JP2002134403A - Aligner for manufacturing semiconductor and semiconductor device manufacturing process using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent a projection optical system from being contaminated by gas generated from an exposed substrate. SOLUTION: In an aligner for manufacturing a semiconductor, that exposes the semiconductor substrate by exposure light emitted from the projection optical system, a slit plate for passing exposure light or a shielding member, shaped like a shutter for preventing contamination on the optical system, is provided in between the projection optical system and the substrate, and a gas barrier film is stacked on a surface of the shielding member on the side of the semiconductor substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor manufacturing exposure apparatus used in a semiconductor device manufacturing process.

[0002]

2. Description of the Related Art In recent years, high integration of semiconductor integrated circuits has been progressing toward the gigabit DRAM generation. With this high integration, the performance required for an exposure apparatus, especially for a projection optical system, has also become higher. Here, the resolution, which is the performance of the exposure apparatus, can be increased by increasing the numerical aperture (NA) of the projection optical system. However, the depth of focus is reduced by increasing the NA. Therefore, the NA cannot be increased to a certain degree or more, and it is required to shorten the exposure wavelength in order to increase the resolution.

[0003] For this reason, a short wavelength Kr is used as a light source for a gigabit DRAM generation exposure apparatus.
The F excimer laser and the ArF excimer laser are promising, and the resist has been shifted to a chemically amplified resist having a higher resolution as the wavelength of the light source becomes shorter. The chemically amplified resist generates an acid by exposure using a light source such as KrF, and uses the acid as a catalyst during a bake treatment (heat treatment) after the exposure. This causes a reaction, whereby the dissolution rate in an alkali developer can be changed to obtain a pattern having a high aspect ratio after development.

Here, the reaction of a positive chemically amplified resist will be briefly described. The resist is composed of a base resin having a protecting group and a photoacid generator, and is composed of KrF or Ar.
When exposed to light from the F light source, the photoacid generator reacts to generate an acid. The acid acts as a catalyst to remove the protecting group, producing a reaction product. The reaction product is vaporized and goes out of the resist film, so that the resist film thickness decreases.

[0005] This phenomenon mainly occurs during heat treatment after exposure, but the above reaction actually occurs during exposure or during the period from exposure to heat treatment. This is because, as a result of improving the sensitivity of the resist in order to increase the throughput of the exposure apparatus, the protecting group is released sensitively to the presence of an acid, and the reaction proceeds at room temperature without heating to a high temperature. It is.

As described above, since the protective group elimination reaction proceeds at room temperature, the reaction product is vaporized from the exposure to the heat treatment to generate a reaction product gas. This gas further reacts with the exposure light. As a result, there is a problem that the projection lens system is contaminated by the generated organic matter. That is, as shown in FIG. 3, when light from a light source passes through an illumination optical system, a reticle, and a projection optical system 31 to a substrate (semiconductor substrate) 30 to be exposed, the resist on the substrate 30 reacts and gas 33 occurs. The generated gas 33 reacts with the light from the light source to generate an organic substance 32, and the organic substance 32 adheres to the surface of the final lens 34 of the projection optical system 31.

As described above, the reaction product gas released out of the film becomes an organic substance through a complicated reaction process including decomposition and recombination by light irradiation, and solidifies on the surface of a projection lens or the like. When the projection lens is contaminated in this way, the resolution performance of the exposure apparatus is reduced, or the line width within the angle of view is varied due to uneven illuminance, and the yield of the manufactured semiconductor device is reduced. There is a problem.

[0008]

SUMMARY OF THE INVENTION The present invention provides an exposure apparatus for manufacturing a semiconductor which can prevent a contamination of a projection optical system when a chemically amplified resist is used and can transfer a pattern with high accuracy and stability for a long period of time. The purpose is to:

[0009]

SUMMARY OF THE INVENTION The present invention provides a semiconductor manufacturing exposure apparatus for exposing a semiconductor substrate with exposure light from a projection optical system.
The present invention relates to an exposure apparatus for manufacturing a semiconductor, wherein a shielding member having a slit-shaped opening for allowing exposure light to pass therethrough is provided, and a gas barrier film is laminated on a surface of the shielding member on a semiconductor substrate side. Here, the shielding member is
It is preferable to use a shielding member that opens an opening through which exposure light passes during exposure and closes the opening during non-exposure.
Further, the gas barrier film is preferably composed of a coating composition containing the following components (a) and (b). (A) Ethylene / vinyl alcohol copolymer (b) General formula (1) R ¹ _mm M (OR ² ) _n ··· (1) (wherein, M is a metal atom, and R ¹ is the same or different. , An organic group having 1 to 8 carbon atoms, R ² is the same or different,
An alkyl group of from 5 to 5 or an acyl group or phenyl group of from 1 to 6 carbon atoms, m and n are each an integer of 0 or more, and m + n is a valence of M) Hydrolyzate of the metal alcoholate, condensate of the metal alcoholate, chelate compound of the metal alcoholate, hydrolyzate of the metal chelate compound, condensate of the metal chelate compound, metal acylate, hydrolysis of the metal acylate At least one selected from the group consisting of a decomposition product and a condensate of the metal acylate. The coating composition preferably further contains a nitrogen-containing organic solvent. Further, the coating composition preferably further contains (c) inorganic fine particles. The exposure apparatus for manufacturing a semiconductor according to the present invention may be one in which a vapor deposition layer of a metal and / or an inorganic compound is further laminated on at least one of the shielding member and the gas barrier film. Next, the present invention relates to a semiconductor device manufacturing process using the semiconductor manufacturing exposure apparatus.

[0010]

FIG. 1 shows a configuration of an exposure section of a KrF successively moving reduction projection exposure apparatus (stepper) according to an embodiment of the present invention. In FIG. 1, reference numeral 11 denotes a projection optical system, and reference numeral 14 denotes a final stage projection lens. Reference numeral 10 denotes a substrate to be exposed (semiconductor substrate).
4, a slit plate (shielding member) 1 having an opening
5 are provided. Here, the size and shape of the opening can be appropriately selected in order to achieve the purpose of exposing the semiconductor substrate.

The slit plate (shielding member) 15 is shown in FIG.
The shutter (shielding member) 25 shown in FIG. The shutter 25 opens an opening through which exposure light passes during exposure, and closes the opening during non-exposure. The shutter 25 has a structure that can be changed according to the numerical aperture (NA) of the projection optical system 21 so that the opening area of the shutter 25 is the minimum area that does not obstruct the optical path of the exposure light. That is, when the NA is large, the opening area of the shutter 25 is set large, and when the NA is small, the opening area of the shutter 25 is set small. Here, the thickness of the shutter 25 is the same as the thickness of the slit plate 15. Further, as the shutter opening / closing structure, a commonly used configuration can be appropriately adopted.

The slit plate 15 or the shutter 25
It is preferable that a gas barrier film (not shown) is laminated on the surface (substrate to be exposed). As the gas barrier film, for example, a coating film composed of a coating composition containing the above components (a) and (b) is preferable. Hereinafter, the coating composition constituting the gas barrier film used in the present invention will be described.

The coating composition (a) component; The ethylene / vinyl alcohol copolymer used as the component (a) in the present invention is a saponified product of a copolymer of ethylene and vinyl acetate, that is, ethylene-vinyl acetate. It is obtained by saponifying a random copolymer, and is obtained from a partially saponified product in which acetic acid groups remain in tens of mol%, from complete saponification in which only a few mol% of acetic acid groups remain or acetic acid groups do not remain. Although not particularly limited, the preferred degree of saponification is 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. Content of repeating units derived from ethylene in ethylene / vinyl alcohol copolymer (hereinafter also referred to as "ethylene content")
Is usually 20 to 50 mol%, preferably 25 to 45 mol%. Specific examples of the ethylene / vinyl alcohol copolymer include EVAL EP-F manufactured by Kuraray Co., Ltd.
101 (ethylene content; 32 mol%), manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content; 2
9 mol%), Soarnol D2935 (ethylene content; 2
9 mol%).

The melt flow index of the above-mentioned (a) ethylene / vinyl alcohol copolymer is 1 to 20 g / 10 minutes at 210 ° C. under a load of 21.168 N. These (a) ethylene / vinyl alcohol copolymers can be used alone or in combination of two or more.

The ethylene / vinyl alcohol copolymer constituting the component (a) itself has excellent gas barrier properties, weather resistance, organic solvent resistance, transparency, gas barrier properties after heat treatment, and the like. In addition, when the ethylene-vinyl alcohol copolymer cures a coating film obtained from the composition of the present invention, a hydroxyl group present in a repeating unit derived from polyvinyl alcohol has a component (b) described below and / or By co-condensing with the component (c), excellent coating film performance can be provided.

The proportion of the component (a) in the coating composition of the present invention is from 10 to 10,000 parts by weight, preferably from 20 to 5, based on 100 parts by weight of the component (b) described below.
000 parts by weight, more preferably 100 to 1,000 parts by weight. If the amount is less than 10 parts by weight, cracks easily occur in the obtained coating film, and the gas barrier property is reduced.
If the amount exceeds 000 parts by weight, the resulting coating film is unfavorably reduced in gas barrier properties under high humidity.

Component (b): Component (b) used in the present invention is a metal alcoholate, a hydrolyzate of the metal alcoholate, or a condensate of the metal alcoholate represented by the above general formula (1). A chelate compound of the metal alcoholate (hereinafter also referred to as “metal chelate compound”), a hydrolyzate of the metal chelate compound, a condensate of the metal chelate compound, a metal acylate, a hydrolyzate of the metal acylate,
And at least one selected from the group of condensates of the metal acylate. That is, the component (b)
Only one of the species may be used, or a mixture of any two or more species may be used. Further, the metal chelate compound is a metal alcoholate and at least one compound selected from β-diketones, β-ketoesters, hydroxycarboxylic acids, hydroxycarboxylates, hydroxycarboxylates, keto alcohols and amino alcohols (Hereinafter also referred to as "chelating agent"). Among these chelating agents, it is preferable to use β-diketones or β-ketoesters,
Specific examples of these include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, and t-acetoacetate. Butyl, 2,4-hexane-dione, 2,4-heptane-
Examples thereof include dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, and 5-methyl-hexane-dione.

The hydrolyzate of the metal alcoholate, the hydrolyzate of the metal chelate compound, and the hydrolyzate of the metal acylate have all the OR ² groups contained in the metal alcoholate hydrolyzed. There is no need to use, for example, one having only one hydrolyzed, two or more having been hydrolyzed, or a mixture thereof. Further, the condensate of the metal alcoholate, the condensate of the metal chelate compound, and the condensate of the metal acylate are a metal alcoholate, a metal chelate compound, and a MO of a hydrolyzate of the metal acylate.
Although the H group is condensed to form an M-OM bond, in the present invention, it is not necessary that all the M-OH groups are condensed, and a slight part of the M-OH group is condensed. , Those having different degrees of condensation, M-OR groups and MO
This concept includes a mixture of condensates in which H groups are mixed. When a condensate is used as the component (b), a product obtained by previously hydrolyzing and condensing the metal alcoholate, the metal chelate compound, and the metal acylate may be used, or a commercially available condensate may be used. May be used. Further, a condensate of a metal alcoholate may be used as it is, or may be reacted with the above chelating agent and used as a condensate of a metal chelate compound. Commercially available condensates of the above metal alcoholates include A-10, B-2, B-4, and B-10 manufactured by Nippon Soda Co., Ltd.
-7 and B-10. It is considered that the component (b) functions to form a co-condensate with the component (a).

In the general formula (1), as the metal atom represented by M, zirconium, titanium and aluminum can be mentioned as preferred, and titanium is particularly preferred. The monovalent organic group having 1 to 8 carbon atoms of R ¹ differs depending on whether the compound represented by the general formula (1) is a metal alcoholate or a metal acylate. When it is a metal alcoholate, for example, methyl, ethyl, n-propyl, i-propyl, n-
Alkyl groups such as butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group; acetyl group, propionyl group, butyryl group , Valeryl group, benzoyl group, acyl group such as trioil group; vinyl group, allyl group, cyclohexyl group, phenyl group, glycidyl group,
In addition to (meth) acryloxy, ureido, amide, fluoracetamide, and isocyanate groups,
Substituted derivatives of these groups can be mentioned. R
Examples of the substituent in the substituted derivative ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group,
-An epoxycyclohexyl group, a (meth) acryloxy group, a ureido group, an ammonium base and the like. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent. In the case of a metal acylate, R ¹ has 1 to ¹ carbon atoms.
As the monovalent organic group of 8, an acetoxyl group, a propionyloxyl group, a butylyloxyl group, a valeryloxyl group,
An acyloxyl group such as a benzoyloxyl group and a trioyloxyl group can be exemplified. When two R ¹ are present in the general formula (1), they may be the same or different from each other.

Examples of the alkyl group having 1 to 5 carbon atoms for R ² include a methyl group, an ethyl group, an n-propyl group,
i-propyl group, n-butyl group, sec-butyl group, t
-Butyl group, n-pentyl group and the like,
Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group,
Examples include a propionyl group, a butyryl group, a valeryl group, and a caproyl group. A plurality of R ² in the general formula (1) may be the same or different from each other.

Among these components (b), specific examples of metal alcoholates and chelate compounds of metal alcoholates include (a) tetra-n-butoxyzirconium,
Zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), zirconium n-butoxytris (ethylacetoacetate), zirconium tetrakis (n-propylacetoacetate), tetrakis (acetyl) Zirconium compounds such as acetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium;

(B) Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, di-i-propoxybis (ethylacetoacetate) titanium, di-i-propoxy.
Bis (acetylacetate) titanium, di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminate) titanium, dihydroxybislactatetitanium, dihydroxytitanium lactate, tetrakis (2 −
Titanium compounds such as ethylhexyloxy) titanium;

(C) Aluminum tri-i-propoxy, aluminum di-i-propoxy ethyl acetoacetate, aluminum di-i-propoxy acetylacetonate, aluminum i-propoxy bis (ethyl acetoacetate), i-propoxy Aluminum compounds such as bis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, and monoacetylacetonate bis (ethylacetoacetate) aluminum; Among these metal alcoholates and chelate compounds of metal alcoholates, preferred are tri-n-butoxyethylacetoacetate zirconium, di-i-propoxybis (acetylacetonato) titanium, di-n-butoxy. Bis (triethanolaminate) titanium, dihydroxybislactatetitanium titanium, di-i-propoxyethylacetoacetate aluminum and tris (ethylacetoacetate) aluminum can be mentioned, and particularly preferred compounds are di-i-propoxy. Titanium compounds such as bis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminate) titanium, and dihydroxybislactatetotitanium;

Further, specific examples of the metal acylate include:
Dihydroxy titanium dibutyrate, di-i-propoxy titanium diacetate, di-i-propoxy titanium dipropionate, di-i-propoxy titanium dimallonate, di-i-propoxy titanium dibenzoylate, di -N-butoxy-zirconium diacetate, di-i-propylaluminum monomalonate, etc., and particularly preferred compounds are dihydroxy.
Titanium compounds such as titanium dibutyrate and di-i-propoxy titanium diacetate. These components (b) are used alone or in combination of two or more.

As the component (b), since the viscosity of the coating solution does not change with time, and it is easy to handle, the component (b) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent described in the hydrophilic solvent described below. It is preferable to use those subjected to a decomposition treatment. By performing such a hydrolysis treatment before mixing with the component (a), the unhydrolyzed component (b), partially hydrolyzed component (b), and partially condensed component (b) The mixture becomes a mixture, and a sharp increase in viscosity due to a shock or the like that occurs when the composition is mixed with the component (a) during preparation of the composition, and an increase in viscosity over time are suppressed. in this case,
The amount of water used is 0.1 mol per mol of R ¹ _mM (OR ² ) _n.
１，1,000 mol, preferably 0.5-500 mol. In the case of a mixed solvent, the mixing ratio of water and the hydrophilic organic solvent is such that water / hydrophilic organic solvent = 10-90 / 90-10
(Weight ratio), preferably 20-80 / 80-20, more preferably 30-70 / 70-30. As the component (b), particularly preferred are di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminate) titanium,
It is obtained by hydrolyzing a titanium compound such as dihydroxybislactate-titanium with the above-mentioned mixed solvent.

The coating composition of the present invention preferably contains a nitrogen-containing organic solvent as required. Examples of the nitrogen-containing organic solvent include hydrophilic nitrogen-containing organic solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, γ-butyrolactone, N-methylpyrrolidone, and pyridine; thymine, glycine, cytosine, and guanine. Nucleic acid bases; hydrophilic nitrogen-containing polymers such as polyvinylpyrrolidone, polyacrylamide, and polymethacrylamide; and copolymers obtained by copolymerizing these components. Of these, N, N-dimethylacetamide, N, N-dimethylformamide and polyvinylpyrrolidone are preferred. By mixing a nitrogen-containing organic solvent, a coating film having a better appearance and a better appearance in thin film coating can be obtained, and inorganic particles and / or
Alternatively, it exerts a catalytic effect when condensing with an inorganic laminate. The proportion of the nitrogen-containing organic solvent used in the total amount of the solvent,
Preferably 1 to 70% by weight, more preferably 1 to 50%
%, Particularly preferably 5 to 50% by weight.

Component (c): The coating composition of the present invention preferably contains inorganic fine particles as the component (c). The inorganic fine particles are a particulate inorganic substance having an average particle diameter of 0.2 μm or less and substantially containing no carbon atoms,
Metal or silicon oxide, metal or silicon nitride, metal boride. Methods for producing inorganic fine particles include, for example, a gas phase method in which silicon tetrachloride is obtained by hydrolysis of oxygen and hydrogen in a flame to obtain silicon oxide, a liquid phase method in which sodium silicate is ion-exchanged, a silica gel mill, and the like. Production methods such as solid phase method obtained by pulverization by,
It is not limited to these methods.

Specific examples of the compound include SiO_Two, A
l_TwoO_Three, TiO_Two, WO_Three, Fe _TwoO_Three, ZnO, N
iO, RuO_Two, CdO, SnO_Two, Bi_TwoO_Three, 3A
l_TwoO_Three・ 2SiO_Two, Sn-In_TwoO_Three, Sb-In
_TwoO_Three, Oxides such as CoFeOx, Si_ThreeN_Four, Fe
_FourNitrides such as N, AlN, TiN, ZrN, TaN,
Ti_TwoB, ZrB_Two, TaB_Two, W_TwoBorides such as B
Is mentioned. The form of the inorganic fine particles may be powder, water, or the like.
Or colloids or sols dispersed in organic solvents.
However, these are not limited. Among these
To co-condensate with component (a) and / or component (b)
In order to obtain excellent coating performance by
Idal silica, colloidal alumina, alumina sol,
Sol, zirconium sol, antimony pentoxide sol, acid
Cerium oxide sol, zinc oxide sol, titanium oxide sol, etc.
Colloidal oxides with hydroxyl groups on the particle surface
It is. The average particle diameter of the inorganic fine particles is preferably 0.2 μm or less.
It is preferably 0.1 μm or less, and the average particle size is 0.2 μm
If it exceeds, the gas barrier property is inferior from the viewpoint of the denseness of the film.
There are cases.

The proportion of the component (c) in the composition of the present invention is as follows:
The amount is preferably from 10 to 900 parts by weight, particularly preferably from 20 to 400 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (b). If it exceeds 900 parts by weight,
The gas barrier properties of the resulting coating film may be reduced.

Optional component; (d) using a curing accelerator for the purpose of curing the composition of the present invention more quickly and for the purpose of easily forming a cocondensate of the component (a) and the component (b). It is more effective to use the curing accelerator (d) in combination to cure at a relatively low temperature and obtain a denser coating film.

The (d) curing accelerator includes inorganic acids such as hydrochloric acid; naphthenic acid, octylic acid, nitrous acid, sulfurous acid,
Alkali metal salts such as aluminate and carbonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide; acidic compounds such as alkyltitanic acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid and phthalic acid; ethylenediamine, hexanediamine , Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, metaphenylenediamine, ethanolamine, triethylamine, various modified amines used as curing agents for epoxy resins, γ-aminopropyltriethoxysilane, γ- (2- aminoethyl) - aminopropyl trimethoxysilane, .gamma. (2-aminoethyl) - aminopropyl methyl dimethoxy silane, amine compounds such as .gamma. anilino trimethoxysilane, (C ₄ H _{9) 2 n (OCOC 11 H 23) 2} , (C 4
H ₉ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ ,
(C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOC
_{4 H 9) 2, (C} 8 H 17) 2 Sn (OCOC
_{11 H 23) 2, (C} 8 H 17) 2 Sn (OCOCH = CHC
OOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = C
HCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC
H = CHCOOC ₈ H ₁₇ ) ₂ , Sn (OCOCC)
Carboxylic acid type organotin compounds such as ₈ H ₁₇ ) ₂ ; (C ₄
H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₄ H
₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C
_{8 H 17) 2 Sn (SCH} 2 COOC 8 H 17) 2, (C 8
_{H 17) 2 Sn (SCH 2} CH 2 COOC 8 H 17) 2,
(C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ ,
(C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₁₂ H ₂₅ ) ₂ ,

[0032] Sulfide type organotin compounds such as;

(C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ S
nO, or (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂
Organic tin oxide such as SnO and ethyl silicate,
Organotin compounds such as reaction products with ester compounds such as dimethyl maleate, diethyl maleate and dioctyl phthalate are used. The proportion of these (d) curing accelerators in the composition is usually from 0.5 to 50 parts by weight, based on 100 parts by weight of the solid content of the composition of the present invention.
Preferably, 0.5 to 30 parts by weight is used.

Further, the composition of the present invention may contain, as a stability improver, β-diketones and / or β-diketones described above.
-Ketoesters can be added. That is,
By coordinating to a metal atom in the metal alcoholate present in the composition as the component (b), the composition acts to control the condensation reaction between the component (a) and the component (b), and the composition obtained It is considered that they act to improve the storage stability of the product. β-diketones and / or β
The amount of the ketoester to be used is preferably 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal atom in the component (b).

The coating composition of the present invention is usually obtained by dissolving and dispersing the above components (a) to (b) and optionally the above optional components in water and / or a hydrophilic organic solvent. Here, specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, and se.
c-butyl alcohol, tert-butyl alcohol,
1 carbon atoms such as diacetone alcohol, ethylene glycol, diethylene glycol, triethylene glycol, etc.
Saturated aliphatic monohydric alcohol or dihydric alcohol having from 8 to 8 carbon atoms such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate;
A saturated aliphatic ether compound having 1 to 8 carbon atoms, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoether acetate, ethylene glycol monobutyl ether acetate;
Ester compounds of polyhydric alcohols; sulfur-containing compounds such as dimethyl sulfoxide; lactic acid, methyl lactate, ethyl lactate,
Examples thereof include hydroxycarboxylic acids or hydroxycarboxylic acid esters such as salicylic acid and methyl salicylate. Of these, preferred are
1 to 1 carbon atoms such as methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, sec-butyl alcohol and tert-butyl alcohol
And 8 saturated aliphatic monohydric alcohols.

These water and / or hydrophilic organic solvent are more preferably used by mixing water and a hydrophilic organic solvent. The preferred solvent composition is water / saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms and water / nitrogen-containing organic solvent. More preferably, water / saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms / nitrogen-containing organic solvent.
By mixing a nitrogen-containing organic solvent, a good coating film having a transparent appearance in a thin film coating can be obtained.

The amount of water and / or hydrophilic organic solvent used is such that the total solid content of the composition is preferably 60% by weight or less. For example, when it is used for forming a thin film, it is usually 5 to 40% by weight, preferably 10 to 30% by weight, and when it is used for forming a thick film, it is usually 20 to 50% by weight. %, Preferably 30
~ 45% by weight. When the total solid content of the composition exceeds 60% by weight, the storage stability of the composition tends to decrease.

As the organic solvent, the above-mentioned water and / or hydrophilic organic solvent is preferable. In addition to the hydrophilic organic solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, tetrahydrofuran, dioxane, etc. Ethers, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate can also be used.

As described above, the coating composition of the present invention is obtained by mixing the above components (a) and (b) and optionally the above optional components in water and / or a hydrophilic organic solvent. Is obtained by hydrolyzing and / or condensing the above components (a) and (b) and, if necessary, component (c) in water and / or a hydrophilic organic solvent. In this case, the reaction conditions are such that the temperature is 20 to 100 ° C, preferably 30 to 80 ° C, and the time is 0.1 to 20 hours, preferably 1 to 10 hours. The weight-average molecular weight of the obtained composition is generally 500 in terms of polymethyl methacrylate by a general GPC method.
１００1,000,000, preferably 1,000 to 300,000. The weight average molecular weight is measured by gel permeation chromatography and is converted into polystyrene.

The coating composition of the present invention includes:
A filler may be separately added and dispersed in order to develop various properties such as coloring, thickening of the obtained coating film, prevention of ultraviolet transmission to the base, imparting corrosion resistance, and heat resistance. However, the filler excludes the component (c). As the filler, for example, organic pigments, other than water-insoluble pigments or pigments such as inorganic pigments, particulate, fibrous or flaky metals and alloys and oxides and hydroxides thereof,
Carbides, nitrides, sulfides and the like. Specific examples of the filler include particles, fibrous or scaly,
Iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide,
Titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, Talc, barium carbonate, calcium carbonate,
Magnesium carbonate, barium sulfate, bentonite, mica, zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, shale green, green earth, manganese green, pigment green, ultramarine, navy blue, pigment green, rock ultramarine, Cobalt blue, Cerulean blue, Copper borate, Molybdenum blue, Copper sulfide, Cobalt purple, Mars purple, Manganese purple, Pigment violet, Lead oxide, Calcium plumbate, Zinc yellow, Lead sulfide, Chrome yellow, Loess, Cadmium yellow, Strontium Yellow, titanium yellow, litharge,
Pigment Yellow, Cuprous Oxide, Cadmium Red, Selenium Red, Chrome Vermillion, Bengala, Zinc White, Antimony White, Basic Lead Sulfate, Titanium White, Lithopon, Lead Silicate,
Zircon oxide, tungsten white, lead zinc white, bunchesone white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, etc. Can be

The average particle size or average length of these fillers is usually 50 to 50,000 nm, preferably 100 to 50,000 nm.
５，5,000 nm. The proportion of the filler in the composition is
Preferably 0.1 to 300 parts by weight, more preferably 1 to 2 parts by weight, based on 100 parts by weight of the total solids of the components other than the filler.
00 parts by weight.

The coating composition of the present invention includes:
Other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, various surfactants,
Additives other than those described above, such as a silane coupling agent, a titanium coupling agent, a dye, a dispersant, a thickener, and a leveling agent can also be blended.

In preparing the coating composition of the present invention, the above components (a) and (b), preferably (a)
A composition containing the components (b) to (c) may be prepared. Preferably, the component (b) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then the component (a) is hydrolyzed. Mix. In this case, there is no change in viscosity of the coating composition over time, and a coating composition excellent in handleability can be obtained. Specific examples of the method for preparing the coating composition of the present invention when the component (c) is used include the following. The component (b) used in these preparation methods may be one which has been hydrolyzed in advance in water or a mixed solvent containing water and a hydrophilic organic solvent. (A) dissolved in water and / or a hydrophilic organic solvent
A method in which the component (c) is added to the components, and then the component (b) is added. (A) dissolved in water and / or a hydrophilic organic solvent
A method in which the component (c) is added to the components, and then the component (b) is added, followed by hydrolysis and / or condensation. (A) dissolved in water and / or a hydrophilic organic solvent
A method in which the component (b) is added to the components, hydrolysis and / or condensation is performed, and then the component (c) is added. A method in which the components (a) to (c) are added all at once to water and / or a hydrophilic organic solvent and dissolved and dispersed. Alternatively, a method of performing hydrolysis and / or condensation after that.

The surface of the shielding member on which the coating film is formed may be subjected to a known surface activation treatment such as a corona discharge treatment, a plasma activation treatment, a glow discharge treatment, a reverse sputtering treatment, a roughening treatment, or ethyleneimine. System, amine system, epoxy system,
It is also possible to perform a primer treatment with a primer agent such as urethane or polyester.

In order to laminate a coating layer formed from the coating composition of the present invention (hereinafter also referred to as “coating of the present invention”) on the surface of the above-mentioned shielding member, a microgravure is applied to the surface of the member. Roll coating such as a coater, spray coating, spin coating, dipping, brushing, bar code, a coating method such as an applicator, etc., by one or more coatings, the dry film thickness is 0.01 to 30 μm, preferably 0.1 A coating film of the present invention having a thickness of 10 to 10 μm can be formed, and heated under a normal environment at a temperature of 50 to 300 ° C., preferably 70 to 200 ° C. for 0.5 to 60 minutes, preferably 1 to 10 minutes. -By drying, condensation is performed, and a coating film (gas barrier film) of the present invention can be formed.

At this time, it is also possible to laminate a vapor deposition layer of a metal and / or an inorganic compound (hereinafter also referred to as a “vapor deposition layer”) on the surface of the shielding member or on the coating film of the present invention. By providing this vapor deposition layer, the gas barrier property is further improved. Here, the above-mentioned vapor-deposited layer includes metals such as aluminum, silicon, titanium, zinc, zirconium, magnesium, tin, copper, and iron, and oxides, nitrides, sulfides, and fluorides of these metals. Aluminum, silicon dioxide, titanium oxide, zirconium oxide, magnesium oxide, tin oxide, zinc sulfide, magnesium fluoride, and the like are used.

As a method of forming the vapor deposition layer, a vapor deposition method such as vacuum vapor deposition, ion plating, and sputtering is used, but vacuum vapor deposition and ion plating are preferable from the viewpoint of production efficiency. The inside of the vapor deposition device is 2 × 10 ^-6 to 8 ×
10 ^-3 Torr (2.7 × 10 ^{-4 to} 1.07 Pa), preferably 8 × 10 ^-6 to 8 × 10 ^-5 Torr (1.1 × 1
After evacuation to 0 ^{-3 to} 1.1 × 10 ^-2 Pa), a vapor deposition process is performed. This vapor-deposited layer has a barrier property against oxygen and water vapor, but aluminum, silicon oxide, aluminum oxide and the like are particularly excellent in gas barrier property. The film thickness of the vapor deposition layer is 1 to 500 nm, preferably 3 to 300 nm. If it is less than 1 nm, the gas barrier property may not be sufficient. On the other hand, if it exceeds 500 nm, the flexibility of the vapor deposition layer is impaired, and cracks and Pinholes are more likely to occur,
Both have poor gas barrier properties. The above-mentioned vapor deposition layer may use a plurality of vapor deposition materials in combination, or may have two or more layers.

Specific examples of the method for forming the gas barrier film of the present invention using the coating composition of the present invention include:
The following methods are mentioned. A method for forming a coating film of the present invention on a surface of a shielding member.
If necessary, a primer may be previously applied on the surface of the shielding member to form a coating film of the present invention, as described above. A method in which a vapor deposition layer is formed on the surface of a shielding member, and the coating film of the present invention is formed on the surface of the vapor deposition layer. In addition, when forming a vapor deposition layer on a surface of a shielding member, you may coat a primer on the surface of a shielding member beforehand as needed. A method for forming a vapor-deposited layer on the coating film surface of the present invention as described above. A method for forming a vapor-deposited layer on the coating film surface of the present invention as described above. A method for forming a coating film of the present invention on the surface of the above-mentioned vapor deposition layer. A method for forming a coating film of the present invention on the surface of the above-mentioned vapor deposition layer. The method of the above-mentioned, wherein the surface of the substrate is one side or both sides.

In the stepper configured as described above, as shown in FIG. 1A, the exposure light 16 from the KrF light source (not shown) is used to project the projection light on which the reticle (not shown) is set. Exposure is performed by irradiating the substrate 10 to be exposed through the system 11.

After the completion of the exposure, as shown in FIG.
The substrate 10 to be exposed moves to the next shot position. At this time, the region already exposed and generating the gas 13 from the resist also moves from directly below the opening of the slit plate 15. Therefore, contamination of the surface of the projection lens 14 by the gas 13 can be prevented.

In the present invention, it is preferable that a coating film (gas barrier film) made of the above coating composition is laminated on the substrate side surface of the slit plate (shielding member) 15. When a gas barrier film (not shown) is laminated on the surface of the slit plate 15 on the substrate side, the gas 13 generated from the resist does not pass through the slit plate 15 and passes through the opening of the slit plate 15 to project the projection optical system 11. Do not move to the side. Therefore, contamination of the surface of the projection lens 14 by the gas 13 can be effectively prevented.

In the present invention, as shown in FIG. 2A, the stepper having a shielding member that opens an opening for allowing exposure light to pass during exposure and closes the opening during non-exposure is used. Similarly, the exposure may be performed by irradiating the substrate to be exposed 20 through the projection optical system 21. After the exposure is completed, as shown in FIG. 2B, the opening of the shutter (shielding member) 25 is immediately closed to prevent the gas 23 generated from the resist on the substrate 20 from moving to the projection optical system 21 side. Thus, the projection lens 2 immediately after the exposure (before the exposure target substrate 20 moves to the next shot position)
4 is prevented from being contaminated by the gas 23.

Subsequently, as shown in FIG. 2C, the substrate 20 to be exposed moves to the next shot position, and the opening of the shutter 25 is opened again to perform the exposure. The region where the gas 23 is generated from the resist moves from directly below the opening of the shutter 25. Therefore, the gas 23 hardly reaches the surface of the projection lens 24. This prevents the projection lens 24 from being contaminated by the gas 23 after the substrate to be exposed 20 has moved to the next shot position.

In the present invention, it is preferable that a film (gas barrier film) made of the above-mentioned coating composition is also laminated on the surface of the shutter (shielding member) 25 on the substrate side. According to this, on the substrate side surface of the shutter 25,
Since the gas barrier film (not shown) is laminated, the gas 23 generated from the resist hardly passes through the shutter 25 and does not move toward the projection optical system 21 through the opening of the shutter 25. Therefore, contamination of the surface of the projection lens 24 by the gas 23 can be effectively prevented.

In the above embodiment, a stepper using a light source such as KrF has been described. However, the present invention can be applied to an exposure apparatus using a light source or a method other than these.

Hereinafter, a semiconductor device manufacturing process using the semiconductor manufacturing exposure apparatus of the present invention will be described. That is, this manufacturing process is used for manufacturing semiconductor chips such as ICs and LSIs, liquid crystal panels, CCDs, thin-film magnetic heads, micromachines, microoptics, and the like. The flow from circuit design to shipment will be described. First, in step 1, the circuit of a semiconductor device is designed. Next, in step 2, a mask (reticle) structure is formed in which a circuit pattern of the designed device is formed. On the other hand, in step 3, a wafer is manufactured using a material such as silicon.

Next, in step 4, a preprocess, that is, a process of forming an actual circuit on the wafer by photolithography using the mask structure and the wafer is performed. Then, in step 5, a post-process, that is, a process of forming a wafer on which circuits are formed into semiconductor chips is performed. The post-process includes an assembly process (dicing and bonding process) and a packaging process. The semiconductor device manufactured in this manner is subjected to various checks such as operation confirmation and durability in step 6,
Shipped in step 7.

The detailed flow of the pre-process of step 4 will be described. First, in step 11, the surface of the wafer is oxidized, and in step 12, an insulating film is formed on the wafer surface by CVD. Next, in step 13, electrodes are formed on the wafer by vapor deposition, and in step 14, ions are implanted into the wafer.

Subsequently, in step 15, a photosensitive agent is applied to the wafer, and in step 16, the circuit pattern of the mask is printed on the wafer and exposed. In this step 16, the use of the stepper or the like of the above embodiment makes it possible to manufacture a highly integrated semiconductor device, which has been difficult in the past.

After the exposure, the circuit pattern on the wafer is developed in a step 17, a portion other than the pattern image developed by the etching is removed in a step 18, and a resist which becomes unnecessary after the etching is removed in a step 19. By repeating these steps, multiple circuit patterns are formed on the wafer.

[0061]

EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these embodiments. Parts and% in Examples and Comparative Examples are based on weight unless otherwise specified. Various measurements in Examples and Comparative Examples were performed by the following methods.

[0062] oxygen permeability manufactured by Modern Controls, Inc., MOCON OXTRAN2
/ 20 was measured in an atmosphere at a temperature of 25 ° C. and a humidity of 90 RH%. Viscosity of coating liquid The viscosity at a liquid temperature of 25 ° C. was measured by a B-type viscometer. The viscosity measurement was performed immediately after the preparation of the coating composition and 24 hours later.

Reference Example 1 (Preparation of Titanium Chelate Compound) To a reactor equipped with a reflux condenser and a stirrer, 100 parts of tetra-i-propoxytitanium and 70 parts of acetylacetone were added, and stirred at 60 ° C. for 30 minutes. The compound was obtained. The purity of the reaction product was 75%.

Reference Example 2 (Preparation of Coating Composition) As the component (a), an ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2935, degree of saponification: 98% or more, ethylene content: 29 mol] %, Melt flow index; 35 g / 10 min], 5% water / n-
100 parts of a propyl alcohol solution (water / n-propyl alcohol weight ratio = 4/6), 2 parts of the titanium chelate compound prepared in Reference Example 1 as the component (b), 16.8 parts of n-propyl alcohol and water 11.2 Mix the parts,
A coating composition of the present invention was obtained. The viscosity immediately after the preparation of the composition was 15 mPa · s.

Reference Example 3 (Application of Coating Composition) An inorganic compound vapor-deposited layer having a thickness of 50 nm was formed on a slit plate by vacuum vapor deposition using silicon dioxide as a vapor deposition source. The coating composition obtained in Reference Example 2 was applied on the slit plate subjected to the corona discharge treatment by a bar coater, and dried at 100 ° C. for 10 minutes using a hot air drier to form a 0.3 μm-thick film. Was formed to obtain a gas-barrier-coated slit plate. The oxygen permeability of the portion other than the opening of the obtained slit plate was 0.1% at 90% humidity.
It was 1 cc / m ² · atm · 24 hr. The oxygen permeability of the portion other than the opening of the slit plate to which the coating composition was not applied was 3.5 cc / m at 90% humidity.
It was ² · atm · 24hr.

Reference Example 4 (Application of Coating Composition) A coating composition was applied on a shutter in the same manner as in Reference Example 3 above. The oxygen permeability of the shutter after application is
0.15 cc / m ² · atm · 24 hr at 90% humidity. The oxygen permeability of the part other than the opening of the shutter to which the coating composition was not applied was 90% humidity.
% Was 4.0 cc / m ² · atm · 24 hr.

Example 1 The slit plate coated in Reference Example 3 was incorporated into the configuration of the exposure section of the KrF sequential movement type reduction projection exposure apparatus (stepper) shown in FIG. It was evaluated visually. The slit lens coated in Reference Example 3 was assembled in a stepper, and after being used for 6 months in a regular operation, the projection lens 14 was inspected. Almost no contamination of the projection lens due to gas was observed, and the light transmittance was 95%, assuming 100% before operation, which was within an acceptable range.

Embodiment 2 In the same manner as in Embodiment 1, the shutter applied in Reference Example 4 was incorporated into the structure of the exposure section of the KrF successively moving reduction projection exposure apparatus (stepper) shown in FIG. Lens contamination by gas was evaluated. Almost no contamination by the gas of the projection lens after use for 6 months was observed, and the light transmittance was 97%, assuming 100% before operation, which was within an acceptable range.

Comparative Example 1 Contamination of the projection lens by gas was evaluated in the same manner as in Example 1 except that no shielding member such as a slit plate and a shutter was used. After 6 months of use, the projection lens is obviously contaminated by gas, and its light transmittance is 1 before operation.
When it was set to 00%, it was 80%, and replacement was necessary. Comparative Example 2 The contamination of the projection lens by gas was evaluated in the same manner as in Example 1 except that a slit plate not coated with the coating composition was used. After 6 months of use, the projection lens was clearly contaminated by gas, and its light transmittance was 70%, assuming 100% before operation, and needed to be replaced. Comparative Example 3 The contamination of the projection lens by gas was evaluated in the same manner as in Example 2 except that a shutter to which the coating composition was not applied was used. After 6 months of use, the projection lens is significantly contaminated by gas, and its light transmittance is 1 before operation.
When it was set to 00%, it was 50%, and replacement was necessary.

[0070]

According to the present invention, a shielding member in which a gas barrier film for preventing contamination of an optical system having an opening for allowing exposure light to pass at the time of exposure is laminated between a projection optical system and a substrate to be exposed. Is provided, the flow of gas generated from the substrate resist to the projection optical system side can be blocked without hindering exposure of the substrate, and a high optical system contamination prevention effect can be obtained. Further, by opening the opening for allowing the exposure light to pass through the shielding member at the time of exposure and closing the opening at the time of non-exposure, a higher effect of preventing contamination of the optical system can be obtained. As a result, the resolution performance and long-term stability of the illuminance of the exposure apparatus can be improved, and a good resist pattern can be stably obtained.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating a configuration of a stepper according to an embodiment of the present invention.

FIG. 2 is a schematic diagram illustrating a configuration of a stepper according to another embodiment of the present invention.

FIG. 3 is an explanatory view showing a contamination structure of a projection lens due to gas generated from a resist.

[Explanation of symbols]

 10, 20 Exposed substrate (semiconductor substrate) 11, 21 Projection optical system 14, 24 Projection lens 15 Shielding member (slit plate) 25 Shielding member (shutter)

Claims (7)

[Claims] 1. A semiconductor manufacturing exposure apparatus for exposing a semiconductor substrate with exposure light from a projection optical system, comprising: a shield having an opening between the projection optical system and the substrate for allowing the exposure light to pass during exposure. An exposure apparatus for manufacturing a semiconductor, comprising: a member; and a gas barrier film laminated on a surface of the shielding member on a semiconductor substrate side. 2. The exposure apparatus for manufacturing a semiconductor device according to claim 1, wherein the shielding member is a shielding member that opens an opening through which exposure light passes during exposure and closes the opening during non-exposure. 3. The exposure apparatus according to claim 1, wherein the gas barrier film comprises a coating composition containing the following components (a) and (b). (A) Ethylene / vinyl alcohol copolymer (b) General formula (1) R ¹ _mm M (OR ² ) _n ··· (1) (wherein, M is a metal atom, and R ¹ is the same or different. , An organic group having 1 to 8 carbon atoms, R ² is the same or different, and has 1 carbon atom.
An alkyl group of from 5 to 5 or an acyl group or phenyl group of from 1 to 6 carbon atoms, m and n are each an integer of 0 or more, and m + n is a valence of M) Hydrolyzate of the metal alcoholate, condensate of the metal alcoholate, chelate compound of the metal alcoholate, hydrolyzate of the metal chelate compound, condensate of the metal chelate compound, metal acylate, hydrolysis of the metal acylate At least one selected from the group consisting of a decomposition product and a condensate of the metal acylate 4. The exposure apparatus according to claim 3, wherein the coating composition further contains a nitrogen-containing organic solvent. 5. The transparent conductive sheet according to claim 3, wherein the coating composition further comprises (c) inorganic fine particles. 6. The exposure apparatus according to claim 1, wherein a vapor deposition layer of a metal and / or an inorganic compound is further laminated on at least one of the shielding member and the gas barrier film. 7. A semiconductor device manufacturing process using the semiconductor manufacturing exposure apparatus according to claim 1. Description: