JP2001015427A - Formation of fine pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a method by which a fine pattern of nanometer order can be formed at a high aspect ratio by using photolithography. SOLUTION: In a method for forming fine pattern, two resist layers are formed on a substrate 1, by successively applying a first resist film 2 composed of an organic high polymer and a second resist layer 3 composed of a photosensitive material to the substrate 1. Then a mask 4, in which fine metallic patterns 6 are formed on a mask substrate 5 composed of a dielectric substance, such as glass, etc., is closely adhered to the resists of the two layers, and the resists are exposed to a near-field light leaking out from the opening of the mask 4, where no metal is formed by irradiating the rear surface of the glass substrate 5 with the light. Thereafter, a pattern is formed by developing the second resist layer 3 with a developing solution, and a fine pattern having a high aspect ratio is formed by dry-etching the first resist film 2 with an O2 plasma through the use of the pattern of the second resist layer 3 as a mask. After working the substrate 1 through etching, vapor deposition, etc., by using the patterns of the two resist layers 2 and 3, the resists of the layers 2 and 3 are removed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming a fine pattern, and more particularly to a method for forming a fine pattern on a substrate by photolithography using near-field light.

[0002]

2. Description of the Related Art The development of optical lithography has been supported by advances in reduction projection exposure technology and resist technology. The performance of the reduced projection exposure technique is mainly determined by two basic quantities, the resolution RP and the depth of focus DOP. If the exposure wavelength of the projection optical system is λ and the numerical aperture of the projection lens is NA, the two basic quantities are RP = k ₁ λ / NA and DOP = k ₂
represented by lambda / NA ^2. In order to increase the resolution of lithography, it is important to reduce the wavelength λ and increase the numerical aperture NA of the projection lens. However, as the NA increases, the resolution increases, but the depth of focus decreases in inverse proportion to the square of the NA.
It has been required to reduce the wavelength λ. Therefore, the exposure wavelength λ changes from g-line (436 nm) to i-line (365 nm).
The wavelength has been shortened to an excimer laser (248n
m, 193 nm) is the mainstream.

However, in lithography using light, the diffraction limit of light is the limit of resolution. Therefore, even if an F ₂ excimer laser having a wavelength of 248 nm is used, miniaturization with a line width of 100 nm is not possible in lithography using a lens array optical system. It is said to be the limit. In order to further obtain a resolution on the order of nanometers, it is necessary to use an electron beam or X-ray (especially SOR light: synchrotron radiation) lithography technology.

[0004] Electron beam lithography can control the formation of patterns on the order of nanometers with high precision, and has a considerably deeper depth of focus than optical systems. Also,
It has the advantage of being able to directly draw on a wafer without a mask, but has the disadvantage of being far from mass production because of low throughput and high cost.

[0005] Further, the X-ray lithography has a resolution and resolution of about one digit compared to the excimer laser exposure, even when exposure is performed at the same magnification of a one-to-one mask or when a reflection type imaging X-ray optical system is used. Accuracy can be improved. However, X-ray lithography has a problem that it is difficult to form a mask, it is difficult to realize, and the cost is high on an apparatus.

In lithography using electron beams or X-rays, it is necessary to develop a resist in accordance with the exposure method, and there are still many problems in sensitivity, resolution, etching resistance and the like.

[0007]

As a method for solving the above-mentioned problems, recently, a near-field light leaking from an opening having a diameter sufficiently smaller than the wavelength of light to be irradiated is used as a light source, a resist is exposed, and development is performed. Thus, a method of forming a fine pattern has been proposed. According to this method,
Regardless of the wavelength of the light source, a spatial resolution on the order of nanometers can be obtained.

However, unlike near-field light, near-field light has a propagation depth of only several tens of nm (for this reason, it is expressed as exuding, not propagating. However, there is a problem that it is impossible to expose a thick resist having a thickness of 1000 nm, and it is difficult to form a resist pattern having a high aspect ratio. Here, the aspect ratio means that the line width of the resist is a and the height is b.
Then, when the resist thickness is constant, it can be said that the larger the aspect ratio, the finer the pattern.

Further, when there is a step on the underlayer, even if the thickness of the resist is thin enough to allow near-field light to reach,
Since it is difficult to apply a uniform thickness in the plane, a portion where light does not reach occurs in the resist, and there arises a problem that high-precision lithography is extremely difficult.

In view of the above circumstances, an object of the present invention is to provide a method for forming a fine pattern having a high aspect ratio in lithography using near-field light.

[0011]

The method for forming a fine pattern according to the present invention comprises a first resist layer which can be removed on a substrate by dry etching, and only a portion irradiated by light irradiation or only a non-irradiated portion is soluble in a developing solvent. A second resist layer having a photosensitive dry etching resistance is laminated on the recording material in this order, and a near-field is applied to the second resist layer of the recording material by means of receiving irradiation light and generating near-field light. By irradiating light in a desired pattern, and then developing the second resist layer to form a pattern of the second resist layer, using the pattern as a mask, dry-etching the first resist layer, A pattern is formed on a recording material substrate.

The thickness of the second resist layer is desirably 100 nm or less.

Further, the method for forming a fine pattern according to the present invention comprises:
It is desirable to use a recording material having an antireflection means for irradiation light on a substrate. In this case, the anti-reflection means
An anti-reflection film formed between the substrate and the first resist layer, or an anti-reflection film formed between the first and second resist layers is desirable.

The means for generating near-field light is a mask for generating near-field light from a metal pattern formed on a material having a light-transmitting property with respect to irradiation light. Light irradiation may be performed by bringing the layer into close contact with or in the vicinity of a region where near-field light reaches.

The means for generating near-field light is an optical stamp in which an uneven pattern is formed on the surface of a material having a light transmitting property to irradiation light, and near-field light is generated from the uneven portion by total reflection. Alternatively, light irradiation may be performed by bringing the uneven pattern into close contact with the second resist layer or as close as possible within a range where near-field light reaches.

Further, the means for generating near-field light is a probe having an opening having a diameter smaller than the wavelength of the irradiation light,
Light irradiation may be performed by scanning the probe on the second resist layer.

Further, it is desirable that the second resist layer and the means for generating near-field light are brought into close contact with each other by performing vacuuming in the exposure apparatus, and the near-field light is irradiated.

Further, the second resist layer and the means for generating near-field light are brought into close contact by performing vacuum evacuation in an exposure apparatus and blowing air from the back surface of the substrate to irradiate near-field light. You may.

Preferably, the first resist layer is subjected to oxygen plasma etching.

The second resist layer is preferably made of a pattern forming material containing a compound having a silicon atom. Also, the content of silicon atoms is desirably 1% or more and 50% or less of the solid content in the second resist layer.

Further, the second resist layer may be made of a pattern forming material containing at least one of a naphthoquinonediazide compound and a diazoketone compound, and a water-insoluble and alkali-soluble silicone-containing polymer.

The second resist layer has a water-insoluble and alkali-soluble silicone-containing polymer, a compound capable of generating an acid upon irradiation with actinic rays or radiation, and a group decomposable by an acid. And a high molecular weight or low molecular weight compound having a property of increasing solubility in an aqueous alkaline developer.

Further, the second resist layer has a water-insoluble silicone-containing polymer having a functional group capable of decomposing by an acid and having a property of increasing the solubility in an aqueous alkaline developer by the action of an acid. And a pattern-forming material containing a compound that generates an acid upon irradiation with actinic rays or radiation and a polymer or a low-molecular compound having a group that can be crosslinked by the acid.

Further, the second resist layer has a water-insoluble silicone-containing polymer having an olefinically unsaturated group and having a property of decreasing the solubility in an aqueous alkaline developer by a polymerization reaction, and an actinic ray or radiation. It may be composed of a pattern-forming material containing a compound capable of initiating a polymerization reaction upon irradiation.

The second resist layer has a water-insoluble and alkali-soluble silicone-containing polymer, a compound capable of initiating a polymerization reaction upon irradiation with actinic rays or radiation, and an olefinically unsaturated group. And a pattern-forming material containing a polymer or a low-molecular compound having a property of decreasing the solubility in an alkali developer.

[0026]

According to the method for forming a fine pattern of the present invention, a conventional photolithography is performed by exposing and developing a resist with near-field light exuding from a pattern having a line width sufficiently smaller than the wavelength of light to be irradiated. Thus, a pattern having a line width of 100 nm or less, which has been regarded as a limit, can be formed.

Hitherto, the resolution of lithography has been determined mainly by the wavelength of the light source. However, the wavelength of the light source for generating near-field light may be anything, so there is no need to develop a new light source, and the cost can be greatly reduced. It is possible.

Further, by using a two-layer resist consisting of a photosensitive resist and a resist composed of an organic polymer under the photosensitive resist, a portion having a step in the base and having no near-field light reaching by the one-layer resist is used. Even if the pattern can be formed, the surface is first flattened with an organic polymer resist, so that the thickness of the photosensitive resist on the upper layer can be made uniform, so that even a large-area pattern can be uniformly irradiated with near-field light. And a precise pattern of the photosensitive resist can be formed. By patterning the underlying organic polymer resist layer by a conventional dry etching method using the photosensitive resist pattern as a mask, a fine pattern having a high aspect ratio can be easily formed.

After the processing of the substrate, the two-layer resist does not deteriorate due to the exposure of the organic polymer resist layer, and thus can be easily peeled off with a known organic solvent used as a resist solvent. It also has the advantage of good productivity.

Therefore, according to the fine pattern forming method of the present invention using near-field light and a two-layer resist, a fine pattern of 100 nm or less can be formed at a high aspect ratio and at low cost.

[0031]

Embodiments of the present invention will be described below in detail with reference to the drawings.

FIG. 1 is a diagram showing a fine pattern forming method according to a first embodiment of the present invention.

As shown in FIG. 1A, a first resist film 2 made of an organic polymer and a second resist layer 3 made of a photosensitive material are sequentially applied on a substrate 1 by spin coating or spraying. A two-layer resist layer 3 'is formed.
Next, as shown in FIG. 1B, a mask 4 having a metal fine opening pattern 6 formed on a mask substrate 5 made of a dielectric material such as glass is brought into close contact with the two-layer resist. Next, when light is irradiated from the back surface of the mask substrate 5 with light such as i-line (365 nm) or the like, and exposure is performed using near-field light 7 that exudes from an opening where the metal of the mask 4 is not formed, as shown in FIG.
The exposed portion of the resist is exposed.

Here, the method of contact exposure will be described with reference to the sectional view of the contact exposure apparatus by vacuum drawing shown in FIG. First, the wafer having the two resist layers 3 'applied on the substrate 1 is mounted on a table of an exposure apparatus, and a mask 4 is mounted on the wafer 1 in close proximity thereto. Before the exposure, as shown in FIG. 2A, an inert gas such as N ₂ is always flowing between the mask and the resist in the apparatus. At the time of exposure, as shown in FIG. 2B, the mask is brought into close contact with the resist by evacuating the space between the mask and the resist. Thereafter, light is irradiated from the back surface of the mask. Then, as shown in FIG. 2c, the mask and the resist are separated by purging N ₂ once again.

Next, as shown in FIG. 1D, by developing the second resist layer 3 with a developing solution, the exposed portion becomes soluble in a developing solvent to form a positive pattern.
Thereafter, as shown in FIG. 1E, using the pattern of the second resist layer 3 as a mask, the first resist layer 2 is dry-etched by O ₂ plasma to form a fine pattern having a high aspect ratio as shown in FIG. 1F. I do. Dry etching may be ion dry etching or gas etching. Thereafter, the substrate is processed by etching or vapor deposition according to the pattern of the two-layer resist 3 ′, and then the two-layer resist is peeled off.

This peeling can be easily carried out by dissolving the first resist because the first resist has not been altered at all by exposure or the like. It is also possible to peel off by plasma ashing.

The photosensitive resist of the second resist layer 3 may be a negative resist in which only a portion irradiated by light is insoluble in a developing solvent, and the thickness of the second resist layer is limited to a near-field light. It is desirable that the depth is approximately equal to or less than the depth.

The organic polymer material of the first resist layer 2 may be any material as long as it can be etched by oxygen plasma, and may be a well-known photoresist. Considering the plasma resistance at the time of etching, an aromatic-containing polymer is desirable.

In this embodiment, a contact exposure apparatus using vacuum evacuation is used. However, as shown in FIG. 3, air is blown from the back surface of the substrate 1 on which the two-layer resist 3 'is formed, and the above-described vacuum is applied. The resist may be brought into close contact with the mask by pulling, and light may be applied from the back surface of the mask to perform exposure by air blowing. FIG. 3 shows a sectional view of the exposure apparatus.

As shown in FIG. 4, the proximity exposure may be performed by exposing the mask 4 and the two-layer resist 3 'in proximity to each other in a range where near-field light can reach. By performing the proximity exposure, problems such as damage to the mask, damage to the wafer, or adhesion of dust to the wafer, which are problems in close contact exposure, can be solved, and the output can be improved.

Next, a second embodiment of the present invention will be described.

FIG. 5 shows a fine pattern forming method using an optical stamp according to a second embodiment of the present invention.

As shown in FIG. 5, on a substrate 11, a first resist layer 12 made of an organic polymer and a second resist layer 13 made of a photosensitive material are sequentially applied. An optical stamp 14 that generates near-field light from the concavo-convex pattern by total reflection is brought into close contact with the second resist layer 13, and the second resist 13 is exposed and developed by the near-field light 17 generated from the convex portion,
Form a pattern. After that, similarly to the first embodiment, the first resist layer 12 is etched using the pattern of the second resist layer 13 as a mask to form a pattern having a high aspect ratio.

The optical stamp has the advantage that it can be produced at low cost because it does not use metal like a mask.

As shown in FIG. 6, a pattern may be formed by the above-described proximity exposure using an optical stamp.

Next, a third embodiment of the present invention will be described.

FIG. 7 shows a method for forming a fine pattern using a probe according to the third embodiment of the present invention.

As shown in FIG. 7, a first resist layer 22 made of an organic polymer and a second resist layer 23 made of a photosensitive material are sequentially applied on a substrate 21. Near-field light 27 is generated from the tip of the probe 24 having an opening having a diameter smaller than the light source wavelength, and the probe 24 is scanned in a pattern while irradiating the light on the second resist. By developing the second resist layer 23, a pattern of the second resist layer 23 is formed.
After that, as in the first and second embodiments, the first resist layer 22 is etched using the pattern of the first resist layer 22 as a mask to form a pattern having a high aspect ratio.

Since the exudation depth of the near-field light is about several tens of nm, there is almost no concern about reflected light. However, in order to protect light scattered from the back surface, the structure of the resist layer is as shown in FIG.
As shown in the figure, in a configuration in which a first resist layer 32 and a second resist layer 33 are formed on a substrate 31 in this order, an anti-reflection film 38 is provided between the substrate 31 and the first resist layer 32.
Alternatively, as shown in FIG. 9, an antireflection film 48 may be provided between the first resist layer 42 and the second resist layer 43 formed on the substrate 41. In each element in the figure, the same reference numerals are given to the same elements as those in the above-described embodiment, and the description is omitted.

In the above embodiment, the substrate is made of Si
Alternatively, a semiconductor substrate such as GaAs or a substrate on which an insulating film such as a SiO ₂ film is formed in the uppermost layer may be used.

Next, the details of the first resist layer and the second resist layer of the recording material of the present invention will be described.

The first resist layer of the present invention is formed from a material that can be dry-etched, particularly an organic polymer material.
It is desirable that the first resist layer does not form an intermediate mixed layer with the second resist layer formed thereon. Therefore, the organic polymer material of the first resist layer does not dissolve in the solvent of the second resist layer. Those which are dissolved at room temperature but are crosslinked like a network by a treatment such as heating and substantially do not form an intermediate mixed layer are preferred.

As an example of the latter, an i-line resist or a g-line resist containing a novolak resin and a naphthoquinonediazide compound and used for manufacturing a semiconductor device or the like is applied to a required film thickness, and then cured by heat treatment. There is a way. Alternatively, there is a method in which a negative resist containing an alkali-soluble resin such as a novolak resin or polyhydroxystyrene, an acid crosslinking agent and a photoacid generator is applied, and then the entire surface is exposed and cured. Alternatively, a negative resist containing an alkali-soluble resin such as a novolak resin or polyhydroxystyrene and a polyfunctional monomer and a photopolymerization initiator or a thermal polymerization initiator is applied, and then the entire surface is exposed or heated. There is also a curing method.

In addition to the above, a composition containing a vinyl polymer having at least one of a naphthyl group and an anthryl group in a side chain, assuming that the material of the first resist layer does not form an intermediate mixed layer with the second resist layer. And a composition comprising a vinyl polymer having at least one of a naphthyl group and an anthryl group in a side chain and having a crosslinkable group, and a crosslinking agent.

An additive (for example, fullerene or its dielectric substance) may be added to the first resist layer for various purposes.

For the second resist layer of the present invention, a photosensitive resist material is used in which only the irradiated portion or only the non-irradiated portion becomes soluble in the developing solvent due to the irradiation of near-field light, and the remaining portion has dry etching resistance. Can be As the resist material, a material containing a compound having a silicon atom and having a silicon content in a solid content of not less than a certain value is preferable.
When performing dry etching with oxygen-containing plasma,
From the viewpoint of oxygen-resistant plasma resistance, the higher the silicon content, the better. However, if the silicon content is too high, the pattern formability, the residue, the edge roughness of the pattern, and the like deteriorate, so the silicon content is 1% or more, preferably 4%. More than 50
% Or less. In particular, it is preferably from 5% to 30%.

As the resist material used for the second resist layer of the present invention, Japanese Patent Nos. 2035509, 2094657,
No. 2597163, No. 2606652, No. 2662461, No. 2646288,
No. 2646289, JP-A-60-191245, 62-247350, 6
2-36661, 62-36662, 62-38452, 62-96526
No. 62-136638, No. 62-153853, No. 62-159141,
62-220949, 62-229136, 62-240954, 63-
91654, 63-195649, 63-195650, 63-218948
No. 63-220241, No. 63-220242, No. 63-241542,
Nos. 63-239440, 63-313149, JP-A-1-44933, 1
-46746, 1-46747, 1-76046, 1-106042,
1-102550, 1-142720, 1-1201653, 1-2222
No. 54, No. 1-283555, No. 2-29652, No. 2-3054, No. 2-9
9954, 3-100553, 4-36754, 4-36755,
4-104252, 4-106549, 4-107460, 4-107562
Nos. 4-130324, 4-245248, 6-27670, 6-1
18651, 6-184311, 6-27671, 6-35199,
6-43655, 6-95385, 6-202338, 6-342209
No. 7-114188, No. 8-29987, No. 8-160620, No. 8-1
No. 60621, No. 8-160623, No. 8-193167, No. 10-319594
No., Tokiko 6-7259, 6-42075, 6-56492, 6-
79160, 6-84432, 7-27211, 7-60266,
7-69610, 7-99435, 71-111582, 7-113772
No., U.S. Pat.Nos. 4,689,289, 4,822,716, EP229629A1,
The resist materials described in Japanese Patent Application Nos. 10-354878, 11-31591, and 11-20224 are exemplified.

Among these, a material which can be developed with an aqueous alkaline developer is preferable because it has no organic waste liquid, has little swelling and can form a good pattern with high developing power. More specifically, it is a pattern forming material containing a water-insoluble and alkali-soluble silicone-containing polymer and a photosensitive compound.

More specifically, a pattern-forming material containing at least one of a naphthoquinonediazide compound and a diazoketone compound and a water-insoluble and alkali-soluble silicone-containing polymer, a water-insoluble and alkali-soluble silicone-containing polymer and an actinic ray or radiation Positive pattern forming material containing a polymer or a low molecular compound having a compound capable of generating an acid upon irradiation and a group decomposable by the acid, and having a property of increasing the solubility in an aqueous alkaline developer by the action of an acid. A water-insoluble silicone-containing polymer having a functional group capable of decomposing by an acid and having a property of increasing the solubility in an aqueous alkaline developer by the action of an acid, and generating an acid upon irradiation with actinic rays or radiation Aqueous alkaline developer having a group that can be crosslinked by a compound and an acid A pattern forming material containing a polymer or low molecular weight compound whose solubility decreases by the action of an acid, which has an olefinically unsaturated group, and whose solubility in an aqueous alkaline developer decreases due to a polymerization reaction. A negative pattern forming material containing a water-insoluble silicone-containing polymer and a compound capable of initiating a polymerization reaction upon irradiation with actinic rays or radiation, or a water-insoluble and alkali-soluble silicone-containing polymer with irradiation with actinic rays or radiation Negative pattern-forming material containing a polymer or low-molecular compound that has a compound capable of initiating a polymerization reaction and an olefinically unsaturated group, and whose solubility in an alkaline developer is reduced by a polymerization reaction Is mentioned.

As the water-insoluble and alkali-soluble silicone-containing polymer, a water-insoluble and alkali-soluble polysiloxane or polysilsesoxane is more preferable.

Examples of the water-insoluble silicone-containing polymer having a functional group capable of decomposing by an acid and having a property of increasing the solubility in an aqueous alkaline developer by the action of an acid include, for example, Japanese Patent Application No. Japanese Patent Application No. 11-24236 and Japanese Patent Application No. 11-277016, polysiloxane or polysilsesquioxane having an acid-decomposable group in the side chain, and Japanese Patent Application No. 11-298606 and Japanese Patent Application No. As described in JP-A-11-293882, a silicon-containing vinyl polymer having an acid-decomposable group in a side chain can be used.

Among the above, particularly, a water-insoluble and alkali-soluble silicone-containing polymer, a compound capable of generating an acid upon irradiation with actinic rays or radiation, and an acid-decomposable group containing an acid-decomposable group in an aqueous alkaline developer A pattern-forming material containing a polymer or a low-molecular compound having a property of increasing the solubility of the compound by an acid is preferred.

Next, the water-insoluble and alkali-soluble silicone-containing polymer will be described, and its chemical formula is shown below. As a water-insoluble and alkali-soluble silicone-containing polymer, a repeating unit represented by the following general formulas [I] and / or [II] as described in Japanese Patent Application Nos. 10-354878 and 11-143614. Those having a unit are exemplified.

[0064]

Embedded image Here, in the general formulas [I] and [II], X is-
A group selected from the group consisting of a C (＝ O) —R group, a —CH (OH) —R group, a —OH group, and a carboxyl group;
A plurality of Xs in the formula may be the same or different. Here, R represents a hydrogen atom or a hydrocarbon group which may have a substituent. R ′ to R ′ ″ ″ may be the same or different, and may have a hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group,
It is a group selected from the group consisting of an aralkyl group and a phenyl group. Y is an alkyl group, an alkoxy group or a siloxyl group. R ₀ represents a hydrogen atom, a halogen atom, or a group selected from the group consisting of an aliphatic hydrocarbon group and an aromatic hydrocarbon group which may have a substituent. r, s, t
Is an integer of 1 to 3, and u, v, and w are 1 or 2. l, m, n and q are each 0 or a positive integer,
p is a positive integer. Rα, Rβ, and Rγ each represent a single bond or — (CH ₂ ) _k — (Zα) _j —Rδ—. Zα
Is -OCO-, -O-, -N (Rε) CO-, -CO
Represents O-, -CON (Rε)-. Rδ represents a single bond, alkylene having 1 to 12 carbon atoms, substituted alkylene, cycloalkylene, arylene, or aralkylene. Rε
Represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms. k is 0 or a positive integer, and j is 0
Or 1. Further, as a water-insoluble and alkali-soluble silicone-containing polymer, as represented by the following general formulas [III] and / or [IV] as described in Japanese Patent Application No. 11-20224 or Japanese Patent Application No. 11-31591. Having a repeating unit to be used.

[0065]

Embedded image Here, in the general formulas (III) and (IV), X is
It is a group selected from the group consisting of a —C (＝ O) —R group, a —CH (OH) —R group, and a carboxyl group, and a plurality of Xs in the formula may be the same or different. Where R is
It represents a hydrogen atom or a hydrocarbon group which may have a substituent. R ′ to R ′ ″ ″ may be the same or different, and may be a hydroxyl group or an optionally substituted alkyl group, cycloalkyl group, alkoxy group, alkenyl group, aralkyl group and phenyl. A group selected from the group consisting of groups. Y is an alkyl group, an alkoxy group or a siloxyl group. R0 represents a hydrogen atom, a halogen atom, or a group selected from the group consisting of an aliphatic hydrocarbon group and an aromatic hydrocarbon group which may have a substituent. l, m,
n and q are each 0 or a positive integer, and p is a positive integer.

Next, the compound which generates an acid upon irradiation with the actinic ray or radiation will be described. Compounds that generate an acid upon irradiation with actinic rays or radiation are decomposed upon irradiation with actinic rays or radiation to generate an acid, as described in Japanese Patent Application Nos. 10-354878 and 11-143614. And a photo-initiator for photo-cationic polymerization, a photo-initiator for photo-radical polymerization, a photo-decolorant for dyes, a photo-discolorant, or an acid generated by known light used in micro-resist and the like. Compounds and mixtures thereof can be appropriately selected and used.

Next, a polymer having an acid-decomposable group and having a property of increasing the solubility in an aqueous alkaline developer by the action of an acid will be described. As a polymer having a group capable of being decomposed by an acid and having a property of increasing the solubility in an aqueous alkaline developer by the action of an acid, Japanese Patent Application Nos. 10-354878 and 11-143614 or Japanese Patent Application Nos. flat
Examples thereof include those having a repeating unit represented by the following general formula [V] as described in JP-A-11-331568.

[0068]

Embedded image Here, in the general formula [V], R _{1 to} R ₃ , R _{5 to} R ₇ , R ₉ to
R ₁₁ may be the same or different and is a hydrogen atom, a halogen atom, a group represented by —COZR ₁₃ , or an alkyl group, an aralkyl group or an alkoxy group which may have a substituent. R ₄ and R ₈ may be the same or different and are a single bond or a divalent to pentavalent group represented by the following formula.

[0069]

Embedded image A _{1 to} A ₅ may be the same or different, and represent a hydrogen atom,
— (R ₁₄ ) _e or a single bond, and at least one of A _{1 to} A ₅ represents a single bond. R ₁₄ represents the above R _{1 to} R ₃ , R ₅ to
The same meaning as R _7, R ₉ ~R _11. R ₁₅ is a single bond or -R
Is a group represented by - ₃₀ -Y _3. Z is a single bond or -O
-, - NH -, - represents a group represented by any one of the - NR _25.
Y ₃ is a single bond, —S—, —O—, or —OC (＝ O)
-. R ₁₃ and R ₂₅ may be the same or different and represent an alkyl group, a cycloalkyl group or an aralkyl group which may have a substituent. R ₃₀ is an alkylene group or a cycloalkylene group which may have a substituent. R ₂ and R ₄ , or R ₆ and R ₈ may be bonded to each other to form a group shown below.

[0070]

Embedded image In the above groups, Y ₀ has the same meaning as R ₄ and R ₈ , and Y ₀ is G
Alternatively, it combines with Q.

G is -OH, -COOH, -CONHC
OR ₁₆ , —CONHSO ₂ —R ₁₆ and —SO ₂ NH—R ₁₆
Represents a group selected from the group consisting of: R ₁₆ is an optionally substituted alkyl group, cycloalkyl group, acyl group or aryl group. Q represents a group selected from the group shown below.

[0072]

Embedded image Y ₂ is —O—, —OC (＝ O) —O— or —COO
Represents one of-. R ₁₈ , R ₁₉ , R ₂₁ , and R ₂₂ may be the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a halogen atom as a substituent. R ₂₀ is a silyl group, an oxysilyl group, or an alkyl group having 1 to 4 carbon atoms which may have a halogen atom as a substituent. R ₂₃ represents a hydroxyl group, a halogen atom, an acyl group, an optionally substituted alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an allyloxyalkyl group, an aralkyloxyalkyl group, or a cycloalkyl-alkyl Group. R ₁₇ is
Represents any of the groups shown below.

[0073]

Embedded image Said R _26, R ₂₇ are each as defined in the above _{R 18, R 19, R 21} , R 22. R ₂₈ is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may have a substituent. R ₂₆ and R ₂₇ and / or R ₂₈ may combine with each other to form a 4- to 9-membered monocyclic or polycyclic ring. R ₂₉
Is a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, acyl group, acylamino group, or alkoxycarbonyl group. R ₁₂ is a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group or an alkoxy group which may have a substituent, or —COZR ₁₃ (Z and R ₁₃ are as defined above). Group or any of the substituents shown below.

[0074]

Embedded image In the above formula, Z and R ₁₅ are as defined above. R ₂₄ has the same meaning as R ₂₉ described above. a, c, and d are each 0 or a positive integer, and b is a positive integer. e is 0 or an integer of 1 to 4, f and g are each an integer of 1 to 4, and h is 1 to 4.
6 is an integer.

Further, as a polymer having a property of increasing the solubility in an aqueous alkaline developer by the action of an acid, a side chain represented by the following general formula [described in Japanese Patent Application No. 11-20224] VI], general formula [VII] or general formula [VII
And those containing a repeating unit containing the group represented by I].

[0076]

Embedded image In the general formulas [VI] to [VIII], Ra, Rb and Rc each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent. s represents an integer of 2 or more.

Further, as a polymer having a property of increasing the solubility in an aqueous alkaline developer by the action of an acid, it is represented by the following general formula [IX] as described in Japanese Patent Application No. 11-31591. And those having a repeating unit.

[0078]

Embedded image In the general formula [IX], R _{1 to} R ₃ and R _{5 to} R ₇ are the same or different and are a hydrogen atom, a halogen atom, —C (＝ O) —Z—R.
A group represented by ₁₃ , or may have a substituent,
It is an alkyl group, an aralkyl group or an alkoxy group. Here, Z is a single bond, -O-, -NH- or -N
(R ₂₅ ) —. R ₁₃ and R ₂₅ are the same or different and each represents an alkyl group, a cycloalkyl group or an aralkyl group which may have a substituent. R ₄ and R ₈ are the same or different and represent a divalent to pentavalent group represented by the following formula.

[0079]

Embedded image In the above formula, A _{1 to} A ₅ are the same or different and are each a hydrogen atom,
—R ₁₄ or a single bond, and at least one of A _{1 to} A ₅
One is a single bond. R ₁₅ is a single bond or —R ₃₀ —Y ₃ —
Is a group represented by Z is a single bond or -O-, -NH
—, And —NR ₂₅ —. d
Is an integer of 0 or more. Here, R ₁₄ is the above R _1-
R _{3 has} the same meaning as R _{5 to} R ₇ . R ₃₀ represents an alkylene group or a cycloalkylene group which may have a substituent. Y ₃ is a single bond, -S-, -O-, or -OC (=
O)-. R ₂₅ has the same meaning as described above. R ₂ and R ₄ and R ₆ and R ₈ may be bonded to each other to form a group shown below.

[0080]

Embedded image In the above formula, Y ₀ has the same meaning as R ₄ and R ₈ , and Y ₀ bonds to G or Q. G is -OH, -COOH, -C
ONHCOR ₁₆ , —CONHSO ₂ —R ₁₆ and —SO ₂ N
It represents a group selected from the group consisting of H-R _16. Where R
₁₆ represents an alkyl group, a cycloalkyl group, an acyl group or an aryl group which may have a substituent. Q is any of the groups represented by the following formulas.

[0081]

Embedded image In the above formula, R ₂₁ and R ₂₂ are the same or different and represent an alkyl group having 1 to 4 carbon atoms which may have a hydrogen atom or a halogen atom as a substituent. R ₂₃ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group which may have a substituent. R ₂₆ and R
₂₇ is the same or different and has the same meaning as R ₂₁ and R ₂₂ . R
₂₈ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may have a substituent. a
Is an integer of 0 or more, and b is a positive integer. f and g are each an integer of 1 to 4.

Next, the compound having a group capable of being crosslinked by an acid, which is used in the present invention, will be described. As a compound having a group capable of being crosslinked by an acid and having a property of decreasing the solubility in an alkaline developer by the action of an acid, for example, a compound obtained by reacting formaldehyde with melamine, benzoguanamine, glycoluril, or the like, Examples thereof include alkyl-modified products, epoxy compounds, aldehydes, azide compounds, organic peroxides, and hexamethylenetetramine. In addition, a partially reacted product of these and an alkali-soluble resin can also be used effectively.

The compound having an olefinically unsaturated group used in the present invention preferably has a boiling point of 100 ° C. or higher at normal pressure.

[Brief description of the drawings]

FIG. 1 is a diagram showing a fine pattern forming method according to a first embodiment of the present invention;

FIG. 2 is a diagram showing a fine pattern forming method using proximity exposure according to the first embodiment of the present invention;

FIG. 3 is a diagram showing a contact exposure apparatus using vacuum evacuation;

FIG. 4 is a diagram showing a contact exposure apparatus using air blowing.

FIG. 5 is a diagram showing a fine pattern forming method using an optical stamp according to a second embodiment of the present invention.

FIG. 6 is a diagram showing a fine pattern forming method using an optical stamp and proximity exposure according to a second embodiment of the present invention.

FIG. 7 is a diagram showing a fine pattern forming method using a probe according to a third embodiment of the present invention.

FIG. 8 is a diagram in which an antireflection film is provided between a substrate and a first resist.

FIG. 9 is a diagram in which an antireflection film is provided between a first resist and a second resist.

[Explanation of symbols]

 1 Substrate 2 First resist layer 3 Second resist layer 4 Mask 5 Glass substrate 6 Metal film 7 Near-field light

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H096 AA25 BA05 BA06 BA10 BA20 CA06 EA02 EA05 GA08 HA23 JA04 KA02 KA08 KA19 LA01 5F046 BA01 BA10 NA02 NA05 NA07 NA17 NA18 PA01

Claims (18)

[Claims] 1. A first resist layer which can be removed by dry etching on a substrate, and a second resist which has a photosensitive dry etching resistance in which only a portion irradiated with light or only a non-irradiated portion is soluble in a developing solvent. A recording material obtained by laminating a resist layer in this order is irradiated with the near-field light in a desired pattern onto the second resist layer of the recording material by means for receiving irradiation light and generating near-field light. Developing a pattern of the second resist layer by developing the second resist layer, and dry-etching the first resist layer using the pattern as a mask, thereby forming a pattern on the recording material substrate. Forming a fine pattern. 2. The second resist layer has a thickness of 100 nm.
2. The method for forming a fine pattern according to claim 1, wherein: 3. The method for forming a fine pattern according to claim 1, further comprising an antireflection means for the irradiation light on the substrate. 4. The method according to claim 3, wherein the antireflection means is an antireflection film formed between the substrate and the first resist layer. 5. The method according to claim 3, wherein the antireflection means is an antireflection film formed between the first resist layer and the second resist layer. 6. The near-field light generating means is a mask for generating near-field light from a metal pattern formed on a material having a light transmitting property with respect to the irradiation light. The method of forming a fine pattern according to any one of claims 1 to 5, wherein light irradiation is performed by closely adhering to the second resist layer or by approaching the area where the near-field light reaches. 7. A method in which said means for generating near-field light forms an uneven pattern on a surface of a material having a light transmitting property with respect to said irradiation light, and generates near-field light from said uneven portion by total reflection. 6. A stamp, wherein light irradiation is performed by bringing the concavo-convex pattern into close contact with the second resist layer or as close as possible within a range where the near-field light reaches.
The method for forming a fine pattern according to claim 1. 8. The method according to claim 1, wherein the means for generating the near-field light is a probe having an opening having a diameter smaller than the wavelength of the irradiation light, and performing the light irradiation by scanning the probe on the second resist layer. 6. One of claims 1 to 5, characterized in that:
The method for forming a fine pattern according to the above item. 9. A method of irradiating the near-field light by bringing the second resist layer and the means for generating the near-field light into close contact by performing vacuuming in an exposure apparatus. 8. The method for forming a fine pattern according to 6 or 7. 10. The method according to claim 1, wherein the second resist layer and the means for generating the near-field light are brought into close contact with each other by performing vacuum evacuation in an exposure apparatus and blowing air from the back surface of the substrate. 8. The method for forming a fine pattern according to claim 6, wherein light is applied. 11. The method according to claim 1, wherein the first resist layer is subjected to oxygen plasma etching. 12. The fine pattern forming method according to claim 1, wherein the second resist layer is made of a pattern forming material containing a compound having a silicon atom. 13. The method according to claim 12, wherein the content of the silicon atoms is 1% or more and 50% or less of the solid content in the second resist layer. 14. The method according to claim 1, wherein the second resist layer is made of a pattern forming material containing at least one of a naphthoquinonediazide compound and a diazoketone compound, and a water-insoluble and alkali-soluble silicone-containing polymer. 14. The method for forming a fine pattern according to any one of 13). 15. The action of the second resist layer, wherein the second resist layer has a water-insoluble and alkali-soluble silicone-containing polymer, a compound that generates an acid upon irradiation with actinic rays or radiation, and a group that can be decomposed by an acid. The method for forming a fine pattern according to any one of claims 1 to 13, comprising a pattern-forming material containing a polymer or a low-molecular compound having a property of increasing solubility in an aqueous alkaline developer. . 16. A water-insoluble silicone-containing polymer having a functional group in which the second resist layer has a group decomposable by an acid and whose solubility in an aqueous alkaline developer is increased by the action of an acid. 2. A pattern-forming material comprising: a compound which generates an acid upon irradiation with actinic rays or radiation; and a polymer or a low-molecular compound having a group which can be cross-linked by the acid.
14. The method for forming a fine pattern according to any one of items 13 to 13. 17. The water-insoluble silicone-containing polymer, wherein the second resist layer has an olefinically unsaturated group and has a property of decreasing the solubility in an aqueous alkaline developer by a polymerization reaction, and an actinic ray or radiation. The method for forming a fine pattern according to any one of claims 1 to 13, comprising a pattern-forming material containing a compound capable of initiating a polymerization reaction upon irradiation with a light. 18. The method according to claim 18, wherein the second resist layer has a water-insoluble and alkali-soluble silicone-containing polymer, a compound capable of initiating a polymerization reaction upon irradiation with actinic rays or radiation, and an olefinically unsaturated group. 14. The method for forming a fine pattern according to claim 1, comprising a pattern forming material containing a polymer or a low molecular compound having a property of decreasing the solubility in an alkali developer by a reaction. .