JP2002244298A - Polymer built-up film, resist comprising polymer built-up film, composite polymer built-up film, resist comprising composite polymer built-up film and method for producing composite polymer built-up film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer built-up film having a high orderly film structure with con trolled molecular orientation, forming a stable coating film and having a smooth film surface and a film thickness adjustable by building-up frequency on a nanometer level and to provide a composite polymer built-up film and a high sensitivity and high resolution resist material comprising the built-up film and a photo-acid generating agent or a polymer built-up film having photo-acid generating function. SOLUTION: The polymer built-up film comprises a copolymer of an N-alkyl substituted acrylamide and tert-butoxycarboxystyrene and a photo-acid generating agent. The composite polymer built-up film comprises a polymer built-up film comprising the above copolymer and a polymer built-up film comprising a copolymer of neopentyl methacrylamide and anthryl methacrylate. A resist material using the polymer built-up film comprising the copolymer of an N-alkyl substituted acrylamide and tert-butoxy carboxystyrene and the photo-acid generating agent and a resist material comprising the composite polymer built-up film comprising the above copolymer and the polymer built-up film comprising the copolymer of neopentyl methacrylamide and anthryl methacrylate are obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polymer cumulative film comprising a copolymer of N-alkyl-substituted acrylamide and tert-butoxycarboxystyrene and a photoacid generator, and a polymer cumulative film comprising the copolymer. A composite polymer cumulative film comprising a neopentyl methacrylamide and a polymer cumulative film comprising an anthryl methacrylate copolymer, and further comprising a copolymer of an N-alkyl-substituted acrylamide and tert-butoxycarboxystyrene and a photoacid generator. Resist material using a polymer cumulative film composed of a polymer and a composite polymer cumulative film composed of a polymer cumulative film composed of a copolymer of neopentyl methacrylamide and anthryl methacrylate and a polymer cumulative film composed of a copolymer of neopentyl methacrylamide and anthryl methacrylate And a method for producing the composite polymer cumulative film.

[0002]

2. Description of the Related Art It has been known that an amphiphilic compound such as a higher fatty acid such as stearic acid forms a monomolecular film having a thickness of one molecule on a water surface. The molecular accumulation film formed by transferring the film to a solid substrate is called a Langmuir-Blodgett film (LB film), a method of controlling the film thickness at the molecular level and producing an organic ultrathin film in which molecules are regularly arranged. It is attracting attention.

Further, in the field of integrated circuit elements, with the densification of integrated circuits, finer resist patterns are required. The LB film has a uniform and highly ordered film structure with controlled molecular orientation, and the film thickness can be controlled at the molecular level. I have.

As an example in which such an LB film is applied to a resist material, as disclosed in Japanese Patent Application Laid-Open No. 62-260140, an LB film is formed using a low molecular weight compound, and a light or electron beam is formed thereon. To polymerize the low molecular weight compound. This is an example of a negative resist, but the sensitivity in the case of light irradiation is not enough,
Since an organic solvent must be used for the developer, there is a problem that practical use is difficult.

Also, polymer LB is used as a positive resist.
An example using a film is disclosed in JP-A-2000-143831. Here, an LB film is formed by preliminarily polymerizing a polymer to be spread on a water surface and transferring it to a substrate. However, also in this case, the sensitivity is low and not at a practical level.

[0006]

SUMMARY OF THE INVENTION The present inventor has studied to develop a novel polymer cumulative film which has solved the above-mentioned problems of the prior art and a highly sensitive resist material using the same.
As a result, N-alkyl substituted acrylamide and tert
-Accumulated polymer film comprising a copolymer of butoxycarboxystyrene and a photoacid generator, and a polymer accumulated film comprising the copolymer and a polymer accumulated film comprising a neopentyl methacrylamide and anthryl methacrylate copolymer And a resist material using a polymer cumulative film comprising a copolymer of N-alkyl-substituted acrylamide and tert-butoxycarboxystyrene and a photoacid generator, and the copolymer. We have found that a resist material consisting of a polymer cumulative film and a composite polymer cumulative film consisting of a polymer cumulative film consisting of neopentyl methacrylamide and anthryl methacrylate copolymer can solve the drawbacks of the conventional technology. Completed the invention. An object of the present invention is to provide a highly ordered film structure in which the molecular orientation is controlled, to form a stable film, the film surface is smooth, and the film thickness can be controlled at the nanometer level which can be adjusted by the number of times of accumulation. It is an object of the present invention to provide a high-sensitivity, high-resolution resist material comprising a molecular accumulation film, a composite polymer accumulation film, and the accumulation film and a photoacid generator or a polymer accumulation film having a photoacid generation function.

[0007]

The present invention is described below. (1) represented by the following formula (1) and having a number average molecular weight of 1,000
A polymer film comprising a copolymer having a molecular weight of 0 to 100,000 and a photoacid generator.

Embedded image (1) (wherein R ₁ and R ₂ may be the same or different and represent hydrogen or a methyl group, R ₃ represents a tert-butoxycarbonyl group, a trimethylsilyl group or a tetrahydropyranyl group, and X represents 0.4 to 0.95, n is 10-1
4 is represented. )

(2) A resist material comprising the polymer cumulative film according to the above (1),

(3) A polymer cumulative film comprising a copolymer represented by the formula (1) described in the above item 1 and having a number average molecular weight of 1,000 to 100,000, and a compound represented by the following formula (2): A composite polymer cumulative film obtained by laminating a polymer cumulative film comprising a copolymer having a number average molecular weight of 1,000 to 100,000 as shown.

Embedded image (2) (where Y represents 0.5 to 0.9)

(4) A resist material comprising the composite polymer cumulative film according to the above (3).

(5) A polymer cumulative film comprising a copolymer represented by the formula (1) described in the above item 1 and having a number average molecular weight of 1,000 to 100,000; (2) having a number average molecular weight of 1,000 to 100,
A method for producing a composite polymer cumulative film, which comprises superposing a polymer cumulative film comprising a copolymer having a molecular weight of 000.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a copolymer represented by the formula (1) is an N-substituted acrylamide and a tert-
Obtained by copolymerization with butoxycarboxystyrene,
R ₁ and R ₂ may be the same or different and each represents hydrogen or a methyl group; R ₃ represents a tert-butoxycarbonyl group, a trimethylsilyl group or a tetrahydropyranyl group; n represents a number of 10 to 14; Is 0.6 ~
Represents 0.95. n may be smaller than 10 or 14
If it is larger, it is not practical because the strength of the obtained LB film is weakened. Similarly, if X is smaller than 0.6, L
The strength of the B film decreases. Further, when X is larger than 0.95, the sensitivity as a resist decreases.

The copolymer represented by the formula (1) can be produced by a known method, and is not particularly limited.
For example, N-substituted acrylamide and substituted styrene are dissolved in an organic solvent together with a radical polymerization initiator such as 2,2-azobisisobutylnitrile.
The polymerization is carried out at 150C for 15 to 30 hours. After completion of the reaction, it is obtained by reprecipitation with acetonitrile or the like and purification.

The number average molecular weight of the copolymer represented by the formula (1) is 1,000 to 100,000. When the number average molecular weight exceeds 100,000, aggregation of the polymer film occurs, so that a highly ordered film structure with controlled molecular orientation cannot be obtained. On the other hand, when the number average molecular weight is less than 1,000, the polymer LB film is in an aggregated state. Instead, the membrane expands.

The copolymer represented by the formula (2) is a copolymer of N-neopentyl methacrylate and 9-anthryl methacrylate. Y represents 0.5 to 0.9. When Y is smaller than 0.5, the strength of the LB film becomes weak. 0.
If it is larger than 9, the sensitivity as a resist decreases.

The copolymer represented by the formula (2) can be produced by a known method and is not particularly limited. For example, N-neopentyl methacrylate and 9-anthryl methacrylate are dissolved in an organic solvent together with a radical polymerization initiator such as 2,2-azobisisobutylnitrile, and after degassing, at 50 to 70 ° C. for 15 to 30 hours. Perform polymerization. After completion of the reaction, purification may be performed by reprecipitation with acetonitrile or the like.

The number average molecular weight of the copolymer represented by the formula (2) is 1,000 to 100,000. When the number average molecular weight exceeds 100,000, aggregation of the polymer film occurs, so that a highly ordered film structure with controlled molecular orientation cannot be obtained. On the other hand, when the number average molecular weight is less than 1,000, the polymer LB film is in an aggregated state. Instead, the membrane expands.

The polymer cumulative film of the present invention can be prepared as follows. The copolymer represented by the formula (1) or (2) is dissolved in an organic solvent, and a required amount of this solution is dropped on a water surface to form a polymer monomolecular film on the water surface, and the organic solvent is completely removed. Allow to evaporate. Next, the polymer monomolecular film is compressed at a constant speed using a Teflon (registered trademark) bar to obtain a monomolecular film densely packed with molecules having a high collapse pressure. Next, while maintaining the accumulated pressure at a predetermined value, the substrate is moved up and down at a predetermined speed so as to pierce the polymer film, and the polymer monomolecular films are accumulated one by one on the substrate to obtain a polymer accumulated film.

Whether or not a monomolecular film is formed can be determined by measuring the occupied area per molecule and the surface pressure calculated from the film area. The surface pressure of the film at the time of accumulation may be any surface pressure within a range where the film forms a solid condensed film from the surface thickness (π) -area (A) curve. However, if the pressure is too high, the molecules constituting the membrane overlap, while if the pressure is too low, stable accumulation cannot be achieved. In order to form a good cumulative film, it is preferable to use a surface pressure of about 10 to 40 mN / m.

As the organic solvent for dissolving the copolymer represented by the formulas (1) and (2), the copolymer is dissolved, and after the film is formed on the water surface, it completely evaporates without remaining on the film surface. Solvents are good. Examples of such solvents include halogenated hydrocarbons such as chloroform, aromatic compounds such as toluene, aliphatic hydrocarbons such as hexane, and esters such as ethyl acetate, from the viewpoint of the solvent evaporation rate during film formation. Halogenated hydrocarbons such as chloroform are preferred.

If the concentration of the copolymer dissolved in the above-mentioned solvent is too high, polymer aggregates are formed and a good film cannot be obtained. On the other hand, if the concentration is too low, the amount of the solvent becomes too large and the water tank becomes contaminated, resulting in high quality. Film cannot be obtained. 0.0001-0.
A concentration of 005 mol / l is preferred.

As the photoacid generator used in the present invention, many known compounds and mixtures thereof can be used. For example, various onium salt compounds such as ammonium salts, diazonium salts, eudonium salts, sulfonium salts, selenium salts, arsonium salts, phenyltrihalomethylsulfone compounds, halomethyltriazine compounds, halomethyloxadiazole compounds, tri (2,3- Organic halogen compounds such as dibromo) isocyanurate;
2-naphthoquinonediazide- (2) -4-sulfonic acid ester or amide compound, nitrobenzyl alcohol sulfonic acid ester compound, oxime sulfonic acid compound, N-hydroxyamide or imide sulfonic acid ester compound, β-ketosulfone Compounds, sulfonic acid generators such as benzoin sulfonic acid compounds, and mixtures thereof can be mentioned.

Among the compounds represented by the formula (2), the 9-anthrylmethyl methacrylate moiety functions as a photoacid generator. That is, when light such as DeepUV is irradiated, an anthrylmethyl group is eliminated, and this reacts with water in the system to generate a proton. The generation of this proton can be confirmed by, for example, immersing a cast film or a cumulative film containing 9-anthrylmethyl methacrylate irradiated with light in a solution containing a merocyanine dye, and measuring the absorption spectrum of the merocyanine dye. The desorption of the anthrylmethyl group is confirmed by directly measuring the absorption spectrum of the light-irradiated cumulative film and eliminating the absorption due to the anthrylmethyl group near 250 nm.

Substrates on which polymer monomolecular films are accumulated include inorganic substrates such as silicon plate, gallium arsenide plate, quartz plate, glass plate, ceramic plate, calcium fluoride plate, polyamide, polysulfone, polyester, polycarbonate, fluorine Organic substrates such as resin, polyimide, polyether sulfone, acetal resin, polyphenylene sulfide, and polyphenylene oxide can be given.

The substrate can be used as it is for accumulating a polymer monomolecular film, but if necessary, the substrate surface can be subjected to a hydrophobic treatment. For the hydrophobic treatment, a method of treating with a silane coupling agent such as dimethyldichlorosilane or hexamethyldisilazane may be used.

The accumulation is performed by accumulating monomolecular films on both sides of the substrate by moving the substrate up and down. By repeating this operation, the thickness of the accumulated film can be set to a desired thickness. Its thickness is from 1 to 1,000 layers, preferably from 10 to 200 layers.

The composite polymer cumulative film of the present invention is composed of the polymer cumulative films represented by the formulas (1) and (2). The structure is such that the polymer cumulative film represented by the formula (1) is 1 to 500.
After the layers are accumulated, a two-layer structure in which 1 to 500 layers of the polymer accumulation film represented by the formula (2) are accumulated thereon may be used. At this time, the polymer cumulative film represented by the formula (2) may be accumulated below the polymer cumulative film represented by the formula (2). Further, 1 to 100 layers of the polymer cumulative film represented by the formula (1) are accumulated, and the polymer cumulative film represented by the formula (2)
100 layers, 1 to 100 layers of the polymer cumulative film represented by the formula (1), and 1 to 100 layers of the polymer cumulative film represented by the formula (2) thereon. It can also be a multilayer structure.

In the case of application as a resist, light, electron beam,
By irradiating energy rays such as X-rays through a mask, a chemical reaction occurs in the polymer accumulation film of the irradiated portion, and a pattern is drawn by utilizing a difference from a non-irradiated portion. Since the copolymer of the present invention has UV absorption in the ultraviolet region, ultraviolet light and far ultraviolet light can be used as a light source. Specifically, a high-pressure mercury lamp or a xenon lamp can be used. In the case of electron beam irradiation, an arbitrary pattern can be drawn by direct drawing without using a mask.

Next, the exposed cumulative film is treated with an organic solvent,
Alternatively, it is immersed in a developing solution such as an aqueous alkali solution and developed.
As the developer, an organic compound of ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, or tetramethyl ammonium hydroxide, KOH,
An aqueous solution of NaOH and sodium carbonate is preferred, and an aqueous solution of tetramethylammonium hydroxide and KOH is particularly preferred. By developing, the exposed portion is washed away, and the unexposed portion remains to obtain a positive pattern.
The concentration of the aqueous solution used for the developer is 0.01 to 10 wt.
%, Preferably at a temperature of 15 ° C to 50 ° C, preferably 20 ° C.
~ 35 ° C.

By applying an etching solution, a portion having no pattern can be etched and etched. The etching solution depends on the substrate to be etched. For example, for gold, iodine /
Using a mixture of ammonium iodide / ethanol / water,
In the case of a silicon oxide film, a mixed solution of hydrogen fluoride / hydrogen peroxide is used. The cumulative film of the present invention has excellent adhesion in the above-mentioned mixed solution, and is not eroded by the etching solution.

The polymer cumulative film and the composite polymer cumulative film of the present invention can be used in addition to a resist, as well as a field-effect transistor, a liquid crystal display device, a light modulation device, a photoelectric tube device, a nonlinear optical device, a chromochromic device, and a two-dimensional magnetic material. It can be applied to fields such as surface coating, protective films for magnetic heads and the like.

[0032]

The present invention will be described in more detail with reference to the following examples.

Synthesis Example 1 Synthesis of a copolymer (copolymer represented by formula 1) consisting of N-dodecylacrylamide and 4-tert-toxylcarboxystyrene: N-dodecylacrylamide
1.0 g (4.44 mol) and 0.978 g (4.44 mol) of 4-tert-butoxycarboxystyrene
Is dissolved in 20 ml of toluene, and 2,2 is used as a reaction initiator.
2'-azobisisobutyronitrile (1/1 of the monomer)
(00 mol) was subjected to radical copolymerization at 60 ° C. for 24 hours. After terminating the polymerization, toluene was distilled off under reduced pressure, and after concentration, purification was repeated using acetonitrile as a reprecipitation solvent to obtain a copolymer. The yield was 0.55 g. The molar ratio of N-dodecylacrylamide and 4-tert-butoxycarboxystyrene in this copolymer was 0.47: 0.5 as a result of ¹ H-NMR spectrum measurement.
It was 3.

Synthesis Examples 2 to 6 Polymers having different compositions were synthesized according to Synthesis Example 1 by changing the charging ratio of N-dodecylacrylamide (D) and 4-tert-butoxycarboxystyrene (B). The results are shown in the table below.

Example 1 Preparation of a polymer cumulative film of a copolymer consisting of N-dodecylacrylamide and 4-tert-butoxycarboxystyrene: For measurement, use a USI Film Balance.
Using Controller FSD-110, 15
℃ chloroform solution of the copolymer synthesized in a water tank on the Synthesis Example 1 was held to expand required amount, and compressed at a constant rate (14cm 2 / ^min) using a Teflon barrier. The occupied area A per molecule calculated from the film area and the surface pressure p were measured. FIG. 1 shows the relationship. In each case, it was found that a monomolecular film (monomolecular film) having a high collapse pressure and densely packed with molecules was formed. Next, when the surface pressure of the membrane is 20
While compressing with a Teflon barrier so as to obtain mN / m, a silicon wafer which has been subjected to a hydrophobic treatment on a polymer monomolecular film having an introduction rate of 4-tert-butoxycarboxystyrene of 53% is moved up and down at a rate of 10 mm / min. As a result, a cumulative ratio of about 0.95 was obtained both at the time of ascending and descending. By repeating ascent and descent while maintaining such conditions, a 40-layer polymer accumulation film on one side was produced on both surfaces of the substrate.

Examples 2 to 6 Copolymers having different compositions synthesized in Synthesis Examples 2 to 6 were similarly occupied by the method described in Example 1 and occupied area per molecule A and surface pressure p calculated from the film area. Was measured. FIG. 1 shows the relationship. Further, a polymer cumulative film was prepared according to the method described in Example 1.

Example 7 The polymer cumulative film (4) on the silicon wafer of Example 1 was used.
(0 layer) was subjected to close contact exposure for 40 minutes through a photomask using a Deep UV lamp. Next, the photomask was removed and its surface was developed with a 10 wt% aqueous solution of tetramethylammonium hydroxide for 20 seconds. The fine pattern was transferred onto the silicon wafer, and a 0.75 μm line was resolved.

Example 8 A copolymer consisting of N-dodecylacrylamide and 4-tert-butoxycarboxystyrene and tri (2,3-
Preparation of mixed cumulative film of dibromopropyl) isocyanuate: For measurement, Film Balanc manufactured by USI Co., Ltd.
e Using Controller FSD-110,
On a water tank maintained at 5 ° C., a copolymer composed of N-dodecylacrylamide and 4-tert-butoxycarboxystyrene synthesized according to Example 1 above, and a photoacid generator tri (2,3-dibromopropyl) A required amount of a mixed chloroform solution with isocyanate was developed and compressed at a constant speed (14 cm ² / min) using a Teflon barrier. The occupied area A per molecule and the surface pressure p calculated from the membrane area were measured. In each case, it was found that a monomolecular film having a high collapse pressure and densely packed with molecules was formed. Next, while compressing the film with a Teflon barrier so that the surface pressure of the film becomes 20 mN / m, the silicon wafer subjected to the hydrophobic treatment is compressed to 10 mm / min.
When the cumulative ratio was measured by moving up and down at a speed of, a cumulative ratio of approximately 0.90 was obtained both at the time of ascending and descending. By repeatedly ascending and descending while maintaining such conditions, a cumulative film of 40 layers on one side was produced on both sides of the substrate.

Example 9 According to Example 8, a 20-layer cumulative film was formed on a silicon wafer subjected to a hydrophobic treatment. Then, using a deep UV lamp, the accumulated film was contact-exposed for 40 minutes through a photomask. Next, remove the photomask and 10wt%
The surface was developed with an aqueous solution of tetramethylammonium hydroxide for 20 seconds. A fine pattern was transferred onto the silicon wafer, and a 1.0 μm line was resolved.

Example 10 According to Example 8, a 20-layer cumulative film was formed on a gold film deposited on a glass substrate. Next, the accumulated film was contact-exposed for 40 minutes through a photomask using deep UV. Next, the photomask was removed, and the surface was developed with a 3% aqueous solution of tetramethylammonium hydroxide for 20 seconds. The transferred fine pattern on the gold film was etched for 30 seconds with an etching solution (iodine / ammonium iodide / ethanol / water) and rinsed with chloroform to obtain an etching pattern.

Synthesis Example 7 Synthesis of a copolymer composed of N-neopentyl methacrylate and 9-anthrylmethyl methacrylate (copolymer represented by formula 2): N-neopentyl methacrylate 0.46
5 g (3.0 mmol) and 9-anthrylmethyl methacrylate 0.
95 g (0.34 mmol) was dissolved in 12 ml of toluene, and radical copolymerization was performed at 60 ° C. for 48 hours using 2, 2′-azobisisobutyronitrile (1/100 mol based on the monomer) as a reaction initiator. . After terminating the polymerization, toluene was distilled off under reduced pressure, and after concentration, purification was repeated using acetonitrile as a reprecipitation solvent to obtain a copolymer. The yield was 0.25 g. The molar ratio of N-neopentylacrylamide to 9-anthrylmethyl methacrylate in this copolymer was 0.90: 0.10 as a result of UV absorption spectrum measurement.

Example 11 Preparation of a cumulative film of a copolymer comprising N-neopentyl methacrylate and 9-anthrylmethyl methacrylate: For measurement, use a Film Balance Controller FSD-110 manufactured by USI Corporation.
A chloroform solution of the copolymer was developed in a required amount on a water tank maintained at 15 ° C., and compressed at a constant speed (14 cm ² / min) using a Teflon barrier. The occupied area A per molecule and the surface pressure p calculated from the membrane area were measured. In each case, it was found that a monomolecular film having a high collapse pressure and densely packed with molecules was formed. Next, when the surface pressure of the monolayer is 20
The cumulative ratio was measured by raising and lowering the hydrophobically treated quartz substrate at a rate of 10 mm / min while compressing with a Teflon barrier to mN / m. By repeating ascent and descent while maintaining such conditions, 120 layers of cumulative films were formed on both surfaces of the substrate.

Example 12 The accumulated film on the quartz substrate of Example 11 was exposed using a deep UV lamp for 10 minutes, 30 minutes, and 90 minutes, changing the time as shown in FIG. Next, the exposed film is exposed to water or
When immersed in a 1 wt% aqueous solution of tetramethylammonium hydroxide for 10 seconds, it was revealed that the exposed portion was dissolved. From this, it can be seen that acid was generated by light irradiation.

Example 13 A required amount of a chloroform solution of a copolymer composed of N-neopentyl methacrylate and 9-anthrylmethyl methacrylate was dropped on a quartz substrate, and the solvent was removed by heat treatment to prepare two cast films. Dee for one cast film
Irradiated with pUV lamp for 30 minutes. Dissolve each membrane in dichloromethane solution containing the required amount of merocyanine dye,
When the UV absorption spectrum was measured, it was clarified that acid was generated in the irradiated cast film.

Example 14 A copolymer composed of N-dodecylacrylamide and tert-butyl-4-vinylphenyl carbonate (A) and N-
Preparation of Composite Polymer Cumulative Film (Hetero-Laminated Cumulative Film) of Copolymer of Neopentyl Methacrylate and 9-Anthrylmethyl Methacrylate (Compound B): First, accumulate 40 layers of the instep cumulative film on a hydrophobically treated quartz substrate. , And accumulate 20 layers of the second party's cumulative membrane on top of that
Twenty layers were added, and finally 20 layers of the second layer were accumulated on the upper layer of the instep. When the UV absorption spectrum was measured, it was found that a linear relationship was obtained between the absorption intensity and the cumulative number of layers, so that a hetero-stacked type cumulative film was formed.

Example 15 Three types of hetero-laminated LB films of different hetero-lamination type were produced on a hydrophobically treated silicon wafer in accordance with the above-described Examples 1 and 11, respectively. One is to accumulate four layers of LB films on a silicon wafer and 56 layers of instep LB films on them. This is called Ichi. Separately 26
The number of layers was accumulated, and the number of layers was 4 and the layer A was accumulated again. This is called 2. Separately, 4 layers of B and 56 layers of A were added. Let's refer to this.

Example 16 The cumulative film produced in Example 14 was irradiated with deep UV light for a predetermined time, then subjected to a heat treatment at 90 ° C. for 30 seconds, and immersed in a 1 wt% aqueous solution of tetramethylammonium hydroxide for 20 seconds. While the unexposed portions remained, the exposed portions dissolved. The change in the cumulative film thickness for each irradiation time obtained in this way was measured with a stylus profilometer.
In the case of the above Example 14, it was clear that the second party had the highest sensitivity.

Example 17 Under the same conditions as in Example 14, 40 LB films of the instep were accumulated on a hydrophobically treated silicon wafer, and the
Four LB films were accumulated. The accumulated film was exposed to a deep UV lamp for 45 minutes, heat-treated at 90 ° C. for 30 minutes, and developed in a 1 wt% aqueous solution of tetramethylammonium hydroxide for 30 seconds. 0.75μ with fine pattern transferred on silicon wafer
A resolution of m lines was obtained.

[0049]

The polymer cumulative film of the present invention can have a highly ordered film structure in which the molecular orientation is controlled, so that a stable film can be obtained. In addition, the film surface is smooth, and the film thickness can be adjusted by the number of times of accumulation and can be controlled at the nanometer level. The resist of the present invention comprises the above-described cumulative film and a photoacid generator or a polymer cumulative film having a photoacid generating function, and is characterized by high sensitivity and high resolution.
Further, since there is no defect in the film, the film is extremely stable even in the etching step.

[Brief description of the drawings]

FIG. 1 is a view showing the relationship between the occupied area per molecule of a copolymer comprising N-dodecylacrylamide and tert-butyl-4-vinylphenyl carbonate and the surface pressure.

FIG. 2 shows N-neopentyl methacrylate and 9-neopentyl methacrylate.
The figure which showed the change of the UV curve by light irradiation and development of the LB film which consists of anthryl methyl methacrylate.

FIG. 3 is a diagram showing sensitivity curves of a polymer cumulative film and a composite polymer cumulative film.

[Explanation of symbols]

The numbers in FIG. 1 represent the introduction ratio of tert-butyl-4-vinylphenyl carbonate in the copolymer consisting of N-dodecylacrylamide and tert-butyl-4-vinylphenyl carbonate. In FIG. 2, p (nPMA / AMMA) is an exposure time for a copolymer consisting of N-neopentyl methacrylate and 9-anthrylmethyl methacrylate, 0, 10, 30, and 90 minutes are exposure times, and H ₂ O is an irradiation for a predetermined time. Post-development with pure water indicates that 1 wt% TMAH was immersed in a 1 wt% aqueous solution of tetramethylammonium hydroxide after irradiation for a predetermined time. Figure 3
Among them, A represents one in Example 15, B represents second in Example 15, and C represents reference to Example 15. p (DDA / tBVPC53) is a copolymer (tBVPC introduction rate: 53%) composed of N-dodecylacrylamide (hereinafter abbreviated as DDA) and tert-butyl-4-vinylphenyl carbonate (hereinafter abbreviated as tBVPC), p (DDA / tBVPC53) / PAG represents the mixed LB film of Example 4.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/00 C08K 5/00 C08L 25/18 C08L 25/18 33/10 33/10 33/24 33 / 24 43/04 43/04 G03F 7/095 G03F 7/095 H01L 21/027 H01L 21/30 502R F term (reference) 2H025 AA00 AA01 AA02 AB16 AC01 AD03 BE00 BG00 DA11 EA07 FA03 FA17 4J002 BC121 BG051 BG121 BQ001 EB116 EN136 EU186 EU196 EU206 EV216 EV246 EV296 FD206 GP03 4J100 AB07Q AL08Q AM17P BA02Q BA22Q BA76Q BC48Q BC53Q CA04 DA01 JA38

Claims (5)

[Claims] 1. A polymer cumulative film comprising a copolymer represented by the following formula (1) and having a number average molecular weight of 1,000 to 100,000 and a photoacid generator. Embedded image (1) (In the formula, R ₁ and R ₂ may be the same or different and each represents hydrogen or a methyl group, R ₃ represents a tert-butoxycarbonyl group, a trimethylsilyl group or a tetrahydropyranyl group, and X represents 0.4 to 0.95, n represents 10 to 14.) 2. A resist material comprising the polymer cumulative film according to claim 1. 3. A polymer cumulative film comprising a copolymer represented by the formula (1) according to claim 1 and having a number average molecular weight of 1,000 to 100,000, and a polymer cumulative film represented by the following formula (2): And a composite polymer cumulative film obtained by stacking a polymer cumulative film made of a copolymer having a number average molecular weight of 1,000 to 100,000. Embedded image (2) (where Y represents 0.5 to 0.9) 4. A resist material comprising the composite polymer cumulative film according to claim 3. 5. A polymer cumulative film comprising a copolymer represented by the formula (1) according to claim 1 and having a number average molecular weight of 1,000 to 100,000, and a formula (2) according to claim 3 And a method for producing a composite polymer cumulative film, comprising superimposing a polymer cumulative film comprising a copolymer having a number average molecular weight of 1,000 to 100,000.