturated hydrocarbon groups, R ² has 3 carbon atoms
~ 6 substituted saturated hydrocarbon group or unsubstituted saturated hydrocarbon group, C3-6 substituted unsaturated hydrocarbon group or unsubstituted unsaturated hydrocarbon group, or C3-6 alicyclic saturated carbon group It is a hydrogen group. The silane compound represented by the general formula (27) has a single hydrolyzable group on the Si atom, and the semiconductor substrate is processed into a monomolecular film to obtain a film having high in-plane uniformity. To be Further, the silane compound represented by the general formula (27) is easily affected by the steric hindrance of the R ¹ or R ² substituent,
This property is reflected in the reaction rate (processing capacity).

Further, as the surface treatment agent capable of forming a hydrocarbon group layer on the surface of the semiconductor substrate and rendering the surface of the semiconductor substrate hydrophobic, one containing a silane compound represented by the following general formula (28) is used. be able to.

[0114]

[Chemical 10] (In the formula, m is an integer of 2 to 6, R ³ is a hydrogen atom or an unsubstituted saturated hydrocarbon group having 1 to 3 carbon atoms, R ^3
1 is a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or
It is an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, and R ² is
Substituted saturated hydrocarbon group or unsubstituted hydrocarbon group having 3 to 6 carbon atoms, substituted unsaturated hydrocarbon group or unsubstituted unsaturated hydrocarbon group having 3 to 6 carbon atoms, or alicyclic ring having 3 to 6 carbon atoms Formula is a saturated hydrocarbon group. The silane compound represented by the general formula (28) has two hydrolyzable groups on the Si atom, is processed into a laminated film on the semiconductor substrate, and has high processing ability. Further, as the silane compound represented by the general formula (28),
It is preferable that m is 3 or 4.

The above general formulas (19), (23) and (27)
Specific examples of the silane compounds represented by (28) and (28) include those represented by (Chemical Formula 11).

[0116]

[Chemical 11]

An experiment similar to that of the third embodiment was conducted using the silane compound shown in (Chemical Formula 11).
Good results were obtained as shown in.

[0118]

[Table 5]

The silane compounds represented by the general formulas (24) and (27) are particularly stable in terms of materials, and the silane compound represented by the general formula (26) is particularly reactive. It has features.

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

According to the first pattern forming method of the present invention, the surface of the semiconductor substrate is treated with the surface treating agent containing the silane compound represented by the general formula (1). Since no alkali component is generated on the surface of the semiconductor substrate, the acid generated from the chemically amplified resist by exposure does not react with the alkali component. Therefore, it is possible to obtain a stable resist pattern shape in which the hardly soluble layer is not formed on the surface.

Further, conventionally, during exposure from exposure to PEB, the acid generated in the chemically amplified resist by exposure generates an alkali component such as HMDS. However, according to the pattern forming method of the invention of claim 1, there is a problem in that the insolubilized layer is formed on the surface of the resist pattern. Since the alkali component does not exist on the surface of the amplified resist, the acid generated in the chemically amplified resist by exposure is not deactivated, and as a result, a stable resist pattern shape in which the surface hardly soluble layer is not formed can be obtained it can.

In the first pattern forming method, as the chemically amplified resist, one having an acid generator and a resin which becomes alkali-soluble by the action of acid is used, or
A generator having an alkali-soluble resin and a compound or resin which becomes alkali-soluble by the action of an acid was used.
Use an acid generator , an alkali-soluble resin, and a compound or resin that causes a cross-linking reaction by the action of acid .
Optimum it is possible to, respectively, two-component system chemically amplified positive resist, 3 chemically amplified positive resist component system,
It is possible to prevent deactivation of acid when a three-component chemically amplified negative resist is used.

According to the second pattern forming method of the present invention, the surface of the semiconductor substrate is covered by the general formulas (2), (3),
Since the surface treatment is performed with the surface treatment agent containing the silane compound represented by (4) or (5), a hydrocarbon group is present between the atom having an unpaired electron present on the surface of the semiconductor substrate and the chemically amplified resist. Spacing by layers is formed, and also
The hydrophobicity of the surface of the semiconductor substrate is improved. From this,
The acid generated from the chemically amplified resist and the unpaired electrons on the surface of the semiconductor substrate become difficult to react, the deactivation of the acid generated from the chemically amplified resist is prevented, and the bottom of the resist pattern is formed. Can be prevented.

In the second pattern forming method, as the chemically amplified resist, one having an acid generator and a resin which becomes alkali-soluble by the action of acid is used, or
A generator having an alkali-soluble resin and a compound or resin which becomes alkali-soluble by the action of an acid was used.
Use an acid generator , an alkali-soluble resin, and a compound or resin that causes a cross-linking reaction by the action of acid .
Optimum it is possible to, respectively, two-component system chemically amplified positive resist, 3 chemically amplified positive resist component system,
It is possible to prevent deactivation of acid when a three-component chemically amplified negative resist is used.

[0145]

[0146]

[0147]

[Brief description of drawings]

FIG. 1 is a flowchart illustrating a process of a pattern forming method according to a first reference embodiment of the present invention.

FIG. 2 is a schematic diagram showing a surface state of a semiconductor substrate when IPTMS is supplied in the pattern forming method according to the first reference embodiment.

FIG. 3 is a schematic view showing a cross-sectional shape of a resist pattern formed by the pattern forming method according to the first reference embodiment.

FIG. 4 is a flowchart illustrating a process of a pattern forming method according to a second reference embodiment of the present invention.

FIG. 5 is a schematic view showing a surface state of a semiconductor substrate when ATMS is supplied in the pattern forming method according to the second reference embodiment.

FIG. 6 is a schematic view showing a cross-sectional shape of a resist pattern formed by the pattern forming method according to the second reference embodiment.

FIG. 7 is a schematic diagram showing a surface state of a semiconductor substrate when IPHDMS is supplied in a pattern forming method according to a third embodiment of the present invention.

FIG. 8 is a schematic view showing a cross-sectional shape of a resist pattern formed by the pattern forming method according to the third embodiment.

FIG. 9A is a scale showing the hydrophobicity of the surface of a semiconductor substrate.
And (b) are equations (Formula 4).
7 is a characteristic diagram showing the relationship between the number of x and the contact angle in FIG.

FIG. 10 is a professional of a pattern forming method according to a first conventional example.
It is a flowchart explaining a process.

FIG. 11 shows a pattern forming method according to a first conventional example.
The surface condition of the semiconductor substrate when HMDS is supplied.
It is a schematic diagram which shows.

FIG. 12 shows a pattern forming method according to a first conventional example.
It is a schematic diagram which shows the cross-sectional shape of the formed resist pattern.
It

FIG. 13 shows a pattern forming method according to a first conventional example.
It is a schematic diagram which shows the cross-sectional shape of the formed resist pattern.
It

FIG. 14: Trimethylsilanol, a degradation product of HMDS
Between the ambient concentration of ammonia and the ambient concentration of ammonia
It is a figure which shows a relationship.

[Explanation of symbols]

1 Semiconductor substrate made of silicon 2 resist pattern 3 Insoluble layer 4 Hem 5 Semiconductor substrate made of BPSG 6 resist pattern 7 Resist pattern

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akiko Katsuyama 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. Chemical Industry Co., Ltd. Synthesis Technology Laboratory (56) Reference JP-A-7-120919 (JP, A) JP-A-7-335603 (JP, A) JP-A-11-511900 (JP, A) International Publication 96 / 15861 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) H01L 21/027 G03F ^7/ 00-7/42

Claims (8)

(57) [Claims] 1. The surface of a semiconductor substrate is represented by the following general formula (1):
A first step of performing a surface treatment with a surface treatment agent containing a silane compound, and a second step of applying a chemically amplified resist to the surface of the surface-treated semiconductor substrate to form a resist film, A third step of forming a resist pattern by exposing the resist film using a mask having a desired pattern shape and then developing the resist film. R ¹ _4-n Si (OR) _n (1) (wherein n is an integer of 1 to 3 and R is a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group) A substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or a substituted alkylcarbonyl group having 1 to 6 carbon atoms or an unsubstituted alkylcarbonyl group, and R ¹ is the same or different. And a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or carbon It is an alicyclic saturated hydrocarbon group having a number of 3 to 6, and when n is 1, at least one of R ¹ is a substituted saturated hydrocarbon group having a carbon number of 2 to 6 or an unsubstituted saturated hydrocarbon group. Hydrogen group, or substituted unsaturated hydrocarbon group having 2 to 6 carbon atoms or non- A switching is not saturated hydrocarbon group, when n is 2 and R is a methyl group, at least one of R ¹ is an unsubstituted saturated carbon of 2 to 6 carbon atoms
A hydrogenated group , or a substituted unsaturated hydrocarbon group having 2 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, and when n is 3, R ¹ is an unsubstituted hydrocarbon group having 2 to 6 carbon atoms.
Saturated hydrocarbon group, substituted unsaturated hydrocarbon group having 2 to 6 carbon atoms
Or an unsubstituted unsaturated hydrocarbon group, or a C3-6
It is an alicyclic saturated hydrocarbon group. ) 2. The pattern forming method according to claim 1, wherein the chemically amplified resist in the second step contains an acid generator and a resin which becomes alkali-soluble by the action of acid. 3. The chemically amplified resist in the second step contains an acid generator, an alkali-soluble resin, and a compound or resin which becomes alkali-soluble by the action of an acid. The method for forming a pattern according to. 4. The chemically amplified resist in the second step contains an acid generator, an alkali-soluble resin, and a compound or resin that causes a crosslinking reaction by the action of an acid. The method for forming a pattern according to. 5. A first step of surface-treating a surface of a semiconductor substrate with a surface-treating agent containing a silane compound represented by the following general formula (2), (3), (4) or (5): The second step of forming a resist film by applying a chemically amplified resist on the surface of the surface-treated semiconductor substrate, and exposing the resist film with a mask having a desired pattern shape, followed by development. And a third step of forming a resist pattern. R ² R ¹ _3-n Si (OR) _n (2) (In the formula, n is an integer of 1 to 3, and R is a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group. A hydrogen group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or a substituted alkylcarbonyl group or an unsubstituted alkylcarbonyl group having 1 to 6 carbon atoms, and R ¹ is the same type. Or a different type, a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or , A C 3-6 alicyclic saturated hydrocarbon group, R ² is a C 3-6 substituted saturated hydrocarbon group or an unsubstituted saturated hydrocarbon group, C 3-6 substituted unsaturated carbon group Hydrogen group or unsubstituted unsaturated hydrocarbon group, or C3-6 A cyclic saturated hydrocarbon group, when n is 2, R ¹ is unsubstituted 1 to 6 carbon atoms
Saturated hydrocarbon group, substituted unsaturated hydrocarbon group having 3 to 6 carbon atoms
Or an unsubstituted unsaturated hydrocarbon group, or a C3-6
It is an alicyclic saturated hydrocarbon group, and R ² has 3 to 6 carbon atoms.
Unsubstituted saturated hydrocarbon group, substituted unsaturated carbon group having 3 to 6 carbon atoms
Hydrogen group or unsubstituted unsaturated hydrocarbon group, or carbon number 3
To 6 alicyclic saturated hydrocarbon group, and when n is 3, R ² is an unsubstituted C 3 to C 6 group.
Saturated hydrocarbon group, substituted unsaturated hydrocarbon group having 3 to 6 carbon atoms
Or an unsubstituted unsaturated hydrocarbon group, or a C3-6
It is an alicyclic saturated hydrocarbon group. ) R ² R ¹ _3-n Si (NR ³ ₂ ) _n (3) (wherein, n is an integer of 1 to ³ , R ³ is the same or different, and is a hydrogen atom or a carbon atom. It is an unsubstituted saturated hydrocarbon group having 1 to 3 carbon atoms, R ¹ is the same or different, and is a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, 1 carbon atom To a substituted unsaturated hydrocarbon group or an unsubstituted unsaturated hydrocarbon group having 6 to 6 carbon atoms, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, and R ² represents a substituted saturated hydrocarbon having 3 to 6 carbon atoms. A group or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 3 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms) ( _{^{R 2 R 1 2 Si) 2}} NR 3 ...... (4) ( where, R ³ is a hydrogen atom or a non-substituted saturated hydrocarbon group having 1 to 3 carbon atoms R ¹ is the same or different and is a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted group An unsaturated hydrocarbon group or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, R ² represents a substituted saturated hydrocarbon group having 3 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, 3 carbon atoms To a substituted unsaturated hydrocarbon group or an unsubstituted unsaturated hydrocarbon group having 6 to 6 carbon atoms, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms. (However, in the formula, m is an integer of 2 to 6, R ³ is a hydrogen atom or an unsubstituted saturated hydrocarbon group having 1 to 3 carbon atoms, R ¹ is a hydrogen atom, and 1 to 6 carbon atoms. A substituted saturated hydrocarbon group or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms And R ² is a substituted saturated hydrocarbon group having 3 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsaturated hydrocarbon group having 3 to 6 carbon atoms or an unsubstituted unsaturated hydrocarbon group, or It is an alicyclic saturated hydrocarbon group of 3 to 6.) 6. The pattern forming method according to claim 5, wherein the chemically amplified resist in the second step contains an acid generator and a resin which becomes alkali-soluble by the action of acid. 7. The chemically amplified resist in the second step contains an acid generator, an alkali-soluble resin, and a compound or resin which becomes alkali-soluble by the action of an acid. The described pattern forming method. 8. The chemically amplified resist in the second step contains an acid generator, an alkali-soluble resin, and a compound or resin that causes a crosslinking reaction by the action of an acid. The method for forming a pattern according to.