JP3387807B2 - Semiconductor device manufacturing method and semiconductor device manufacturing apparatus - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device manufacturing method and manufacturing apparatus, and more particularly to a semiconductor device manufacturing method and manufacturing apparatus in which a resist pattern is formed on a semiconductor substrate.

[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 measure for enabling fine processing in a lithographic 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 chemistry utilizing generation of acid is used. A technique for forming a resist pattern composed of an amplification type resist is being developed (“Coloring Material”, Vol. 67 No. 7, pp.
446-455 (1994)).

In addition, since a semiconductor device manufacturing process always includes a pattern forming step with a low degree of miniaturization, a resist pattern made of a conventional non-chemically amplified resist is also formed.

A pattern forming process using a chemically amplified resist and a pattern forming process using a non-chemically amplified resist in a conventional method for manufacturing a semiconductor device will be described below with reference to FIGS.

First, referring to FIGS. 10 and 11,
A pattern forming process using a chemically amplified resist will be described.

FIG. 10 shows a process flow of a step of forming a resist pattern made of a chemically amplified resist, and FIGS. 11A and 11B show a semiconductor formed in the step of forming a resist pattern made of a chemically amplified resist. The surface condition of the substrate is shown.

As shown in FIG. 11A, hexamethyldisilazane (hereinafter abbreviated as HMDS) as a surface treatment agent is supplied to the surface of the semiconductor substrate 1 made of silicon to supply the surface of the semiconductor substrate 1. Is made hydrophobic, and the semiconductor substrate 1
To improve the surface adhesion. This surface treatment is performed by bubbling liquid HMDS with nitrogen gas and then at 60 ° C.
It is performed by spraying HMDS for 30 seconds on the surface of the semiconductor substrate 1 which is heated to the above. If you do this,
As shown in FIG. 1 (b), H of the OH group on the surface of the semiconductor substrate 1 is replaced with Si (CH ₃ ) ₃ (trimethylsilyl group), the surface of the semiconductor substrate 1 becomes hydrophobic, and The adhesion is improved and NH ₃ (ammonia) is produced.

Next, 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 Abbreviated as PEB.)
And development are sequentially performed to form a resist pattern.

Next, referring to FIGS. 12 and 13,
A pattern forming method using a non-chemically amplified resist will be described.

FIG. 12 shows a process flow of a step of forming a resist pattern made of a non-chemically amplified resist,
FIG. 13 shows the surface state of the semiconductor substrate formed in the step of forming a resist pattern made of a non-chemically amplified resist.

First, as shown in FIG. 13A, H as a surface treatment agent is applied to the surface of the semiconductor substrate 1 made of silicon.
MDS is supplied to make the surface of the semiconductor substrate 1 hydrophobic so that the adhesion of the semiconductor substrate 1 is improved. This process
After bubbling liquid HMDS with nitrogen gas,
HMDS is applied to the surface of the semiconductor substrate 1 heated to 60 ° C.
It is performed by spraying for 0 seconds. By doing so, as shown in FIG. 13B, H of the OH group on the surface of the semiconductor substrate 1 becomes 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 non-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 P
EB and development are sequentially performed to form a resist pattern.

[0014]

FIG. 14 shows a schematic cross-sectional shape of a resist pattern 6 made of a chemically amplified resist formed in the former step. The surface of the resist pattern 6 has a poorly soluble layer 7 formed thereon. Are formed. Thus, when the hardly-solubilized layer 7 is formed on the surface of the resist pattern 6, the dimensional fluctuation of the resist pattern 6 and the etching failure in the subsequent process are caused, which causes a decrease in the yield of semiconductor devices. On the other hand, in the resist pattern made of the non-chemically amplified resist, since the hardly soluble layer is not formed on the surface portion, no particular problem occurs.

As described above, as a factor for forming the hardly-solubilized layer 7 on the surface portion of the resist pattern 6 made of the chemically amplified resist, an alkaline component can be mentioned. That is, when an alkaline component is present on the surface of the resist pattern 6, the acid generated by exposure is deactivated to form the hardly soluble layer 7, and the surface portion of the resist pattern 6 has a T-top shape. This means that the pattern may not be resolved if the alkaline component is large (SA
MacDonald et al., Proc.SPIE, vol.1446, p.2 (1991).)
It can be understood from the fact that the insoluble layer is not formed on the surface portion of the resist pattern made of the non-chemically amplified resist.

The present inventors analyzed impurities in the environment in a clean room in order to investigate the cause of generation of the ammonia component as an alkaline component which adversely affects the chemically amplified resist, and as shown in FIG. It was found that there is a positive correlation between the environmental concentration of trimethylsilanol, which is a decomposition product of HMDS, and the environmental concentration of ammonia. From this, the alkaline component that adversely affects the shape of the chemically amplified resist pattern is H which is the surface treatment agent for the semiconductor substrate.
It is speculated that MDS has a cause.

Therefore, when a resist pattern made of a chemically amplified resist is formed on a semiconductor substrate surface-treated with a surface treatment agent which does not generate an alkaline component, the resist pattern made of the chemically amplified resist is formed by a conventional method. The amount of the hardly soluble layer was smaller than that in the case of forming, but the hardly soluble layer was still generated.

In view of the above, it is an object of the present invention to prevent a hardly soluble layer from being formed on the surface of a resist pattern made of a chemically amplified resist.

[0019]

By the way, it is presumed that the alkali component which has a bad influence on the resist pattern made of the chemically amplified resist is caused by HMDS, but in the same clean room, the non-chemically amplified resist is used. When HMDS is used as a surface treatment agent in the surface treatment step when forming a resist pattern, the HMDS
It is considered that the alkaline component generated from S spreads in the clean room, and the hardly soluble layer is formed on the surface portion of the resist pattern made of the chemically amplified resist.

The present invention has been made based on the above findings, and not only the surface treatment step at the time of forming a resist film made of a chemically amplified resist, but also a resist film made of a non-chemically amplified resist. A surface treatment agent that does not generate an alkaline component is also used in the surface treatment step during formation.

In the method of manufacturing a semiconductor device according to the present invention, the surface of a semiconductor substrate is surface-treated with a surface-treating agent containing a silane compound represented by the following general formula (1) in a clean room and then surface-treated. A first resist film forming step of forming a first resist film by coating a chemically amplified resist on the surface of the semiconductor substrate, and forming a desired pattern shape for the first resist film in the clean room. A first exposure step of performing exposure using a mask provided therein; a first development step of developing the exposed first resist film to form a first resist pattern in the clean room; In the above, after the surface treatment of the surface of the semiconductor substrate with a surface treatment agent containing a silane compound represented by the following general formula (1), the surface treatment is performed. A second resist film forming step of forming a second resist film by applying a non-chemically amplified resist on the surface of the formed semiconductor substrate, and a desired pattern for the second resist film in the clean room. A second exposure step of exposing using a mask having a shape; and a second development step of developing the exposed second resist film in the clean room to form a second resist pattern. ing.

R ¹ _4-n Si (OR) _n (1) (wherein n is an integer of 1 to 3 and R is a carbon number of 1 to 1)
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 It is a hydrogen group or an unsubstituted unsaturated hydrocarbon group, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms. According to the method for manufacturing a semiconductor device of the present invention, the above general formula (1) is used in both the first resist film forming step and the second resist film forming step performed in the same clean room. Since the surface treatment is performed with the surface treatment agent containing the silane compound, no ammonia component is generated in both of the above steps, and therefore, no alkali component is present in the clean room in which the method for manufacturing a semiconductor device according to the present invention is performed. In this case, the surface treatment agent used in the first resist film forming step and the surface treatment agent used in the second resist film forming step may be the same or different.

In the method of manufacturing a semiconductor device according to the present invention, the silane compound is more preferably represented by the following general formula (2).

[0024]

[Chemical 3]

(Wherein R ¹ , R ² and R ³ are the same or different and are a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, and 1 to 6 carbon atoms. A substituted unsaturated hydrocarbon group or an unsubstituted unsaturated hydrocarbon group, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, wherein R ⁴ , R ⁵ and R ⁶ are the same or different. , 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, having 3 to 6 carbon atoms Alicyclic saturated hydrocarbon group or OR ⁷ (R ⁷ 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 having 1 to 6 carbon atoms) A group or an unsubstituted unsaturated hydrocarbon group, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms. It is.)

Since the silane compound represented by the general formula (2) has a low energy level of the electrophilic orbit, the reactivity between the trimethylsilyl group of the silane compound and the OH group on the substrate becomes high. Therefore, as described above, the silicon atom constituting the silane compound having a carbonyl group reacts with the silanol group, which is a compound having an active hydrogen atom, at an extremely high reaction rate.

For example, as the silane compound represented by the general formula (2), 4-trimethylsiloxy-3-pentene-
When 2-one was mixed with 0.5 equivalent of cyclohexanol and the reaction rate was measured, it showed an extremely high reactivity of 100% in 1 hour. By the way, when the same measurement was performed using hexamethyldisilazane known as a conventional surface treatment agent, the reactivity was as low as 43.9% in 24 hours.

In the method of manufacturing a semiconductor device according to the present invention, the chemically amplified resist may contain an acid generator and a resin which becomes alkali-soluble by the action of acid.

The chemically amplified resist may contain an acid generator, an alkali-soluble resin, and a compound or resin which becomes alkali-soluble by the action of acid.

The above chemically amplified resist may contain an acid generator, an alkali-soluble resin, and a compound or resin that causes a crosslinking reaction by the action of acid.

Further, the non-chemically amplified resist may contain a naphthoquinonediazide compound and a novolac resin.

The semiconductor device manufacturing apparatus according to the present invention is provided in a clean room, and after the surface of the semiconductor substrate is surface-treated with a surface treatment agent containing a silane compound represented by the following general formula (1): A first coating device for forming a first resist film by coating a chemically amplified resist on the surface of a surface-treated semiconductor substrate; and a first coating device provided in the clean room for the first resist film. And a first exposure device that exposes using a mask having a desired pattern shape, and is provided in the clean room. The exposed first resist film is developed to form the first resist pattern. And a surface treatment agent containing a silane compound represented by the following general formula (1). A second coating device for forming a second resist film by coating a non-chemically amplified resist on the surface of the surface-treated semiconductor substrate after the treatment, and the second coating device provided in the clean room. A second exposure device that exposes the second resist film using a mask having a desired pattern shape, and a second exposure device that is provided in the clean room and develops the exposed second resist film.
And a second developing device for forming the resist pattern.

R ¹ _4-n Si (OR) _n (1) (where n is an integer of 1 to 3 and R is a carbon number of 1 to 1)
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 It is a hydrogen group or an unsubstituted unsaturated hydrocarbon group, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms. According to the semiconductor device manufacturing apparatus of the present invention, both the first coating device and the second coating device provided in the same clean room contain the silane compound represented by the general formula (1). Since the surface treatment is performed by the surface treatment agent, no ammonia component is generated in both of the above-mentioned devices, so that there is no alkali component in the clean room in which the semiconductor device manufacturing apparatus according to the present invention is installed.
The first coating device and the second coating device may be the same device or different devices.

In the semiconductor device manufacturing apparatus according to the present invention, the silane compound is more preferably represented by the following general formula (2).

[0035]

[Chemical 4]

(Wherein R ¹ , R ² and R ³ are the same or different and are a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, 1 to 6 carbon atoms). A substituted unsaturated hydrocarbon group or an unsubstituted unsaturated hydrocarbon group, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, wherein R ⁴ , R ⁵ and R ⁶ are the same or different. , 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, having 3 to 6 carbon atoms Alicyclic saturated hydrocarbon group or OR ⁷ (R ⁷ 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 having 1 to 6 carbon atoms) A group or an unsubstituted unsaturated hydrocarbon group, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms. It is.)

When the surface treatment is carried out using the silane compound represented by the general formula (2), the reaction rate between the Si atom and the silanol group existing on the semiconductor substrate becomes faster as described above.

In the apparatus for manufacturing a semiconductor device according to the present invention, the chemically amplified resist may contain an acid generator and a resin which becomes alkali-soluble by the action of acid.

Further, the chemically amplified resist may contain an acid generator, an alkali-soluble resin, and a compound or resin which becomes alkali-soluble by the action of acid.

Further, the chemically amplified resist may contain an acid generator, an alkali-soluble resin, and a compound or resin which causes a crosslinking reaction by the action of acid.

Further, the non-chemically amplified resist may contain a naphthoquinone diazide compound and a novolac resin.

[0042]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows a schematic plan structure of a clean room in which a semiconductor device manufacturing apparatus according to the present invention is arranged. In the clean room, the surface of the semiconductor substrate is surface-treated with a surface treatment agent containing a silane compound, and then a chemically amplified resist is applied to the surface of the semiconductor substrate to form a first resist film. Coating apparatus, a first exposure apparatus for pattern-exposing the first resist film formed by the first coating apparatus, and a first exposure apparatus for developing the first resist film exposed by the first exposure apparatus. No. 1 developing device and a surface treatment of the surface of a semiconductor substrate with a surface treatment agent containing a silane compound, and then a non-chemically amplified resist is applied to the surface of the semiconductor substrate to form a second resist film. Second coating device, a second exposure device that performs pattern exposure on the second resist film formed by the second coating device, and develops the second resist film exposed by the second exposure device. First A developing device is provided for. The first coating device and the second coating device may be the same device or different devices, but here, as the same device, manufactured by Tokyo Electron Ltd .: Mark 8
Was used. In the clean room, the first and second coating devices, the first and second exposure devices, and the first and second exposure devices are provided.
In addition to the second developing device and a large number of processing devices, they are not shown.

(First Reference Embodiment) Referring to FIGS. 2 to 4, the first half step of the method for manufacturing a semiconductor device according to the first reference embodiment of the present invention, which is performed using the above-described semiconductor device manufacturing apparatus, will be described below. While explaining. The first half of the process is a process of forming a first resist pattern made of a chemically amplified resist by using the first coating device, the first exposure device, and the first developing device.

FIG. 2 shows a flow of steps for forming a resist pattern made of a chemically amplified resist, which is shown in FIG.
(B) shows the surface state of the semiconductor substrate when subjected to surface treatment with a surface treatment agent according to the first referential embodiment, FIG. 4
Shows a schematic cross-sectional shape of a resist pattern made of a chemically amplified resist formed on a semiconductor substrate surface-treated with the surface-treating agent according to the first reference embodiment.

First, by the first coating device, as shown in FIG.
4, 4-trimethylsiloxy-3-penten-2-one as a surface treatment agent is supplied to the surface of the semiconductor substrate 1 made of silicon (that is, 4-trimethylsiloxy-3-penten-2-one). Bubbling with nitrogen gas and spraying on the surface of the semiconductor substrate heated to 90 ° 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. 3B, H of the OH group on the surface of the semiconductor substrate 1 is replaced by Si (CH ₃ ) ₃ (trimethylsilyl group), and CH ₃ COCH ₂ COCH ₃ (acetylacetone) becomes Is generated. After that, a chemically amplified resist is applied to the surface of the semiconductor substrate 1 by the first application device to form a first resist film.

Next, the first exposure device is used to expose the first resist film using a desired mask.

Next, PEB and development are sequentially performed on the exposed first resist film by the first developing device to form a first resist pattern. Then the first
Using the resist pattern of, the next process such as a predetermined etching process and a predetermined film forming process is performed.

When the first resist pattern is formed as described above, the insoluble layer is not formed on the surface portion of the first resist pattern 2 as shown in FIG. That is, FIG. 4 shows that after the surface of the semiconductor substrate 1 is surface-treated with 4-trimethylsiloxy-3-penten-2-one using the first coating apparatus, the surface-treated semiconductor substrate 1 is processed.
A positive chemically amplified resist (KRF K2G, manufactured by Japan Synthetic Rubber Co., Ltd.) is applied on the above to a thickness of 0.7 μm to form a first resist film, and then a first exposure device is used. Then, the first resist film is exposed by a KrF excimer laser stepper with NA: 0.5, and then the first developing device is used to expose the exposed first resist film at 100 ° C. 2 shows a cross-sectional shape of a 0.25 μm line-and-space pattern when PEB was performed for 90 seconds at a temperature of 2 ° C. and development was performed using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. .

[0049] As described above, in the first half of the process of the first reference embodiment, in order to perform a surface treatment with 4-trimethylsiloxy-3-penten-2-one as a surface treatment agent, an alkali component such as ammonia The surface of the semiconductor substrate 1 can be made hydrophobic without generating
Therefore, it is possible to prevent the hardly soluble layer from being formed on the surface portion of the first resist pattern 2 and obtain a stable pattern shape.

[0050] Hereinafter, will be described with reference to FIGS. 5 to 7 for the second half step of the method for manufacturing the semiconductor device according to a first referential embodiment of the present invention performed using the apparatus for manufacturing a semiconductor device. The latter half of the process is a process of forming a second resist pattern made of a non-chemically amplified resist by using the second coating device, the second exposure device, and the second developing device.

FIG. 5 shows a flow of steps for forming a resist pattern made of a non-chemically amplified resist.
7B shows a surface state of the semiconductor substrate when the surface treatment is performed by the surface treatment agent according to the first reference embodiment, and FIG.
2 shows a schematic cross-sectional shape of a second resist pattern made of a non-chemically amplified resist formed on a semiconductor substrate surface-treated with the surface-treating agent according to the first reference embodiment.

First, by the second coating device, as shown in FIG.
4, 4-dimethyl-n-hexylsiloxy-3-penten-2-one as a surface treatment agent is supplied to the surface of the semiconductor substrate 1 made of silicon (that is, 4
-Dimethyl-n-hexylsiloxy-penten-2-one was bubbled with nitrogen gas and sprayed on the surface of the semiconductor substrate heated to 90 ° C. for 30 seconds) to make the surface of the semiconductor substrate 1 hydrophobic to make the semiconductor substrate 1. Adhesion is improved. By doing so, as shown in FIG. 6B, H of the OH group on the surface of the semiconductor substrate 1 is changed to Si (CH ₃ ).
₂ (CH ₂₎ is replaced by the ₅ CH ₃ (dimethyl -n- hexyl silyl _{group), CH 3 COCH 2 COCH 3} ( acetylacetone) is generated. After that, a non-chemically amplified resist is applied to the surface of the semiconductor substrate 1 by the second coating device to form a second resist film.

Next, the second exposure device is used to expose the second resist film using a desired mask.

Next, PEB and development are sequentially performed on the exposed second resist film by the second developing device to form a second resist pattern. Then the second
Using the resist pattern of, the next process such as a predetermined etching process and a predetermined film forming process is performed.

When the second resist pattern was formed as described above, as shown in FIG. 7, the second resist pattern 3 having a good shape with no peeling portion was formed on the semiconductor substrate 1. That is, in FIG. 7, the surface of the semiconductor substrate 1 is surface-treated with 4-dimethyl-n-hexylsiloxy-3-penten-2-one using the second coating apparatus, and then the surface-treated semiconductor substrate 1 is used. Non-chemical amplification type positive resist (PFI-38 manufactured by Sumitomo Chemical Co., Ltd.) on top of
To a film thickness of 1.0 μm to form a second resist film, and then using a second exposure apparatus, an i-line stepper with NA: 0.6 is applied to the second resist film. Exposed,
Next, PEB was performed for 90 seconds at a temperature of 100 ° C. using the second developing device, and then 0.30 μm when developed using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. The cross-sectional shape of the line and space pattern is shown.

As described above, in the latter half step of the first reference embodiment, the surface treatment is carried out using 4-dimethyl-n-hexylsiloxy-3-penten-2-one as the surface treatment agent, so that ammonia is used. Adhesion between the second resist pattern 3 and the semiconductor substrate 1 can be improved without generating an alkaline component such as the above, and a good pattern shape without peeling can be obtained.

As described above, in the method of manufacturing the semiconductor device according to the first reference embodiment, the surface treatment step for forming the first resist pattern of the chemically amplified resist and the non-chemically amplified resist are used. made in any of a surface treatment step for forming the second resist pattern, for use a surface treatment agent that does not generate an alkali component, because the alkaline component is not generated in both surface treatment process described above, the first reference embodiment There is no alkaline component in the clean room in which the semiconductor device manufacturing method according to the present invention is performed. Therefore, the hardly soluble layer is not formed on the surface of the first resist pattern made of the chemically amplified resist, and the first resist pattern having a good pattern shape can be obtained.

[0058] In the method of manufacturing the semiconductor device according to a first referential embodiment, in the surface treatment step for forming the second resist pattern of a non-chemically amplified resist, as a surface treatment agent 4-dimethylamino - Since n-hexylsiloxy-3-penten-2-one is used, it is possible to form a second resist pattern made of a non-chemically amplified resist having excellent adhesion.

(Second Reference Embodiment) Hereinafter, the first half step of the method for manufacturing a semiconductor device according to the second reference embodiment of the present invention, which is performed by using the above-described semiconductor device manufacturing apparatus, will be described with reference to FIG. To do. The first half step is a step of forming a first resist pattern made of a chemically amplified resist using the first coating device, the first exposure device, and the first developing device.

[0060] Figure 8 is a schematic cross-sectional shape of the pattern of the first resist pattern of a chemically amplified resist formed on a semiconductor substrate was subjected to surface treatment with a surface treatment agent according to the second referential embodiment There is.

First, using the first coating apparatus, as in the first reference embodiment, 4-trimethylsiloxy-3-penten-2-one as a surface treatment agent is applied to the surface of the semiconductor substrate 1 made of silicon. Is supplied to make the surface of the semiconductor substrate 1 hydrophobic so that the adhesion of the semiconductor substrate 1 is improved. By doing so, as in the first reference embodiment, H of the OH group on the surface of the semiconductor substrate 1 is replaced by Si (CH ₃ ) ₃ (trimethylsilyl group), and CH ₃ COCH ₂ COCH ₃ (acetylacetone) is produced. It After that, a chemically amplified resist is applied to the surface of the semiconductor substrate 1 by the first application device to form a first resist film.

Next, the first exposure device is used to expose the first resist film using a desired mask.

Next, PEB and development are sequentially performed on the exposed first resist film by the first developing device to form a first resist pattern. Then the first
Using the resist pattern of, the next process such as a predetermined etching process and a predetermined film forming process is performed.

When the first resist pattern is formed as described above, the insolubilized layer is not formed on the surface portion of the first resist pattern 4 as shown in FIG. That is, FIG. 8 shows that the surface of the semiconductor substrate 1 is surface-treated with 4-trimethylsiloxy-3-penten-2-one using the first coating device, and then the surface-treated semiconductor substrate 1 is processed.
A positive chemically amplified resist (KRF K2G, manufactured by Japan Synthetic Rubber Co., Ltd.) is applied on the above to a thickness of 0.7 μm to form a first resist film, and then a first exposure device is used. Then, the first resist film is exposed by a KrF excimer laser stepper with NA: 0.5, and then the first developing device is used to expose the exposed first resist film at 100 ° C. 2 shows a cross-sectional shape of a 0.25 μm line-and-space pattern when PEB was performed for 90 seconds at a temperature of 2 ° C. and development was performed using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. .

[0065] As described above, in the first half of the process of the second referential embodiment, for performing the surface treatment with 4-trimethylsiloxy-3-penten-2-one as a surface treatment agent, an alkali component such as ammonia The surface of the semiconductor substrate 1 can be made hydrophobic without generating
Therefore, it is possible to prevent the hardly soluble layer from being formed on the surface portion of the first resist pattern 4, and to obtain a stable pattern shape.

[0066] Hereinafter, the second half step of the method for manufacturing the semiconductor device according to a second referential embodiment of the present invention will be described with reference to FIG performed using the apparatus for manufacturing a semiconductor device. The latter half of the process is a process of forming a second resist pattern made of a non-chemically amplified resist by using the second coating device, the second exposure device, and the second developing device.

[0067] Figure 9 shows a schematic cross-sectional shape of the resist pattern of a non-chemically amplified resist formed on a semiconductor substrate was subjected to surface treatment with a surface treatment agent according to the second referential embodiment.

First, using the second coating apparatus, as in the first half of the second reference embodiment, 4-trimethylsiloxy-3-pentene as a surface treatment agent is applied to the surface of the semiconductor substrate 1 made of silicon. 2-ON is supplied to make the surface of the semiconductor substrate 1 hydrophobic so that the adhesion of the semiconductor substrate 1 is improved. In this way, similarly to the first half of the process of the second reference embodiment, H of the OH groups of the surface of the semiconductor substrate 1 is Si (CH
₃ ) ₃ (trimethylsilyl group), CH ₃ CO
CH ₂ COCH ₃ (acetylacetone) is produced.
Then, a chemically amplified resist is applied to the surface of the semiconductor substrate 1 by the second coating device to form a second resist film.

Next, the second exposure device is used to expose the second resist film using a desired mask.

Next, PEB and development are sequentially performed on the exposed second resist film by the second developing device to form a second resist pattern. Then the second
Using the resist pattern of, the next process such as a predetermined etching process and a predetermined film forming process is performed.

When the second resist pattern was formed as described above, as shown in FIG. 9, the second resist pattern 5 having a good shape with no peeling portion was formed on the semiconductor substrate 1. That is, FIG. 9 shows that after the surface of the semiconductor substrate 1 is surface-treated with 4-trimethylsiloxy-3-penten-2-one using the second coating apparatus, the surface of the semiconductor substrate 1 is not coated on the surface-treated semiconductor substrate 1. 1.0 μm of chemically amplified positive resist (PFI-38 manufactured by Sumitomo Chemical Co., Ltd.)
To form a second resist film, and then, using a second exposure device, apply N to the second resist film.
A: exposed by i-line stepper of 0.6, then the second
PEB was performed for 90 seconds at a temperature of 100 ° C. using the developing device of No. 3, and 0.30 μm line-and-space when developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution. The cross-sectional shape of the pattern is shown.

[0072] As described above, in the second half of the process of the second referential embodiment, for performing the surface treatment with 4-trimethylsiloxy-3-penten-2-one as a surface treatment agent, an alkali component such as ammonia It is possible to improve the adhesion between the second resist pattern 5 and the semiconductor substrate 1 without generating the above, and it is possible to obtain a good pattern shape without a peeled portion.

As described above, in the method for manufacturing a semiconductor device according to the second reference embodiment, the surface treatment step for forming the first resist pattern made of the chemically amplified resist and the non-chemically amplified resist are used. made in any of a surface treatment step for forming the second resist pattern, for use a surface treatment agent that does not generate an alkali component, because the alkaline component is not generated in both surface treatment process described above, the first reference embodiment The concentration of ammonia in the clean room where the semiconductor device manufacturing method according to
It was a very small value of μg / m ³ . For this reason,
The insoluble layer is not formed on the surface of the first resist pattern made of the chemically amplified resist, and the first resist pattern having a good pattern shape can be obtained.

[0074] In the method of manufacturing the semiconductor device according to a second referential embodiment, in the surface treatment step for forming the second resist pattern of a non-chemically amplified resist, 4-trimethyl as a surface treatment agent siloxy -3-
Since penten-2-one is used, it is possible to form a second resist pattern made of a non-chemically amplified resist having excellent adhesion.

[0075] In the second referential embodiment, when forming the surface treatment step, and the second resist pattern of a non-chemically amplified resist for forming the first resist pattern of a chemically amplified resist Since the same surface treatment agent is used in each of the surface treatment steps, both surface treatment steps can be performed using the same coating apparatus. By doing so, the throughput of the treatment process can be improved and the footprint of the treatment device can be reduced as compared with the case where both surface treatment processes are performed by using different coating devices arranged in different treatment zones.

[0076] In the first and second reference embodiment, the first half of the process in the chemically amplified resist has been subjected to each of the patterning of the non-chemically amplified resist later in the process, in any of the reference embodiment , non-chemically amplified resist in the first half of the process, in the second half of the process may be performed each patterning a chemically amplified resist, it is possible to obtain good results similar to those of the first and second reference embodiment.

[0077] In the first and second reference embodiment, using a surface treatment agent to produce a reaction decomposition product consisting of acetylacetone, also, in the first reference embodiment, the surface of the semiconductor substrate hydrophobic using a surface treatment agent to produce a trimethylsilyl group or dimethyl -n- hexyl silyl group as a material, in the second referential embodiment, use of the surface treatment agent to produce a trimethylsilyl group the surface of the semiconductor substrate as a material for the hydrophobic However, the surface treatment agent is not limited to these. That is, the surface treatment agent containing the silane compound represented by the following general formula (1) can be widely used.

R ¹⁴ _-n Si (OR) _n (1) 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.

As a first example of the silane compound represented by the above general formula (1), a compound represented by the following general formula (3) can be mentioned.

R ¹ ₃ SiOR (3) However, as for the meanings of R and R ¹ , the above general formula (1)
Is the same as.

The silane compound represented by the above general formula (3) has one hydrolyzable group on the Si atom,
The semiconductor substrate is processed into a monomolecular film to obtain a film with high in-plane uniformity. Further, the silane compound represented by the general formula (3) is easily affected by the steric hindrance of the R ¹ substituent, and this property is reflected in the reaction rate (processing ability).

Silane compound represented by the above general formula (3)
Among them, the silane compound used in the present invention specifically includes the compounds shown in [Chemical Formula 5] and [Chemical Formula 6].

[0083]

[Chemical 5]

[0084]

[Chemical 6]

As a second example of the silane compound represented by the general formula (1), those represented by the following general formula (4) can be mentioned.

R ¹ ₂ Si (OR) ₂ (4) However, the meanings of R and R ¹ are as defined in the general formula (1) above.
Is the same as.

The silane compound represented by the above general formula (4) has two hydrolyzable groups on the Si atom,
The semiconductor substrate is processed into a laminated film and has high processing capability.

Silane compound represented by the above general formula (4)
Among them, the silane compound used in the present invention is specifically the compound represented by [Chemical Formula 7].

[0089]

[Chemical 7]

As a third example of the silane compound represented by the general formula (1), those represented by the following general formula (5) can be mentioned.

R ¹ Si (OR) ₃ (5) However, the meanings of R and R ¹ are as defined in the general formula (1) above.
Is the same as.

The silane compound represented by the general formula (5) has three hydrolyzable groups on the Si atom,
Although the semiconductor substrate is processed into a laminated film and has high processing capacity, the unreacted silane compound may be hydrolyzed by moisture in the air to form a gel, which may cause particle contamination depending on the processing method. become.

Silane compound represented by the above general formula (5)
Among them, the silane compound used in the present invention is specifically the compound represented by [Chemical Formula 8].

[0094]

[Chemical 8]

The silane compound represented by the general formula (3) is particularly stable in terms of material, and the silane compound represented by the general formula (5) is particularly highly reactive. .

As the surface treatment agent, those containing a silane compound represented by the following general formula (2) can be used.

[0097]

[Chemical 9]

(Provided that R ¹ , R ² and R ³ are the same or different and are a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, and 1 to 6 carbon atoms. A substituted unsaturated hydrocarbon group or an unsubstituted unsaturated hydrocarbon group,
Alternatively, it is an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, and R
⁴ , R ⁵ and R ⁶ are the same or different and are a hydrogen atom,
Substituted saturated hydrocarbon group having 1 to 6 carbon atoms or unsubstituted saturated hydrocarbon group, substituted unsaturated hydrocarbon group having 1 to 6 carbon atoms or unsubstituted unsaturated hydrocarbon group, alicyclic saturated group having 3 to 6 carbon atoms Hydrocarbon group or OR ⁷ (R ⁷ 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) It is an unsaturated hydrocarbon group or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms.). )

Silane compound represented by the above general formula (2)
Among these, examples of the silane compound used in the present invention include compounds represented by [Chemical Formula 10], [Chemical Formula 11] and [Chemical Formula 12].

[0100]

[Chemical 10]

[0101]

[Chemical 11]

[0102]

[Chemical 12]

In [Chemical Formula 10], [Chemical Formula 11] and [Chemical Formula 12], (a) is 3-dimethylvinylsiloxytrifluoromethyl-2-propene-1-trifluoromethyl-
1-one, (b) is 3-triethylsiloxytrifluoromethyl-2-propen-1-trifluoromethyl-1-one, and (c) is 3-dimethyl (3 ′, 4 ′,
4′-trifluoro-3′-butenyl) siloxytrifluoromethyl-2-propen-1-trifluoromethyl-1-one, and (d) is 3-dimethyl (2′-cyanoethyl) siloxytrichloromethyl-2. -Propene-
1-trichloromethyl-1-one and (e) is 4-
Dimethylcyclohexylsiloxy-3-pentene-2-
ON , (j) is 4-t-butyldimethylsiloxy-3-penten-2-one, (k) is 2-isopropyldimethylsiloxy-1-methoxycarbonyl-1.
-Propene.

[0104] 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.

Examples of the constituent components of the above chemically amplified resist are given below, but the constituent components are not limited to the following.

<Chemical amplification type positive resist of two-component system> Resin which becomes soluble in alkali by the action of acid: poly (t-butoxycarbonyloxystyrene-co-hydroxystyrene) poly (t-butoxycarbonylmethyloxystyrene) -co-
Hydroxystyrene) Poly (tetrahydropyranyloxystyrene-co-hydroxystyrene) Acid generator: onium salt, nitrobenzyl sulfonate 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)

[0109]

[Chemical 13]

Acid generator: onium salt, nitrobenzyl sulfonic acid ester compound <Three-component chemically amplified negative resist> Alkali-soluble resin: polyvinylphenol, polymethacrylic acid ○ Crosslinking reaction occurs by the action of acid Compound or resin ...
Melamine compound, melamine resin ○ acid generator …… onium salt, nitrobenzyl sulfonate compound

[0111]

According to the semiconductor device manufacturing method of the present invention, the first method is performed in the same clean room.
In both of the resist film forming step and the second resist film forming step, the surface treatment is performed with the surface treating agent containing the silane compound represented by the general formula (1). Therefore, the method for manufacturing a semiconductor device according to the present invention. Since no alkaline component is present in the clean room where the process is carried out, the hardly soluble layer is not formed on the surface of the first resist pattern made of the chemically amplified resist, and a resist pattern having a good pattern shape can be obtained.

Further, there is no need to form the first resist film and the second resist film in different environments due to the concern that the alkaline component may adversely affect the first resist pattern made of the chemically amplified resist, so that the throughput is improved. Can be improved. In particular, in the case where the same surface treatment apparatus is used for the surface treatment in the first resist film formation step and the second resist film formation step, the throughput of the treatment step is further improved and the footprint of the treatment apparatus is reduced. You can In this case, the same surface treatment agent may be used or different surface treatment agents may be used.

According to the semiconductor device manufacturing apparatus of the present invention, the first coating device and the second coating device provided in the same clean room have the surface containing the silane compound represented by the general formula (1). Since the surface treatment is performed by the treatment agent, there is no alkaline component in the clean room in which the semiconductor device manufacturing apparatus according to the present invention is installed. Therefore, the surface portion of the first resist pattern made of the chemically amplified resist is hardly soluble. A layer is not formed, and a resist pattern having a good pattern shape can be obtained.

In the method or apparatus for manufacturing a semiconductor device according to the present invention, when the silane compound is the silane compound represented by the general formula (2), the energy level of the electrophilic orbit of the silane compound is low. High reactivity between the trimethylsilyl group of the silane compound and the silanol group on the semiconductor substrate. For this reason, since many silyl groups of the silane compound adhere to the surface of the semiconductor substrate, the surface of the semiconductor substrate becomes hydrophobic, the adhesion between the semiconductor substrate and the resist pattern is greatly improved, and the film does not peel off. A reliable resist pattern can be obtained.

In the semiconductor device manufacturing method or manufacturing apparatus according to the present invention, the chemically amplified resist contains an acid generator,
By containing a resin which becomes alkali-soluble by the action of an acid, it is possible to prevent deactivation of the acid when a two-component chemically amplified positive resist is used.

When the chemically amplified resist contains an acid generator, an alkali-soluble resin, and a compound or resin which becomes alkali-soluble by the action of acid, the acid when the three-component chemically amplified positive resist is used. Deactivation can be prevented.

When the chemically amplified resist contains an acid generator, an alkali-soluble resin, and a compound or resin that causes a crosslinking reaction by the action of an acid, a three-component chemically amplified negative resist is used. The deactivation of acid can be prevented.

When the non-chemically amplified resist contains the naphthoquinonediazide compound and the novolac resin, the adhesiveness of the resist pattern containing the naphthoquinonediazide compound and the novolak resin can be improved.

[Brief description of drawings]

FIG. 1 is a schematic plan view showing a layout of a semiconductor device manufacturing apparatus according to the present invention.

2 is a flowchart describing the first half of the steps of a method of manufacturing a semiconductor device according to a first referential embodiment of the present invention.

[3] (a), the surface state of the semiconductor substrate when the supply (b) in the method for manufacturing a semiconductor device according to the first referential embodiment, 4-trimethylsiloxy-3-penten-2-one It is a schematic diagram which shows.

FIG. 4 is a schematic view showing a cross-sectional shape of a first resist pattern made of a chemically amplified resist formed by the method for manufacturing a semiconductor device according to the first reference embodiment.

5 is a flow diagram illustrating the latter half steps of the method of manufacturing the semiconductor device according to a first referential embodiment of the present invention.

6 (a), (b) in the method for manufacturing a semiconductor device according to the first reference embodiment, the semiconductor substrate at the time of supplying the 4-dimethyl -n- hexyl siloxy-3-penten-2-one It is a schematic diagram which shows the surface state of.

FIG. 7 is a schematic diagram showing a cross-sectional shape of a second resist pattern made of a non-chemically amplified resist formed by the method for manufacturing a semiconductor device according to the first reference embodiment.

FIG. 8 is a first view of a chemically amplified resist formed by a method of manufacturing a semiconductor device according to a second reference embodiment of the present invention.
FIG. 3 is a schematic view showing a cross-sectional shape of the resist pattern of FIG.

FIG. 9 is a schematic view showing a cross-sectional shape of a second resist pattern made of a non-chemically amplified resist formed by the method for manufacturing a semiconductor device according to the second reference embodiment.

FIG. 10 is a flow diagram illustrating a first half process of a conventional semiconductor device manufacturing method.

FIG. 11 is a schematic view showing a surface state of a semiconductor substrate when HMDS is supplied in the first half step of the conventional method for manufacturing a semiconductor device.

FIG. 12 is a flowchart illustrating a latter half of the conventional method for manufacturing a semiconductor device.

FIG. 13 is a schematic view showing a surface state of a semiconductor substrate when HMDS is supplied in the latter half step of the conventional method for manufacturing a semiconductor device.

FIG. 14 is a schematic view showing a cross-sectional shape of a resist pattern made of a chemically amplified resist formed by a conventional semiconductor device manufacturing method.

FIG. 15 is a diagram showing a correlation between the environmental concentration of trimethylsilanol, which is a decomposition product of HMDS, and the environmental concentration of ammonia.

[Explanation of symbols]

1 Semiconductor substrate 2 First resist pattern 3 Second resist pattern 4 First resist pattern 5 Second resist pattern 6 resist pattern 7 Insoluble layer

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiromi Osaki Inventor Hiromi Nakagusuku-gun, Niigata Prefecture Nishi-Fukushima 28-1, Shinjuku Chemical Industry Co., Ltd. Synthetic Technology Laboratory (56) Reference JP-A-7-335603 (JP, A) JP-A-7-120919 (JP, A) JP-A-9-218516 (JP, A) JP-A-9-102458 (JP, A) JP-A-10-270306 (JP, A) JP-A-6 −3828 (JP, A) Tokuheihei 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 (12)

(57) [Claims] 1. A surface of a semiconductor substrate is subjected to a surface treatment with a surface treatment agent containing a silane compound represented by the following general formula (1) in a clean room, and then the surface of the surface-treated semiconductor substrate is chemically amplified. A first resist film forming step of applying a resist to form a first resist film; and a step of exposing the first resist film in the clean room using a mask having a desired pattern shape Exposure step, a first developing step of developing the exposed first resist film in the clean room to form a first resist pattern, and After the surface treatment with the surface treatment agent containing the silane compound represented by the formula (1), the surface of the surface-treated semiconductor substrate is non-chemically increased. A second resist film forming step of applying a width type resist to form a second resist film, and exposing the second resist film in the clean room using a mask having a desired pattern shape. A semiconductor device comprising: a second exposure step; and a second development step of developing the exposed second resist film in the clean room to form a second resist pattern. Manufacturing method. R ¹ _4-n Si (OR) _n (1) (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 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. Which 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 carbon It is an alicyclic saturated hydrocarbon group of the formulas 3 to 6 , and when n = 1, at least one of R ¹
Is a substituted saturated hydrocarbon group having 2 to 6 carbon atoms or unsubstituted
Saturated hydrocarbon group or substituted unsaturated hydrocarbon having 2 to 6 carbon atoms
A containing group or unsubstituted unsaturated hydrocarbon group, a n = 2 and if R is a methyl group, the R ¹
At least one of them is an unsubstituted saturated carbon having 2 to 6 carbon atoms.
Hydrogenated group or substituted unsaturated hydrocarbon group containing 2 to 6 carbon atoms
Or an unsubstituted unsaturated hydrocarbon group, and when n = 3, R ¹ is an unsubstituted C 2-6 unsubstituted hydrocarbon group.
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 method for manufacturing a semiconductor device according to claim 1, wherein the silane compound is represented by the following general formula (2). [Chemical 1] (However, R ¹ , R ² and R ³ are the same or different and are a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsubstituted hydrocarbon group having 1 to 6 carbon atoms. A saturated hydrocarbon group or an unsubstituted unsaturated hydrocarbon group, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, wherein at least one of R ¹ , R ² and R ³ has a carbon number
2-6 substituted saturated hydrocarbon groups or unsubstituted saturated hydrocarbons
Elementary group, or substituted unsaturated hydrocarbon group having 2 to 6 carbon atoms
Is an unsubstituted unsaturated hydrocarbon group, R ⁴ , R ⁵ and R ⁶ are the same or different and are 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 or an unsubstituted unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, or OR ⁷ (R ⁷ is a hydrogen atom or a carbon number 1 ~ 6 substituted saturated hydrocarbon group or unsubstituted saturated hydrocarbon group, C1-6 substituted unsaturated hydrocarbon group or unsubstituted unsaturated hydrocarbon group, or C3-6 alicyclic saturated hydrocarbon group It is a group.) ) 3. The method of manufacturing a semiconductor device according to claim 1, wherein the chemically amplified resist contains an acid generator and a resin which becomes alkali-soluble by the action of an acid. 4. The chemically amplified resist according to claim 1, which contains an acid generator, an alkali-soluble resin, and a compound or resin which becomes alkali-soluble by the action of an acid. Manufacturing method of semiconductor device. 5. The chemically amplified resist according to claim 1, which contains an acid generator, an alkali-soluble resin, and a compound or resin that causes a crosslinking reaction by the action of an acid. Manufacturing method of semiconductor device. 6. The method of manufacturing a semiconductor device according to claim 1, wherein the non-chemically amplified resist contains a naphthoquinonediazide compound and a novolac resin. 7. A surface of a semiconductor substrate, which is provided in a clean room, is surface-treated with a surface-treating agent containing a silane compound represented by the following general formula (1), and then surface-treated. A first coating device for coating a chemically amplified resist on the first resist film to form a first resist film; and a mask provided in the clean room and having a desired pattern shape for the first resist film. A first exposure device for performing exposure by using the first exposure device, provided in the clean room, for developing the exposed first resist film to form a first resist pattern, and the clean room After the surface treatment of the surface of the semiconductor substrate with a surface treatment agent containing a silane compound represented by the following general formula (1), the surface-treated semiconductor is A second coating device for coating a non-chemically amplified resist on the surface of the body substrate to form a second resist film, and a desired pattern for the second resist film, which is provided in the clean room. A second exposure device for exposing using a mask having a shape; and a second development provided in the clean room for developing the exposed second resist film to form a second resist pattern. An apparatus for manufacturing a semiconductor device, comprising: R ¹ _4-n Si (OR) _n (1) (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 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 of the formulas 3 to 6 , and when n = 1, at least one of R ¹
Is a substituted saturated hydrocarbon group having 2 to 6 carbon atoms or unsubstituted
Saturated hydrocarbon group or substituted unsaturated hydrocarbon having 2 to 6 carbon atoms
A containing group or unsubstituted unsaturated hydrocarbon group, a n = 2 and if R is a methyl group, the R ¹
At least one of them is an unsubstituted saturated carbon having 2 to 6 carbon atoms.
Hydrogenated group or substituted unsaturated hydrocarbon group containing 2 to 6 carbon atoms
Or an unsubstituted unsaturated hydrocarbon group, and when n = 3, R ¹ is an unsubstituted C 2-6 unsubstituted hydrocarbon group.
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. ) 8. The apparatus for manufacturing a semiconductor device according to claim 7, wherein the silane compound is represented by the following general formula (2). [Chemical 2] (However, R ¹ , R ² and R ³ are the same or different and are a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 6 carbon atoms or an unsubstituted saturated hydrocarbon group, a substituted unsubstituted hydrocarbon group having 1 to 6 carbon atoms. A saturated hydrocarbon group or an unsubstituted unsaturated hydrocarbon group, or an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, wherein at least one of R ¹ , R ² and R ³ has a carbon number
2-6 substituted saturated hydrocarbon groups or unsubstituted saturated hydrocarbons
Elementary group, or substituted unsaturated hydrocarbon group having 2 to 6 carbon atoms
Is an unsubstituted unsaturated hydrocarbon group, R ⁴ , R ⁵ and R ⁶ are the same or different and are 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 or an unsubstituted unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 6 carbon atoms, or OR ⁷ (R ⁷ is a hydrogen atom or a carbon number 1 ~ 6 substituted saturated hydrocarbon group or unsubstituted saturated hydrocarbon group, C1-6 substituted unsaturated hydrocarbon group or unsubstituted unsaturated hydrocarbon group, or C3-6 alicyclic saturated hydrocarbon group It is a group.) ) 9. The semiconductor device manufacturing apparatus according to claim 7, wherein the chemically amplified resist contains an acid generator and a resin which becomes alkali-soluble by the action of acid. 10. The chemical amplification resist according to claim 7, wherein the chemical amplification resist contains an acid generator, an alkali-soluble resin, and a compound or resin which becomes alkali-soluble by the action of an acid. Semiconductor device manufacturing equipment. 11. The chemically amplified resist according to claim 7, wherein the chemically amplified resist contains an acid generator, an alkali-soluble resin, and a compound or resin that causes a crosslinking reaction by the action of an acid. Semiconductor device manufacturing equipment. 12. The apparatus for manufacturing a semiconductor device according to claim 7, wherein the non-chemically amplified resist contains a naphthoquinonediazide compound and a novolac resin.