JP2007328333A - Image forming method through reaction development - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an improved image forming method through reaction development by which a negative photoresist can be efficiently produced. <P>SOLUTION: A photoresist layer containing a condensation polymer containing a carbonyl group (C=O) bonded to a hetero atom in the main chain thereof, an anion regenerant such as an N-substituted maleimide compound and a photoacid generator such as diazonaphthoquinone is disposed on a substrate and masked with a desired pattern, this pattern surface is irradiated with ultraviolet radiation, and development is performed with a developer comprising tetra-substituted ammonium hydroxide, a low molecular alcohol and a water-containing solvent. Exposed and unexposed portions of the photoresist layer after the irradiation with ultraviolet radiation are noticeably different in solubility in the developer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photoresist technique that can be used for manufacturing a semiconductor integrated circuit, a printed wiring board, a liquid crystal panel, and the like, and more particularly, a polymer having a carbonyl group bonded to a hetero atom in the main chain and a photoacid generator. The present invention relates to a photoresist technique in which a film is formed using an anion regenerator, irradiated with light, and a negative image is formed through a development process.

Photoresists are commonly used in photolithographic organic polymers used in the related art in photographic deck processing, for the production of printed circuit boards and printed circuit boards, or for the production of semiconductor laminates in microelectronics. .
In order to create circuit structures in the manufacture of microelectronic semiconductor integrated components, the semiconductor substrate is imaged with a photoresist layer coated with a photoresist and subsequent development creates a photoresist relief structure. This relief structure is used on a semiconductor substrate as a mask for creating an actual circuit pattern by etching-doping or coating using a metal or other semiconductor or insulating substrate. Thereafter, the photoresist mask is usually removed. A microchip relief structure is formed on the substrate using a plurality of such processing cycles.
Two different types of photoresists are known: a positive resist and a negative resist. The difference between the two types is that the exposed area of the positive photoresist is removed by the development process, leaving the unexposed area as a layer on the substrate. On the other hand, the irradiation area of the negative working photoresist remains as a relief structure.

The inventors have already developed a photoresist using a resin having a carbonyl group (C═O) bonded to a hetero atom in the main chain without having any special reactive group in the side chain of the resin skeleton. For this purpose, a new means called “reactive development image forming method” was developed (Patent Document 1).
This “reactive development image forming method” is a kind of positive photoresist technology. First, a resin containing a carbonyl group (C═O) having a photoresist layer bonded to a hetero atom (C═O) in the main chain and a photoacid generator Then, the layer is appropriately masked in a desired pattern and then irradiated with ultraviolet rays. The photoacid generator generates an acid by this ultraviolet irradiation. When this is washed with a developer containing an alkali (particularly a nucleophilic amine), a salt is formed by reacting with the acid produced by the alkali (particularly the nucleophilic amine), and the polarity of the exposed area Will increase. As a result, an alkali (particularly a nucleophilic amine) in the developing solution attacks the carbonyl group bonded to the hetero atom constituting the main chain of the polymer in the exposed region. This attack breaks the main chain at the carbonyl group. Due to the cleavage of the main chain, the polymer is reduced in molecular weight and dissolved in the developer.

JP2003-76013

  The present inventors have developed a method capable of efficiently producing a negative photoresist as an improved method of the “reactive development image forming method” (Patent Document 1).

  The inventors use a polymer having an imide group in the main chain, mix a diazonaphthoquinone compound as a photoacid generator and an N-substituted maleimide compound as an anion regenerator, and irradiate with ultraviolet rays. , Developed using a developer composed of tetramethylammonium hydroxide (TMAH), N-methyl-2-pyrrolidone (NMP), a low molecular alcohol and water, a developer for exposed and unexposed areas after UV irradiation It has been found that there is a significant difference in solubility in and a negative photoresist can be formed by utilizing the difference.

That is, in the present invention, a photoresist layer containing a condensed polymer containing a carbonyl group (C═O) bonded to a hetero atom (C═O) in the main chain, an anion regenerating agent and a photoacid generator is provided on a substrate, and a desired pattern is formed. The pattern surface is irradiated with ultraviolet light, and the photoresist layer is processed with a developer. The anion regenerant is represented by the following formula:
(In the formula, X represents a substituent represented by the following formula,
In the formula, Y represents —NR ¹ ₂ , —OR ¹ (excluding —OH), —CR ¹ ₃ or —SR ¹ (excluding —SH), and R ¹ is independently selected. And represents a hydrogen atom, an aliphatic group or an aromatic group. ), A compound represented by the following formula: R ² -CONHR ¹
Or R ² —COCH (R ¹ ) ₂
(Wherein R ² independently represents an aliphatic group or an aromatic group, and R ¹ is defined in the same manner as described above),
(In the formula, at least one of R ³ represents an aliphatic group or an aromatic group, the other represents a hydrogen atom, and Z represents an oxygen atom (—O—) or a sulfur atom (—S—).) Or a compound represented by the following formula: CH (R ⁴ ) ₂ C (R ¹ ) ₂ OCO—N (R ¹ ) ₂
(Wherein at least one of R ⁴ represents an electron withdrawing group, and the other represents a hydrogen atom, an aliphatic group or an aromatic group. R ¹ is defined in the same manner as described above). The developing solution is a reaction development image forming method comprising a solvent containing a tetra-substituted ammonium hydroxide, a low molecular alcohol and water.

  Moreover, this invention is a negative photoresist structure which has a photoresist layer formed by said method on the board | substrate, and the film thickness of this photoresist layer is 0.1-500 micrometers. A relief structure having a desired pattern can be formed as the photoresist layer.

The reaction mechanism of the “reactive development image forming method” of the present invention is considered as follows. Hereinafter, this reaction mechanism is represented by polyetherimide (PEI) as a polymer, N-phenylmaleimide (PMI) as an anion regenerant, diazonaphthoquinone (DNQ) as a photoacid generator, and TMAH ((CH _{3 4} NOH)), methanol (MeOH) as the low molecular alcohol and NMP as the solvent, but is not intended to limit the present invention.
A mask having a desired pattern is applied to the formed resin containing the polymer, the anion regenerating agent, and the photoacid generator, and ultraviolet rays are irradiated. After the irradiation, development is performed with a developer composed of a solvent containing tetra-substituted ammonium hydroxide, a low molecular alcohol, and water. In the developer, a part of TMAH exists as hydroxyl anion (HO ⁻ ).

First, the unexposed portion will be described. The reaction formula is shown below.
N-phenylmaleimide (PMI) contained in the resin reacts with TMAH-derived hydroxyl anion (HO ⁻ ) in the developer to form an anion represented by the following formula (1), and this anion reacts with water. In addition to the compound represented by the following formula (2), a hydroxyl anion (HO ⁻ ) is generated. This hydroxyl anion reacts with N-phenylmaleimide (PMI) again to repeat the formation of compound (2) and the regeneration of the hydroxyl anion.
On the other hand, the produced compound (2) forms an anion represented by the following formula (4) through a compound represented by the following formula (3) by reaction with the hydroxyl anion (HO ⁻ ). This anion reacts with water. To generate hydroxyl anions. This hydroxyl anion also reacts with N-phenylmaleimide again. That is, the hydroxyl anion is continuously regenerated through N-phenylmaleimide.
The hydroxyl anion regenerated in this way attacks the imide group of the polymer (PEI), and the polymer is dissolved and removed in NMP by the production of polyamic acid represented by the following formula (5) and the subsequent low molecular weight. it is conceivable that.

Next, the exposure unit will be described. The reaction formula is shown below. Diazonaphthoquinone (DNQ) contained in the resin is irradiated with ultraviolet rays to produce indenecarboxylic acid (6). This indenecarboxylic acid reacts with TMAH ((CH ₃ ) ₄ NOH)) to produce a highly hydrophilic salt (7).
On the other hand, N-phenylmaleimide (PMI) contained in the resin reacts with TMAH-derived hydroxyl anion (HO ⁻ ), as in the case of the unexposed portion, and is once shown by the following formulas (8) and (9). Although anions are formed, these anions react with indenecarboxylic acid (6) to produce indenecarboxylic acid anions (10) with low reactivity. That is, in the exposed area, a large amount of hydroxyl anion (HO ⁻ ) is not reproduced as in the unexposed area.
Accordingly, the polymer (PEI) is attacked by the TMAH-derived hydroxyl anion (HO ⁻ ), but the degree thereof is considered to be lower than that of the unexposed area. Further, since the salt (7) of the indenecarboxylic acid to be produced is very hydrophilic, it prevents the NMP, which is an organic solvent, from penetrating into the resin. Therefore, the degree to which the polymer component dissolves in the NMP is also compared with the unexposed area. And low. As a result, the polymer is considered to remain undissolved.

A condensed polymer containing a carbonyl group (C═O) bonded to a heteroatom in the main chain means an imide bond, a carbonate bond, an ester bond, a urethane bond, an amide bond, or these bonds, respectively, in the main chain of the polymer. A polymer containing a plurality.
Examples of the polymer that is the subject of the present invention include polyetherimide, polyamide, polyamideimide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalate, polyarylate, polyurethane, and copolymers related thereto. Can be mentioned.
The polymer to which the reaction development image forming method of the present invention can be preferably applied is a carboxyl group which reacts with a functional group capable of reacting with a base (for example, a carboxyl group or a phenolic hydroxyl group), an acid or a base, and the like. Or a reactive group capable of generating a phenolic hydroxyl group (such as an ester or phenolic ether bonded to a protecting group) or a group that undergoes a crosslinking reaction upon irradiation with light (such as an acryloyl group or a methacryloyl group).

The polymer used in the present invention further contains an anion regenerating agent and a photoacid generator.
This anion regenerant is subjected to Michael addition, hydrogen abstraction, or nucleophilic attack by the hydroxyl anion in the developing solution during development (for example, (1) or (4) of the above formula [Chemical Formula 5]). In addition, it is preferable that it remains in the film without being volatilized during pre-baking.
This anion regenerant is any of the following compounds.
(1) Compound having a structure represented by the following formula:

In the above formula, X represents a substituent represented by the following formula.
In the formula, Y represents —NR ¹ ₂ , —OR ¹ (excluding —OH), —CR ¹ ₃ or —SR ¹ (excluding —SH), preferably —NR ¹ ₂ or — Represents CR ¹ ₃ .
In these formulas, each R ¹ independently represents a hydrogen atom, an aliphatic group or an aromatic group, preferably an aromatic group, more preferably a phenyl group. Examples of the aliphatic group include alkyl groups such as a methyl group, a propyl group, a hexyl group, and a cyclohexyl group.

(2) Compound having a structure represented by the following formula:
R ² -CONHR ¹
Or R ² —COCH (R ¹ ) ₂
In the formula, each R ² independently represents an aliphatic group or an aromatic group. Examples of the aliphatic group include alkyl groups such as a butyl group, an isobutyl group, and a hexyl group, and examples of the aromatic group include a phenyl group and a phenylene group.
R ¹ is defined as above.

(3) Compound having a structure represented by the following formula:
In the formula, at least one of R ³ represents an aliphatic group or an aromatic group, and the other represents a hydrogen atom. Examples of the aliphatic group include alkyl groups such as an oxymethylene group and an octyl group, and examples of the aromatic group include a phenyl group and a phenylene group.
Z represents an oxygen atom (—O—) or a sulfur atom (—S—).

(4) Compound having a structure represented by the following formula:
^{_{CH (R 4) 2 C (}} R 1) 2 OCO-N (R 1) 2
In the formula, at least one of R ⁴ represents an electron withdrawing group, and the other represents a hydrogen atom, an aliphatic group, or an aromatic group. Examples of the aliphatic group include an alkyl group, and examples of the aromatic group include a phenyl group and a phenylene group. Examples of the electron withdrawing group include a fluorenyl group, an organic sulfoxide group, a cyano group, a nitro group, an ester group, a carbonyl group, an amide group, and a pyridyl group, preferably a fluorenyl group. Examples of the aromatic group include a phenyl group and a phenylene group.
R ¹ is defined as above.

  Examples of such an anion regenerating agent include N-substituted maleimide, N-substituted citraconimide, N-substituted succinimide, N-substituted crotonamide, N, N′-substituted fumaramide, and 4-substituted-3-butene-2. -One, N-substituted benzamide, N-substituted isovaleramide, α-substituted acetophenone, polyamideimide, epoxy resin (for example, bisphenol A diglycidyl ether), N-fluorenylmethoxycarbonyl protected amine and the like.

Further, the structure defined above may be appropriately chemically bonded to the polymer. Examples of such a polymer include a polyimide having a maleimide structure as a side chain, a maleimide polyimide at both ends (an example of a chemical formula is shown in the following formula), and the like.

As an anion regenerant, the following formula
An N-substituted maleimide compound represented by the formula (wherein R ¹ is defined in the same manner as described above) is more preferable.

  Preferred anion regenerants include, for example, N-methylmaleimide, N-ethylmaleimide, N- (n-propyl) maleimide, N- (n-hexyl) maleimide, N- (n-octyl) maleimide, N-laurylmaleimide N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide (N-substituted maleimide compound), N-phenylcitraconimide, N-phenylsuccinimide, N, N'-m-phenylenebismaleimide, N-phenyl Crotonamide, bis (N-phenyl) fumaramide, divinylsulfone, ethyl acetoacetate, 4-phenyl-3-buten-2-one, N-phenylisovaleroamide, N-methylbenzamide, polyamideimide, bisphenol A diglycidyl ether N- (9-fluorenylmethylcarbonyl) -2-methoxyethylamine, 1,4-diphenyl Nyl-1,4-butanedione and the like can be mentioned.

  The photoacid generator used in the present invention may be any one that generates acid upon light irradiation. Examples of the photoacid generator include quinonediazide compounds, onium salts, sulfonic acid esters, and organic halogen compounds. The quinonediazide compound includes 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid and a low-molecular aromatic hydroquinone compound such as 2,3,4-trihydroxy. Examples include benzophenone, 2,3,4,4′-tetrahydroxybenzophenone and trihydroxybenzene, such as 1,3,5-trihydroxybenzene, or an ester-forming compound of cresol. Examples of onium salts include triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate. These are used with esters such as t-butyl benzoate. Among these, 1,2-naphthoquinone-2-diazide-5-sulfonic acid-p-cresol ester is particularly preferable.

The anion regenerator is preferably used in an amount of 1 to 40% by weight, more preferably 10 to 20% by weight based on the total solid content in the photoresist (a mixture of polymer, anion regenerator and photoacid generator).
The photoacid generator is used in the photoresist in an amount of 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 30% by weight based on the total solid content.

The photoresist of the present invention may contain additives such as coupling agents, leveling agents, plasticizers, other film-forming resins, surfactants and stabilizers. The total amount of these additives does not exceed 25% by weight based on the total solid content of the photoresist.
The photoresist of the present invention is formulated by mixing or dissolving the components in a solvent or solvent mixture by a method known per se. Once the components are dissolved in the solution, the resulting photoresist solution may be filtered using a filtration membrane having 0.1-1 μm pores.

  Solvents suitable for the production of photoresist solutions are in principle all solvents in which the non-volatile components of the photoresist, such as polymers and photoacid generators and other additives, are sufficiently soluble and do not irreversibly react with these components. It is. Suitable solvents include, for example, aprotic polar solvents such as N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”), butyrolactone, cyclohexanone, diacetoxyethylene glycol, sulfolane, tetramethylurea, N, N-dimethyl. Acetamide, dimethylformamide, dimethyl sulfoxide, acetonitrile, diglyme, phenol, cresol, toluene, methylene chloride, chloroform, tetrahydrofuran, dioxane, acetone and the like.

A photoresist layer can be formed on the substrate using such a photoresist solution. As the substrate, any organic material such as resin, inorganic material, metal, etc. may be used, but a copper substrate or a silicon substrate is preferable.
Coating onto the substrate is usually done by dipping, spraying, roll coating or spin coating. The resulting layer thickness depends on the viscosity, solids content and spin coating speed of the photoresist solution. The photoresist of the present invention can make a layer and a relief structure having a layer thickness of 0.1 to 500 μm, preferably 1 to 100 μm. The thin layer in the multi-layer circuit can be 1-50 μm as a temporary photoresist or as an insulating layer.
After the photoresist is applied to the substrate, it is usually pre-dried at a temperature range of 50 to 120 ° C. An oven or a heating plate can be used. The drying time in the oven is 5 to 60 minutes.

Thereafter, the photoresist layer is irradiated with ultraviolet rays after being masked with a desired pattern. Ultraviolet rays refer to electromagnetic waves having a central wavelength of 250 to 450 nm, preferably 300 to 400 nm. Usually actinic light is used, but high-energy radiation such as X-rays or electron beam rays can also be used. Direct irradiation or via an exposure mask can be performed. A radiation beam can also be applied to the surface of the photoresist layer.
Usually, radiation is performed using an ultraviolet lamp. It is preferable to use a commercially available radiation apparatus such as a contact or non-contact exposure machine, a scanning projection type exposure apparatus or a wafer stepper.

After the exposure, the photoresist layer is developed with a developer.
The developer used in the present invention comprises a solvent containing tetra-substituted ammonium hydroxide, a low molecular alcohol and water.
This tetra-substituted ammonium hydroxide turns the alcohol component in the developer into an alkoxide.
This tetra-substituted ammonium hydroxide is represented by the following formula.
NR ' ₄ OH
In the formula, R ′ may be the same or different and each represents a hydrocarbon group, preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms.
Preferred tetra-substituted ammonium hydroxides include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide.

  Part of this low molecular alcohol becomes an alkoxide in the developer. Therefore, an alcohol having a molecular weight of 150 or less, particularly an alkyl alcohol having 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms per hydroxyl group, is preferably used. Examples of such low molecular alcohols include methanol, ethanol, 1-propanol, 2-propanol, butanol, octanol, ethylene glycol, 2-methoxyethanol, 2-ethoxyethanol and the like.

  The “solvent containing water” in the developer is a solvent that is compatible with water or a low molecular alcohol and has the ability to dissolve the polymer, the photoacid generator, and the anion regenerant. Examples of such a solvent include NMP, dimethylformamide, dimethyl sulfoxide, tetramethylurea, butyrolactone, diacetoxyethylene glycol, cyclohexanone, polyethylene glycol (number average molecular weight of about 500 or less).

  The composition of a preferred developer is tetra-substituted ammonium hydroxide (such as TMAH) / organic solvent (such as NMP) / water / alcohol (such as methanol), and the weight ratio thereof is preferably 0.2 to 0.6 / It is 1.0 / 0.5-2.0 / 2.0-5.0, More preferably, it is 0.4 / 1.0 / 1.0-1.6 / 3.6.

Development is performed in consideration of the type of polymer and other components, the type of developer, exposure energy, type of development, preliminary drying temperature, development temperature, and development time.
You may wash | clean with a suitable solvent after image development.
The negative photoresist of the present invention can have a polymer coating having a layer thickness of 0.1 to 500 μm, preferably 1 to 100 μm, and a sharp contoured relief structure.

The following examples illustrate the invention, but are not intended to limit the invention. In this example, a photoresist was formed by the following method and observed. The photoresist was produced by filtering the photoresist formulation of each example through a filter membrane having a pore size of 3 μm. This photoresist composition was applied by spin coating on the surface of a copper foil having a diameter of 10 cm that had not been surface-treated. Subsequently, it dried in the infrared hot air dryer. On this photoresist compound coating film, a test pattern (10-200 μm line and space pattern) for a negative photomask is placed, and using a 2 kw ultra-high pressure mercury lamp irradiation device (Oak Seisakusho product: JP-2000G), Irradiation was performed with an exposure amount that would produce an image.
The coating film after the irradiation was immersed or sonicated in the developer, washed with pure water, dried with an infrared lamp, and the resolution was observed. In some examples, the formed photoresist was observed by SEM (manufactured by Hitachi, Ltd., scanning electron microscope: S-2600N, acceleration voltage: 15-20 kV).

To 4.0 g of N-methylpyrrolidone (Mitsubishi Chemical, NMP), 1.0 g of polyetherimide (manufactured by Aldrich, weight average molecular weight 27,000, chemical formula is shown below) (hereinafter referred to as “PEI”) was added. After being dissolved, 0.3 g of diazonaphthoquinone photosensitizer PC-5 (R) (manufactured by Toyo Gosei Co., Ltd., 1,2-naphthoquinone-2-diazido-5-sulfonic acid-p-cresol ester) as a photoacid generator, and 0.2 g of N-phenylmaleimide (manufactured by Wako Pure Chemical Industries, Ltd., first grade) (hereinafter referred to as “PMI”) was added and stirred with a stirrer at room temperature for about 1 hour to prepare a photoresist composition. This solution was applied onto a 35 μm electrolytic copper foil (shine surface) by spin coating (1200 rpm / 10 sec + 2000 rpm / 30 sec), prebaked with a far-infrared hot air circulation dryer (90 ° C./10 min), and then the membrane A photosensitive PEI coating with a thickness of about 10 μm was obtained.

This was irradiated with light in the i-line to g-line band through a PET photomask by an ultraviolet exposure machine (Oak). The exposure measured with an illuminometer for the i-line band was 100 mJ / cm ² .
After exposure, TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.6 / 3.6 (weight ratio) prepared using tetramethylammonium hydroxide (TMAH, 10% methanol solution, manufactured by Tokyo Chemical Industry Co., Ltd.) ) Was used for development at 50 ° C. under ultrasonic treatment and washed with 100 g of ion-exchanged water for 1 minute. As a result, a negative image was obtained. The development time at this time was 9 minutes and 27 seconds. The resolution was 10 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

After adding 1.0 g of PEI to 4.0 g of NMP and dissolving, add 0.3 g of photosensitizer PC-5 (R) and 0.01 g of PMI, and stir with a stirrer at room temperature for about 1 hour. A product was prepared. Pre-baking and exposure were performed in the same manner as in Example 1.
The exposed PEI coating is developed at 40 ° C under ultrasonic treatment using 100g of developer consisting of TMAH / NMP / ion exchange water / methanol = 0.4 / 1.0 / 1.6 / 3.6 (weight ratio). Then, it was washed with 100 g of ion exchange water for 1 minute. As a result, a negative image was obtained. The development time at this time was 2 minutes 21 seconds. The resolution was 15 μm with a line and space pattern. The SEM photograph of this photoresist is shown in Fig. 2.

After adding 1.0 g of PEI to 4.0 g of NMP and dissolving it, 0.15 g of photosensitizer PC-5 (R) and 0.2 g of PMI are added and stirred with a stirrer at room temperature for about 1 hour. A product was prepared. Pre-baking and exposure were performed in the same manner as in Example 1.
The exposed PEI coating is developed at 50 ° C under ultrasonic treatment using 100g of developer consisting of TMAH / NMP / ion exchange water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio). Then, it was washed with 100 g of ion exchange water for 1 minute. As a result, a negative image was obtained. The development time at this time was 6 minutes. The resolution was 20 μm with a line and space pattern.

After adding 1.0 g of PEI to 4.0 g of NMP and dissolving it, add 0.15 g of photosensitizer PC-5 (R) and 0.01 g of PMI and stir with a stirrer at room temperature for about 1 hour. A product was prepared. Pre-baking and exposure were performed in the same manner as in Example 1.
The exposed PEI coating is developed at 50 ° C under ultrasonic treatment using 100g of developer solution consisting of TMAH / NMP / ion exchange water / methanol = 0.4 / 1.0 / 1.6 / 3.6 (weight ratio). Then, it was washed with 100 g of ion exchange water for 1 minute. As a result, a negative image was obtained. The development time at this time was 10 minutes 30 seconds. The resolution was 15 μm with a line and space pattern.

  In the exposed PEI coating film obtained by the same operation as in Example 3, using a developing solution 100 g consisting of TMAH / NMP / ion-exchanged water / ethanol = 0.4 / 1.0 / 1.6 / 3.6 (weight ratio), dipping According to the method, development was performed at 50 ° C. and washed with 100 g of ion-exchanged water for 1 minute. As a result, a negative image was obtained. The development time at this time was 8 minutes. The resolution was 10 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

  A developer comprising TMAH / NMP / ion-exchanged water / ethanol = 0.4 / 1.0 / 1.6 / 3.6 (weight ratio) on an exposed PEI coating film (film thickness 26.5 μm) obtained by the same operation as in Example 1. Using 100 g, development was carried out at 50 ° C. under ultrasonic treatment, and washed with 100 g of ion-exchanged water for 1 minute. As a result, a negative image was obtained. The development time at this time was 2 minutes 22 seconds. The resolution was 40 μm with a line and space pattern.

The photosensitive PEI coating film obtained by the same operation as in Example 1 was irradiated with light in the i-line to g-line band through a PET photomask with an ultraviolet exposure machine. The exposure measured with an illuminometer for the i-line band was 2000 mJ / cm ² . After exposure, use 100g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 10 minutes and 45 seconds. The resolution was 30 μm with a line and space pattern.

Fluorine-containing polyimide instead of PEI (previously reported (T. Miyagawa, T. Fukushima, T. Oyama, T. Iijima, M. Tomoi, J. Polym. Sci., Part A: Polym. Chem., 41, 861-871 (2003).) Using a weight average molecular weight of 50,000, the chemical formula is shown in the following formula, the same operation as in Example 1 was performed to prepare a photoresist formulation. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coating film. After exposure, use 100g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio) and develop at 50 ° C by immersion method. Washed for minutes. As a result, a negative image was obtained. The development time at this time was 1 minute 45 seconds. The resolution was 30 μm with a line and space pattern.

It was synthesized according to polyarylate (previously reported (T. Oyama, A. Kitamura, E. Sato, M. Tomoi, J. Polym. Sci. Part A: Polym. Chem., 44, 2694 (2006)) instead of PEI. Using the weight average molecular weight of 29,000, the chemical formula is shown in the following formula), the same operation as in Example 1 was performed to prepare a photoresist composition. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coated film having a film thickness. After exposure, use 100g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 1 minute 45 seconds. The resolution was 30 μm with a line and space pattern.

To 4.66 g (50 mmol) of aniline dissolved in 50 mL of THF, 5.27 g (50 mmol) of crotonic acid chloride was slowly added dropwise at 0 ° C. in the presence of 13.82 g (100 mmol) of potassium carbonate, and further reacted at room temperature for 5 hours. Thereafter, inorganic salts were removed by filtration. The crude crystals obtained by evaporation of the filtrate were recrystallized using hexane / chloroform = 5/2 (vol / vol), and further dried under reduced pressure (40 ° C./14 h), and N-phenylcrotonamide was obtained. Was obtained as a white solid (yield: 76%, melting point: 114.2 ° C. to 115.8 ° C., the structure was confirmed by ¹ H-NMR).
Using the N-phenylcrotonamide obtained above instead of PMI, the same operation as in Example 1 was performed to prepare a photoresist formulation. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coating film. After exposure, use 100g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 1 minute 44 seconds. The resolution was 30 μm with a line and space pattern.

  The exposed PEI coating film obtained in Example 1 was subjected to ultrasonic treatment using 100 g of a developer consisting of TMAH / NMP / ion exchange water / 2-ethoxyethanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio). Under processing, development was performed at 50 ° C. and washed with 100 g of ion-exchanged water for 1 minute. As a result, a negative image was obtained. The development time at this time was 2 minutes and 45 seconds. The resolution was 30 μm with a line and space pattern.

  To the exposed PEI coating film obtained by the same operation as in Example 1, using 100 g of a developer composed of TMAH / dimethylformamide / ion-exchanged water / ethanol = 0.4 / 1.0 / 1.6 / 3.6 (weight ratio), Development was carried out at 50 ° C. by the dipping method, followed by washing with 100 g of ion exchange water for 1 minute. As a result, a negative image was obtained. The development time at this time was 4 minutes and 45 seconds. The resolution was 15 μm with a line and space pattern.

After adding 1.0 g of PEI to 4.0 g of NMP and dissolving it, add 0.15 g of photosensitizer PC-5 (R) and 0.2 g of PMI and stir with a stirrer at room temperature for about 1 hour. A product was prepared. Pre-baking and exposure were performed in the same manner as in Example 1.
100 g of developer consisting of TMAH / polyethylene glycol (manufactured by Junsei Chemical Co., Ltd., number average molecular weight: 400) / ion exchange water / ethanol = 0.4 / 1.0 / 1.6 / 3.6 (weight ratio) on the exposed PEI coating Was developed at 50 ° C. by an immersion method and washed with 100 g of ion-exchanged water for 1 minute. As a result, a negative image was obtained. The development time at this time was 6 minutes 45 seconds. The resolution was 10 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

Using 4-phenyl-3-buten-2-one (manufactured by Aldrich) instead of PMI, the same operation as in Example 1 was performed to prepare a photoresist composition. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coating film. Light in the i-line to g-line band was irradiated by an ultraviolet exposure machine through a PET photomask. The exposure measured with an illuminometer for the i-line band was 2000 mJ / cm ² . After exposure, use 100g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 4 minutes. The resolution was 30 μm with a line and space pattern.

Using N-phenylsuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of PMI, the same operation as in Example 1 was performed to prepare a photoresist composition. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coating film. Light in the i-line to g-line band was irradiated by an ultraviolet exposure machine through a PET photomask. The exposure measured with an illuminometer for the i-line band was 2000 mJ / cm ² . After exposure, use 100g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 1 minute 55 seconds. The resolution was 30 μm with a line and space pattern.

A 200 mL four-necked flask equipped with a stirrer and a dropping funnel was charged with 4.66 g (50 mmol) of aniline, 13.82 g (100 mmol) of potassium carbonate, and 100 mL of THF. It was slowly added dropwise in the bath. After completion of dropping, the mixture was stirred at room temperature for 5 hours, and inorganic salts were removed by filtration. The filtrate was evaporated to obtain crude crystals of N-phenylisovaleroamide (PVA) as a light brown solid. The obtained crude crystals were recrystallized with hexane / chloroform = 10/7 (v / v). Finally, it was dried under reduced pressure (60 ° C.) to obtain PVA as a white solid (yield: 61%, melting point: 112.8-114.7 ° C., structure confirmed by 1H-NMR).
Using the PVA obtained above instead of PMI, the same operation as in Example 1 was performed to prepare a photoresist formulation. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coating film. Light in the i-line to g-line band was irradiated by an ultraviolet exposure machine through a PET photomask. The exposure measured with an illuminometer for the i-line band was 2000 mJ / cm ² . After exposure, use 100g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 2 minutes. The resolution was 30 μm with a line and space pattern.

Using N-methylbenzamide (manufactured by Aldrich) instead of PMI, the same operation as in Example 1 was performed to prepare a photoresist composition. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coating film. Light in the i-line to g-line band was irradiated by an ultraviolet exposure machine through a PET photomask. The exposure measured with an illuminometer for the i-line band was 2000 mJ / cm ² . After exposure, use 100g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 3 minutes 15 seconds. The resolution was 25 μm with a line and space pattern.

A photoresist formulation was prepared in the same manner as in Example 1 except that polyamideimide (Japanese Patent Application Laid-Open No. 2004-59694) was used instead of PMI. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coating film. Light in the i-line to g-line band was irradiated by an ultraviolet exposure machine through a PET photomask. The exposure measured with an illuminometer for the i-line band was 2000 mJ / cm ² . After exposure, use 100g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 3 minutes. The resolution was 25 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

Using bisphenol A diglycidyl ether (manufactured by Japan Epoxy Resin Co.) instead of PMI, the same operation as in Example 1 was performed to prepare a photoresist composition. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coating film. Light in the i-line to g-line band was irradiated by an ultraviolet exposure machine through a PET photomask. The exposure measured with an illuminometer for the i-line band was 2000 mJ / cm ² . After exposure, use 100g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 3 minutes and 30 seconds. The resolution was 30 μm with a line and space pattern.

To a 100 mL eggplant flask, 0.630 g (8.4 mmol) of 2-methoxyethylamine, 530 mg (5.0 mmol) of sodium carbonate and 15 mL of distilled water were added and vigorously stirred. To this solution, 2.16 g (8.4 mmol) of 9-fluorenylmethyl chloroformate dissolved in 10 mL of THF was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After concentrating the reaction solution with an evaporator, 75 mL of ethyl acetate was added, and this solution was extracted twice with 25 mL of water, 25 mL of 5% citric acid aqueous solution and 25 mL of saturated sodium chloride aqueous solution. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the resulting crude product was recrystallized from hexane. Thereafter, drying under reduced pressure (35 ° C./3 hours) gave N- (9-fluorenylmethylcarbonyl) -2-methoxyethylamine (yield: 12%, melting point: 84.6-86.7 ° C., structure: 1H— Confirmed by NMR).
Using the N- (9-fluorenylmethylcarbonyl) -2-methoxyethylamine obtained above instead of PMI, the same operation as in Example 4 was performed to prepare a photoresist formulation. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coating film. Light in the i-line to g-line band was irradiated by an ultraviolet exposure machine through a PET photomask. The exposure measured with an illuminometer for the i-line band was 100 mJ / cm ² . After exposure, use 100g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 4 minutes and 36 seconds. The resolution was 40 μm with a line and space pattern.

Using 1,4-diphenyl-1,4-butanedione (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of PMI, the same operation as in Example 1 was performed to prepare a photoresist composition. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coating film. Light in the i-line to g-line band was irradiated by an ultraviolet exposure machine through a PET photomask. The exposure measured with an illuminometer for the i-line band was 2000 mJ / cm ² . After exposure, use 100g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 4 minutes and 15 seconds. The resolution was 50 μm with a line and space pattern.

2 is a view showing an SEM photograph of a photoresist formed in Example 1. FIG. 6 is a view showing an SEM photograph of a photoresist formed in Example 2. FIG. 10 is a view showing an SEM photograph of a photoresist formed in Example 5. FIG. 4 is a view showing an SEM photograph of a photoresist formed in Example 13. FIG. 16 is a view showing an SEM photograph of a photoresist formed in Example 18. FIG.

Claims (6)

A step of providing a photoresist layer containing a condensed polymer containing a carbonyl group (C═O) bonded to a hetero atom (C═O) in the main chain, an anion regenerating agent and a photoacid generator on a substrate, and masking with a desired pattern. It comprises a step of irradiating the pattern surface with ultraviolet light, and a development step of treating the photoresist layer with a developer.
(In the formula, X represents a substituent represented by the following formula,
In the formula, Y represents —NR ¹ ₂ , —OR ¹ (excluding —OH), —CR ¹ ₃ or —SR ¹ (excluding —SH), and R ¹ is independently selected. And represents a hydrogen atom, an aliphatic group or an aromatic group. ), A compound represented by the following formula: R ² -CONHR ¹
Or R ² —COCH (R ¹ ) ₂
(Wherein R ² independently represents an aliphatic group or an aromatic group, and R ¹ is defined in the same manner as described above),
(In the formula, at least one of R ³ represents an aliphatic group or an aromatic group, the other represents a hydrogen atom, and Z represents an oxygen atom (—O—) or a sulfur atom (—S—).) Or a compound represented by the following formula: CH (R ⁴ ) ₂ C (R ¹ ) ₂ OCO—N (R ¹ ) ₂
(Wherein at least one of R ⁴ represents an electron withdrawing group, and the other represents a hydrogen atom, an aliphatic group or an aromatic group. R ¹ is defined in the same manner as described above). A reactive development image forming method, wherein the developer comprises a solvent containing tetra-substituted ammonium hydroxide, a low molecular alcohol and water. The photoacid generator is 1,2-naphthoquinone-2-diazide-5-sulfonic acid-p-cresol ester, and the anion regenerating agent is represented by the following formula:
The method according to claim 1, wherein R ¹ is an N-substituted maleimide compound represented by the same definition as above. A negative photoresist structure having a photoresist layer formed by the method according to claim 1 or 2 on a substrate, wherein the thickness of the photoresist layer is 0.1 to 500 μm. The photoresist structure according to claim 3, wherein a relief structure having a desired pattern is formed on the photoresist layer. A substrate having a photoresist layer with a film thickness of 0.1 to 500 μm, wherein the photoresist layer contains a carbonyl group (C═O) bonded to a hetero atom in the main chain, an anion regenerating agent And a photoacid generator, the anion regenerant is represented by the following formula:
(In the formula, X represents a substituent represented by the following formula,
In the formula, Y represents —NR ¹ ₂ , —OR ¹ (excluding —OH), —CR ¹ ₃ or —SR ¹ (excluding —SH), and R ¹ is independently selected. And represents a hydrogen atom, an aliphatic group or an aromatic group. ), A compound represented by the following formula: R ² -CONHR ¹
Or R ² —COCH (R ¹ ) ₂
(Wherein R ² independently represents an aliphatic group or an aromatic group, and R ¹ is defined in the same manner as described above),
(In the formula, at least one of R ³ represents an aliphatic group or an aromatic group, the other represents a hydrogen atom, and Z represents an oxygen atom (—O—) or a sulfur atom (—S—).) Or a compound represented by the following formula: CH (R ⁴ ) ₂ C (R ¹ ) ₂ OCO—N (R ¹ ) ₂
(Wherein at least one of R ⁴ represents an electron withdrawing group, and the other represents a hydrogen atom, an aliphatic group or an aromatic group. R ¹ is defined in the same manner as described above). A board. The photoacid generator is 1,2-naphthoquinone-2-diazide-5-sulfonic acid-p-cresol ester, and the anion regenerating agent is represented by the following formula:
6. The substrate according to claim 5, which is an N-substituted maleimide compound represented by (wherein R ¹ is defined in the same manner as described above).