JP2007328234A - Pattern forming method, TFT array substrate, and liquid crystal display element - Google Patents

Abstract

A pattern forming method, a TFT array substrate, and a liquid crystal display element suitable for manufacturing a liquid crystal display (LCD) and a plasma display (PDP) for a large screen are provided.
A positive photosensitive composition comprising at least a resin that exhibits alkali solubility by the action of an acid, and a photoacid generator that generates an acid that absorbs at least light having a wavelength of 405 nm. And at least a positive photosensitive layer forming step for forming a positive photosensitive layer on the surface of the substrate, and at least a polyvinyl alcohol having a mass average molecular weight of 8,000 to 100,000 on the surface of the positive photosensitive layer. A protective film forming step of forming a protective film; an exposure step of exposing the positive photosensitive layer from the protective film side; and a developing step of developing the positive photosensitive layer exposed by the exposure step. And a TFT array substrate and a liquid crystal display element formed by the pattern forming method.
[Selection] Figure 1

Description

  The present invention relates to a pattern forming method, a TFT array substrate, and a liquid crystal display element suitable for manufacturing a liquid crystal display (LCD) for large screens and a plasma display (PDP).

With the trend toward larger and higher definition substrates such as liquid crystal displays (LCDs) and plasma display panels (PDPs), etching photoresists used in the manufacture of thin film transistors (TFTs) and electrode plates have increased sensitivity. Adhesion with various substrates and higher resolution are desired.
Conventionally, as an exposure method used in the photolithography method, an exposure method using a photomask is generally used. However, mask exposure due to uniform exposure technology in response to an increase in the size of the substrate, misalignment of the photomask, and adhesion of foreign matters during the process is a problem.
Therefore, based on exposure patterns formed from digital data such as wiring patterns, a digital exposure method that performs patterning by directly scanning laser light in the ultraviolet to visible region such as semiconductor lasers and gas lasers onto the photosensitive layer is being studied. Has been.
If the digital exposure method is used in the manufacturing process of the thin film transistor (TFT), there is a possibility that high efficiency of the TFT manufacturing can be achieved. Therefore, the digital exposure method has attracted attention. In order to construct a TFT manufacturing system by this digital exposure method, a high-resolution resist suitable for the digital exposure method has become necessary.
Further, unlike the mask exposure method, the digital exposure method needs to scan the entire surface of the photosensitive layer, and therefore requires a resist material with high sensitivity and high resolution.

As a resist material corresponding to the digital exposure method as described above, conventionally, a combination of o-quinonediazide and cresol novolac resin is known (for example, see Patent Documents 1 and 2).
However, since the sensitivity of the resist material is limited, a chemically amplified resist that is a combination of a photoacid generator and an acid-decomposable resin is promising (see, for example, Patent Documents 3 to 5).
However, in this case, there is no description regarding the use of the chemical amplification resist for TFT production. In the chemical amplification resist, pattern formation is performed by exposure and baking after the exposure (to promote the action of the catalyst). If the substrate is left in the air atmosphere (hereinafter referred to as “air exposure after exposure”) until the heat treatment is performed, the line width of the resist pattern is affected by the influence of trace contaminants in the air atmosphere. There is a problem that the profile, resolution, and the like greatly change from the desired one (hereinafter referred to as “PED (Post Exposure Delay) phenomenon”). The cause of the PED phenomenon is considered to be that the acid catalyst generated in the exposure region is neutralized by a basic substance in the atmosphere and deactivated. In order to prevent the occurrence of the PED phenomenon as much as possible, conventionally, a sample that has been exposed is stored in an atmosphere such as a vacuum or a nitrogen atmosphere (hereinafter referred to as a “special storage atmosphere”), so Methods were taken to prevent the effects of pollutants.

However, in the method of storing the exposed sample in the special storage atmosphere as described above, (1) an apparatus for forming the special storage atmosphere and a space for it are required. In the case of a vacuum atmosphere, it is not easy to put the sample in and out of the atmosphere. (3) It is necessary to modify the exposure apparatus itself in order to put the exposed sample in a special storage atmosphere without contacting the atmosphere at all. Due to the problems such as being there, it is not always a satisfactory method in terms of preventing the PED phenomenon simply and inexpensively.
In addition, many proposals have been made to suppress the influence of trace contaminants in the air atmosphere by adding an amine-based compound, so-called quencher, to the chemically amplified resist (for example, Patent Documents 6 to 6). 8). However, in this case, since the acidic substance generated in the exposed region by the acid generator is neutralized by the amine compound, the decomposition of the resin decomposed by the acid is delayed, resulting in a problem that the sensitivity is lowered. there were.

Further, a method is disclosed in which a protective film is provided on the photosensitive layer to prevent the PED phenomenon in the air atmosphere during temporary storage from exposure to baking (for example, Patent Documents 9 to 9). 11). However, in Patent Documents 9 to 10, there is no description about applicability to a blue-violet laser, and a water-insoluble resin such as a sulfonic acid group or a carboxy group-containing resin that has low sensitivity to the blue-violet laser is used. Therefore, there is a problem that the coating film easily absorbs moisture in the air during storage after coating the protective layer and the surface tackiness is high, and the handleability of the protective film and the ability to protect against contaminants are poor. Further, in Patent Document 11, since a resin having an average molecular weight of 5,000 or less is used as the protective layer, the protective film obtained in this case also has a high surface tack property and inferior protective ability. There were problems such as.
Also in Patent Document 2, a thermoplastic resin layer is provided on the surface of the photosensitive layer. In this case, it is used as a cushion layer for absorbing unevenness of the base material, and for preventing the PED phenomenon. Is not described at all.

  Therefore, it is highly sensitive to blue-violet laser exposure, can prevent the PED phenomenon after exposure well, easily and at low cost, and can form high-resolution and high-definition patterns. However, a system that can realize high productivity, low cost production, and high yield production has not been provided yet, and its rapid development is desired.

JP 2000-206571 A JP 2002-341525 A JP 2004-86122 A JP 2005-106991 A Japanese Patent Laid-Open No. 2004-199031 JP-A-10-133375 JP 2000-206681 A JP 2004-354610 A JP 7-295228 A JP-A-8-305031 JP-A-5-507154

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention is a pattern forming method that is highly sensitive to blue-violet laser exposure, can prevent the PED phenomenon after exposure well, easily and at low cost, and can form a high resolution and high definition pattern. An object of the present invention is to provide a TFT array substrate capable of high productivity and low-cost production by using the pattern forming method, and a liquid crystal display device using the TFT array substrate.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that in lithography pattern formation using a positive photoresist, a resin that exhibits alkali solubility by the action of an acid and light having a wavelength of at least 405 nm. A positive photosensitive layer made of a positive photosensitive composition containing at least a photoacid generator that absorbs and generates an acid is exposed to a blue-violet laser and developed to form a resist pattern. In doing so, by providing a protective film containing a water-soluble resin having a weight average molecular weight of 8,000 to 100,000 on the positive photosensitive layer, a factor that deactivates the acid catalyst generated in the exposed region (for example, It is possible to protect the positive-type photosensitive layer after exposure from trace contaminants such as basic substances and acidic substances), and equipment and facilities for storage in a special storage atmosphere. Without the need for a good PED phenomenon after exposure, and was obtained a finding that it is possible to inexpensively prevent a simple.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> A positive photosensitive composition comprising at least a resin that exhibits alkali solubility by the action of an acid, and a photoacid generator that generates an acid that absorbs at least light having a wavelength of 405 nm. A positive photosensitive layer forming step of forming at least a positive photosensitive layer on the surface of the substrate,
A protective film forming step of forming a protective film containing at least polyvinyl alcohol having a mass average molecular weight of 8,000 to 100,000 on the surface of the positive photosensitive layer;
An exposure step of exposing the positive photosensitive layer from the protective film side;
And a development step of developing the positive photosensitive layer exposed in the exposure step.
In the pattern forming method according to <1>, a positive photosensitive layer is formed on a substrate by the positive photosensitive layer forming step. Through the protective film forming step, a protective film containing at least polyvinyl alcohol having a mass average molecular weight of 8,000 to 100,000 is formed on the surface of the positive photosensitive layer. In the exposure step, the positive photosensitive layer is exposed from the protective film side. In the development step, the positive photosensitive layer exposed in the exposure step is developed to form a pattern. As a result, it is highly sensitive to blue-violet laser exposure, and the PED phenomenon after exposure can be satisfactorily and easily prevented at low cost by the protective film, and a high-definition and high-definition pattern can be formed. It is suitable for forming a TFT array substrate and a liquid crystal display element using the TFT array substrate.
<2> The pattern forming method according to <1>, wherein the positive photosensitive layer is formed by applying a positive photosensitive composition to a surface of a substrate and drying.
<3> The pattern forming method according to any one of <1> to <2>, wherein the resin that exhibits alkali solubility by the action of an acid includes a resin having a phenolic hydroxyl group in which a part of the phenolic hydroxyl group is protected. It is.
<4> The pattern forming method according to <3>, wherein the protecting group for the phenolic hydroxyl group is any one of an acetal group, a ketal group, and a sterically hindered ester group.
<5> The pattern forming method according to any one of <1> to <4>, wherein the photoacid generator includes an oxime sulfonate photoacid generator.
<6> The pattern forming method according to any one of <1> to <5>, wherein the content of the photoacid generator is 0.01 to 5% by mass.
<7> The pattern forming method according to any one of <1> to <6>, wherein the protective film further contains polyvinylpyrrolidone.
<8> The pattern forming method according to <1> to <7>, wherein the content of polyvinyl alcohol is 50 to 90% by mass of the total solid content of the protective film.
<9> The pattern forming method according to any one of <1> to <8>, wherein the saponification rate of the polyvinyl alcohol is 75 to 95 mol%.
<10> The pattern forming method according to any one of <1> to <9>, wherein the protective film has a thickness of 0.1 to 3.0 μm.
<11> The pattern forming method according to any one of <1> to <10>, including an intermediate layer forming step of forming an intermediate layer on the positive photosensitive layer.
<12> The pattern forming method according to any one of <1> to <11>, further including a post-exposure heating step in which the exposed positive photosensitive layer is subjected to a heat treatment before the development step.
<13> The pattern forming method according to any one of <1> to <12>, further including a post-development heating step in which a heat treatment is performed on the positive photosensitive layer after the development step.

<14> Exposure is emitted from the light irradiation unit to the positive photosensitive layer while moving at least one of an exposure head having at least a light irradiation unit and a light modulation unit and a positive photosensitive layer. The pattern forming method according to any one of <1> to <13>, wherein the light is irradiated from the exposure head while being modulated in accordance with pattern information by the light modulation unit.
<15> The light modulation unit is capable of controlling any less than n pixel elements arranged continuously from n pixel elements in accordance with pattern information. This is a pattern forming method.
<16> The pattern forming method according to any one of <14> to <15>, wherein the light modulation unit is a spatial light modulation element.
<17> The pattern forming method according to <16>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<18> The pattern forming method according to any one of <14> to <17>, wherein the exposure is performed through an aperture array.
<19> The pattern forming method according to any one of <14> to <18>, wherein the exposure is performed while relatively moving the exposure light and the positive photosensitive layer.
<20> The pattern forming method according to any one of <14> to <19>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
<21> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects and couples the laser beams irradiated from the plurality of lasers to the multimode optical fiber. <14> to the pattern forming method according to any one of <20>.
<22> The pattern forming method according to <21>, wherein the wavelength of the laser beam is 365 to 445 nm.
<23> The pattern forming method according to any one of <1> to <22>, which is used for manufacturing a thin film transistor array for a liquid crystal display device.

<24> A TFT array substrate formed by the pattern forming method according to any one of <1> to <23>.
<25> A liquid crystal display element using the TFT array substrate according to <24>.

  According to the present invention, conventional problems can be solved, high sensitivity to blue-violet laser exposure, the PED phenomenon after exposure can be prevented well and easily at low cost, high resolution and high definition A pattern forming method capable of forming a simple pattern, a TFT array substrate capable of high productivity and low-cost production by using the pattern forming method, and a liquid crystal display device using the TFT array substrate can be provided.

(Pattern forming method, TFT array substrate and liquid crystal display element)
The pattern forming method of the present invention comprises at least a positive photosensitive layer forming step, a protective film forming step, an exposure step, and a development step, preferably an intermediate layer forming step, a post-exposure heating step, A post-development heating step, and further comprising other steps appropriately selected as necessary.
The TFT array substrate of the present invention is manufactured by the pattern forming method of the present invention.
The liquid crystal display element of the present invention uses the TFT array substrate of the present invention, and further includes other members as necessary.
Hereinafter, details of the TFT array substrate and the liquid crystal display element of the present invention will be clarified through the description of the pattern forming method of the present invention.

[Positive photosensitive layer forming step]
The positive photosensitive layer forming step includes a positive photosensitive layer including at least a resin that exhibits alkali solubility by the action of an acid and a photoacid generator that generates an acid that absorbs at least light having a wavelength of 405 nm. In this step, a positive photosensitive layer is formed on the surface of the substrate using the conductive composition.

The method for forming the positive photosensitive layer is not particularly limited and may be appropriately selected depending on the purpose. For example, a method of forming by coating, at least one of pressing and heating each sheet-like layer is used. By carrying out, a laminating method, a combination thereof, and the like can be mentioned.
In the positive photosensitive layer forming step, a positive photosensitive layer can be formed on the surface of the substrate by applying the positive photosensitive composition to the surface of the substrate and drying.

  There is no restriction | limiting in particular as the method of the said application | coating and drying in the said positive photosensitive layer formation process, According to the objective, it can select suitably, For example, the said positive photosensitive composition is on the surface of the said base material. Can be dissolved, emulsified or dispersed in water or a solvent to prepare a positive photosensitive composition solution, and the solution is directly applied and dried to form a photosensitive laminate.

  There is no restriction | limiting in particular as a solvent of the said positive photosensitive composition solution, According to the objective, it can select suitably, For example, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, (gamma) -butyrolactone, methyl ethyl ketone, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate , Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxy , N- methylpyrrolidone, tetrahydrofuran, and the like. These may be used individually by 1 type and may use 2 or more types together.

The coating method is not particularly limited and can be appropriately selected depending on the purpose. For example, using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. The method of apply | coating is mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

  There is no restriction | limiting in particular as thickness of the said positive photosensitive layer, According to the objective, it can select suitably, 0.5-10 micrometers is preferable, 0.75-6 micrometers is more preferable, and 1-3 micrometers is especially preferable.

<Positive photosensitive layer>
The positive photosensitive layer formed in the positive photosensitive layer forming step includes a resin that exhibits alkali solubility by the action of an acid, and a photoacid generator that generates an acid that absorbs at least light having a wavelength of 405 nm. And at least an additive, an additive, and, if necessary, other components.

-(A) Resin that exhibits alkali solubility by the action of acid-
The resin that exhibits alkali solubility by the action of an acid (hereinafter sometimes referred to as an acid-decomposable resin A) is a resin having a group that is decomposed by the action of an acid (also referred to as an acid-decomposable group). It is a compound which has a structure in which an acid-decomposable group is introduced into a compound having a molecular weight distribution obtained by polymerizing and becomes alkali-soluble by the action of an acid.

  The resin having an acid-decomposable group is preferably a resin having an acid-decomposable group in at least one of the main chain and side chain of the resin, and among these, a resin having an acid-decomposable group in the side chain is more preferred. preferable.

As the base resin of the resin having an acid-decomposable group in the side chain, the alkali-soluble resin having either —OH or —COOH in the side chain and any of —R ⁰ —COOH and —Ar—OH group. Resins are preferred. However, -R 0 ^- represents one of the aliphatic and aromatic hydrocarbon divalent or higher which may have a substituent, -Ar- is one of the substituents of the monocyclic and polycyclic Represents a divalent or higher aromatic group that may be present.

As the base resin, an alkali-soluble resin having a phenolic hydroxyl group is particularly preferable. Examples of the alkali-soluble resin having a phenolic hydroxyl group used in the present invention include o-, m- and p-hydroxystyrene (collectively referred to as hydroxystyrene), and o-, m- and p-. A co-polymer containing at least 30 mol%, preferably 50 mol% or more of a repeating unit corresponding to any one selected from hydroxy-α-methylstyrene (collectively referred to as hydroxy-α-methylstyrene). It is preferably either a polymer or a homopolymer thereof. In addition, as the alkali-soluble resin having a phenolic hydroxyl group, a resin in which the benzene nucleus of the repeating unit is partially hydrogenated is also preferable. Among these, p-hydroxystyrene homopolymer is more preferable.
Preferred monomers for preparing the copolymer by copolymerization other than the above-mentioned hydroxystyrene and hydroxy-α-methylstyrene include acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, acrylonitrile, methacrylic acid. Ronitrile, maleic anhydride, styrene, α-methylstyrene, acetoxystyrene, alkoxystyrenes, and alkylstyrenes are preferable, and styrene, acetoxystyrene, and t-butylstyrene are exemplified.

The acid-decomposable resin A is not particularly limited as long as it is a resin whose solubility in an alkaline developer is increased by the action of an acid, and can be appropriately selected according to the purpose. For example, the following general formula ( Preferred examples include compounds represented by A-1) to (A-4).
However, in the general formulas (A-1) to (A-4), W represents a group that is decomposed by the action of an acid (hereinafter referred to as an acid-decomposable group). R ¹⁴ represents a group that is not decomposed by the action of an acid (hereinafter referred to as an acid stabilizing group).
Moreover, in the said general formula (A-1) and general formula (A-3), x, y, and z represent the molar composition ratio of a repeating unit, respectively, and are x + y + z = 1. Moreover, in the said general formula (A-2) and (A-4), x and y represent the molar composition ratio of each repeating unit, and are x + y = 1.

  Examples of the acid-decomposable group represented by W in the general formulas (A-1) to (A-3) include groups represented by the following general formulas (X-1) to (X-4). Among them, among these, a group represented by the following general formula (X-1) is preferable.

However, in said general formula (X-1), R < ⁴ > and R < ⁵ > represents either a hydrogen atom or an alkyl group each independently. Z represents an alkyl group. m represents an integer of 1 to 20.

However, in the general formulas (X-2) to (X-4), R, R ′ and R ″ may be the same or different, are alkyl groups, and may have a substituent. R ′ and R ″ may be bonded to each other to form a ring (for example, a 3 to 12 membered ring).

The alkyl group as R ⁴ and R ⁵ in the general formula (X-1) may be linear, branched or cyclic, and may have a substituent.
As said linear alkyl group, C1-C30 is preferable and C1-C20 is more preferable, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n- A hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, etc. are mentioned.
As said branched alkyl group, C1-C30 is preferable, C1-C20 is more preferable, for example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group I-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group, and the like.
The cyclic alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, And tetracyclododecanyl group.

The alkyl group as Z in the general formula (X-1) may be linear, branched or cyclic, and may have a substituent.
As said linear alkyl group and branched alkyl group, C1-C10 is preferable, for example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t- Butyl, n-pentyl, i-pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-heptyl, i-heptyl, t-heptyl, n- Examples include octyl group, i-octyl group, t-octyl group, n-nonyl group, i-nonyl group, t-nonyl group, n-decanyl group, i-decanyl group, t-decanyl group, and the like.
The cyclic alkyl group preferably has 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  Here, although the specific example of group represented by the said general formula (X-1) is shown below, this invention is not limited to these.

  The alkyl group as R, R ′ and R ″ in the general formulas (X-2) to (X-4) preferably has 1 to 12 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, t-hexyl group, n-heptyl group, i-heptyl group, t-heptyl group, n-octyl group, i-octyl group, t-octyl group, n-nonyl group, i-nonyl group, t-nonyl group, n-decanyl group, An i-decanyl group, a t-decanyl group, etc. are mentioned.

  In addition, examples of the substituent for each group include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, the above cycloalkyl group, a methoxy group, an ethoxy group, and hydroxyethoxy. Group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, alkoxy group such as t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, benzyl group, phenethyl group, Aralkyl groups such as cumyl groups, aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, acyl groups such as cyanamyl groups and valeryl groups, acyloxy groups such as butyryloxy groups, the above alkenyl groups, vinyloxy groups, propenyloxy Group, allyloxy group, butenyloxy group Alkenyloxy group, an aryloxy group such as phenoxy group, an aryloxycarbonyl group such as benzoyloxy group, and the like. These substituents may further have a substituent.

In the general formulas (A-1) to (A-3), the acid stabilizing group represented by R ¹⁴ represents at least one of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and an acyloxy group.
In the acid stable group of R _14, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, or a t-butyl group. Can be mentioned.
Preferred examples of the alkoxy group include alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an n-butoxy group, an isobutoxy group, and a sec-butoxy group. It is done.
Preferred examples of the acyloxy group include those having 2 to 7 carbon atoms such as an acetoxy group, a propnoyloxy group, a butanoyloxy group, and a benzoyloxy group.

The acid-decomposable resin A may be any resin as long as alkali developability is increased by the action of an acid, but has an acid-decomposable group represented by the general formula (X-1), Preferable examples include resins that decompose by action and increase the solubility in an alkaline developer (hereinafter sometimes referred to as resins having a group represented by the general formula (X-1)).
In the acid-decomposable resin A, the content of the repeating unit (structural unit) having a group represented by any one of the general formulas (X-1) to (X-4) is based on all repeating units. 5 to 50 mol% is preferable, and 5 to 30 mol% is more preferable.

  In the acid-decomposable resin A having a group represented by any one of the general formulas (X-1) to (X-4), any one of the general formulas (X-1) to (X-4) Other acid-decomposable groups may be included in addition to the group represented by

  As a method for producing the acid-decomposable resin A containing a group represented by any one of the general formulas (X-1) to (X-4), a corresponding vinyl ether is synthesized and used in an appropriate solvent such as tetrahydrofuran. It can be obtained by reacting with an alkali-soluble resin having a dissolved phenolic hydroxyl group by a known method. The reaction is usually carried out in the presence of an acidic catalyst, preferably an acidic ion exchange resin, hydrochloric acid, p-toluenesulfonic acid, or a salt such as pyridinium tosylate. The corresponding vinyl ether can be synthesized from an active raw material such as chloroethyl vinyl ether by a method such as a nucleophilic substitution reaction, or can be synthesized using a mercury or palladium catalyst. Moreover, it can synthesize | combine also by the method of acetal exchange using corresponding alcohol and vinyl ether as another different method. In this case, it is carried out in the presence of an acid such as p-toluenesulfonic acid or pyridinium tosylate by giving a substituent to be introduced to alcohol, mixing a relatively unstable vinyl ether such as t-butyl vinyl ether as vinyl ether. .

  In the acid-decomposable resin A, examples of the repeating unit having a group represented by the general formula (X-1) include a repeating unit represented by the following general formula (Y-1).

However, in the general formula (Y-1), the substituent W ₁ represents a group represented by the general formula (X-1).

  Although the specific structure of the repeating unit represented by the said general formula (Y-1) is illustrated below, this invention is not limited to these.

  As a preferable repeating unit copolymerizable with the general formula (Y-1), a repeating unit represented by any one of the following general formula (Y-2) and the following general formula (Y-3) can be exemplified. . By allowing the acid-decomposable resin A to contain a repeating unit represented by any one of the general formula (Y-2) and the following general formula (Y-3), the acid-decomposable resin A is caused by the action of an acid. It is possible to control the solubility in an alkaline developer when decomposed. In addition, by introducing the repeating unit, the obtained pattern can achieve a profile with excellent rectangularity. Furthermore, it is effective for adjusting the amount of the repeating unit represented by the general formula (Y-1).

In the general formula (Y-2) ~ (Y -3), R 14 is an acid stable group such a hydrogen atom, a halogen atom an alkyl group, an alkoxy group, and at least one acyloxy group To express.
Preferred examples of the alkyl group in the acid stabilizing group for R ¹⁴ include those having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group. It is done.
Preferred examples of the alkoxy group include alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an n-butoxy group, an isobutoxy group, and a sec-butoxy group. It is done.
Preferred examples of the acyloxy group include those having 2 to 7 carbon atoms such as an acetoxy group, a propnoyloxy group, a butanoyloxy group, and a benzoyloxy group.

  Specific examples of the polymerizable monomer of the repeating unit represented by the general formula (Y-3) include compounds represented by the following formula, but the present invention is not limited thereto. .

  The resin containing the repeating unit represented by any one of the general formula (Y-2) and the general formula (Y-3) is obtained by reacting a phenol resin or its monomer with an acid anhydride in the presence of a base. Or by reacting with the corresponding halide in the presence of a base.

  Examples of the acid-decomposable resin A include a copolymer composed of the general formula (Y-1) and the general formula (Y-2), the general formula (Y-1), and the general formula (Y-2). ) And the general formula (Y-3), a general formula (Y-1), a general formula (Y-2) and a copolymer consisting of t-butyl acrylate, and the like. Among them, the acid-decomposable resin A is represented by the following formula, the repeating unit represented by the general formula (Y-1), the repeating unit represented by the general formula (Y-2), and the general formula. A blend containing an acid-decomposable resin A ′ composed of a structural unit represented by (Y-3) is preferred.

However, in the above ^{formula, R 14} represents an acid-stable group. W ₁ represents a group represented by the general formula (X-1). x and y represent an integer of 1 to 100, and z represents an integer of 0 to 100, where x + y + z = 100.

Specific examples of the acid-decomposable resin A ′ composed of the general formula (Y-1) and the general formula (Y-2) include a copolymer represented by the following formula. However, it is not limited to these.
However, in said formula, x and y represent the molar composition ratio of a repeating unit, respectively, and are x + y = 1.

  In the acid-decomposable resin A ′ comprising the repeating unit represented by the general formula (Y-1) and the general formula (Y-2), the content ratio of the repeating unit represented by the general formula (Y-1) Is preferably 10 mol% or more and 45 mol% or less, more preferably 15 mol% or more and 40 mol% or less.

  As a content ratio of each repeating unit in the acid-decomposable resin A composed of the general formula (Y-1), the general formula (Y-2), and t-butyl acrylate, the general formula (Y-1) is: 20 mol% or less, t-butyl acrylate is preferably 5 mol% or more and 25 mol% or less, general formula (Y-1) is 5 mol% or more and 20 mol% or less, and t-butyl acrylate is 10 mol. % To 20 mol% is more preferable.

  The x, y, z ratio of the acid decomposable resin A ′ that may be contained in the acid decomposable resin A preferably satisfies the following conditions.

When z = 0
0.05 <x / (x + y) <0.50,
More preferably,
0.1 <x / (x + y) <0.45,

If z> 0,
0.05 <x / (x + y + z) <0.35,
More preferably,
0.005 <z / (x + y + z) <0.25,

If x ≧ z,
0.5 <x / (x + z) <0.95,
More preferably,
0.1 <x / (x + y + z) <0.25 and 0.01 <z / (x + y + z) <0.15,

If x ≧ z,
0.5 <x / (x + y) <0.85

  When the acid-decomposable resin A used in the present invention satisfies the above conditions, the rectangularity of the pattern profile is improved, and in particular, the development defect is improved.

  Any one of the repeating structural unit represented by the general formula (Y-1), the general formula (Y-2), or the general formula (Y-3), and the repeating structural unit from other polymerizable monomer may be of a single type. You may make it exist in resin, and you may make it exist in resin combining 2 or more types. In addition, the acid-decomposable resin A contained in the positive photosensitive composition used in the present invention contains an alkali-soluble group such as a phenolic hydroxyl group, a carboxyl group in order to maintain good developability for an alkali developer. Other suitable polymerizable monomers may be copolymerized so that groups can be introduced.

  Specific examples of such acid-decomposable resin A are shown below, but the present invention is not limited to these.

However, in said formula, x and y represent the molar composition ratio of a repeating unit, respectively, and are x + y = 1.

However, in said formula, x, y, and z represent the molar composition ratio of a repeating unit, respectively, and are x + y + z = 1.

  The acid-decomposable resin A includes a repeating unit having a group represented by the general formula (X-1), a repeating unit having a group represented by the following general formula (X-5), and the following: A resin having at least one of the repeating units having a group represented by the general formula (X-6) is preferable from the viewpoint of obtaining a stable prevention effect of the PED phenomenon and improving the sensitivity.

However, the general formula (X-5) _{in, R 20} represents an alkyl group. In the general formula (X-6), R ₂₁ and R ₂₂ each independently represents an alkyl group.
The alkyl group for R _{20 to} R ₂₂ may be linear or branched, and preferably has 1 to 8 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group , Isobutyl group and sec-butyl group.
The alkyl group for R _{20 to} R ₂₂ may have a substituent. Examples of the substituent include an alkoxy group (preferably having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, and a hydroxy group. Ethoxy group, linear or branched propoxy group, linear or branched butoxy group), halogen atom (for example, fluorine atom, chlorine atom, iodine atom), cyano group, hydroxy group, carboxy group, nitro group, aryl group (preferably C6-C14, for example, a phenyl group, a naphthyl group, an aryloxy group (preferably C6-C14), an alkylthio group (preferably C1-C4), etc. are mentioned.

  The repeating unit having a group represented by the general formula (X-5) and the repeating unit having a group represented by the general formula (X-6) are represented by the following general formula (Y-4). Repeating units are preferred.

However, in the said general formula (Y-4), R is a hydrogen atom, a halogen atom, and the linear or branched alkyl group which may have a substitution which has 1-4 carbon atoms. Represents one of the following. A plurality of R may be the same or different. A is a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group, and a single group or two or more Represents any combination of groups. The group as A preferably has 20 or less carbon atoms, and more preferably a single bond. Y represents a group represented by the general formula (X-5) or (X-6).

  Specific examples of the repeating unit having a group represented by the general formula (X-5) and the repeating unit having a group represented by the general formula (X-6) will be given below. These are not limiting.

  The repeating unit having the group represented by the general formula (X-1), the repeating unit represented by the general formula (X-5), and the repeating unit represented by the general formula (X-6) are shown below. Specific examples of the acid-decomposable resin A having at least one of the units are given, but the present invention is not limited to these.

However, in the above formula, x, y and z in the formula of the ternary copolymer each represent a molar composition ratio of repeating units, and x + y + z = 1. In the formula of the quaternary copolymer, w, x, y, and z each represent a molar composition ratio of repeating units, and w + x + y + z = 1.

  As the acid-decomposable resin A, a preferred unit is a repeating unit having a group represented by the general formula (X-1), a repeating unit represented by the general formula (X-5) and a general formula ( X-6) In the resin having at least one of the repeating units represented by the formula (X-1), the content of the repeating unit having the group represented by the general formula (X-1) is the total repeating unit constituting the resin. On the other hand, 5 mol% or more and 50 mol% or less are preferable, and 5 mol% or more and 30 mol% or less are more preferable. The content of the repeating unit having the group represented by the general formula (X-5) and the repeating unit having the group represented by the general formula (X-6) is, as a total amount, in all the repeating units constituting the resin. On the other hand, 5 mol% or more and 30 mol% or less are preferable, and 5 mol% or more and 20 mol% or less are more preferable.

The molecular weight of the acid-decomposable resin A is usually 2,000 or more in terms of weight average (Mw: polystyrene standard), preferably 3,000 to 200,000, and more preferably 5,000 to 70,000.
Further, the dispersity (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 3.5, and particularly preferably 1.0 to 3.0. The smaller the degree of dispersion, the better the heat resistance and image formability (pattern profile, defocus latitude, etc.).

  As content of the said acid-decomposable resin A, 50-99 mass% is preferable with respect to solid content except the coating solvent of the whole composition in the said positive photosensitive composition, and 75-98 mass% is. More preferred. When the content is less than 50% by mass, the exposed portion may be insufficiently soluble in an alkaline developer, resulting in poor resolution and sensitivity. When the content is more than 99% by mass, the content of the photoacid generator is low. Since it is low, sufficient sensitivity may not be obtained.

<(B) Acid generator>
The acid generator B is not particularly limited as long as it is a compound that absorbs at least light having a wavelength of 405 nm and generates an acid, and can be appropriately selected according to the purpose. Sensitivity and storage stability From the above viewpoint, oxime sulfonates represented by the following general formula (II-1) to general formula (II-4) are preferable.
However, in said general formula (II-1)-(II-4), n represents the integer in any one of 1 and 2. X ⁰ represents any of — (CH ₂ ) m—X and —CH═CH ₂ . m represents an integer of 2, 3, 4, 5 and 6.
When n is 1, R ¹ is any ^one of a phenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and heteroaryl; hydrogen (provided that R ² is not hydrogen at the same time); C _{1 to} C ₁₈ An alkyl group, one or more C ₃ -C ₃₀ cycloalkylene groups, and —O—, —S—, —NR ⁹ —, — (CO) —, —O (CO) —, —S (CO) —. ^{, -NR 9 (CO) -,} - SO -, - SO 2 -, and -OSO ₂ - C ₂ ~C ₁₈ alkyl group which is interrupted by either, either; C ₃ -C ₃₀ cycloalkyl Any one of a group; a C ₁ -C ₈ haloalkyl group, a C ₂ -C ₁₂ alkenyl group, a C ₄ -C ₃₀ cycloalkenyl group, and a camphoryl group.
When n is 2, R ¹ is a phenylene group, a naphthylene group, or the following formula:
, Diphenylene group, oxydiphenylene group, and the following formula:
Any of the following: direct bond and the following formula:
Any one of;
Here, except for the case where all of R ¹ are hydrogen and a direct bond, a group having either an —O—C— bond or an —O—Si— bond that is cleaved by the action of an acid, May be substituted. R ₁ is a C ₂ -C ₁₈ alkanoyl group; optionally one or more C ₁ -C ₁₈ alkyl groups, C ₁ -C ₈ haloalkyl groups, C ₃ -C ₃₀ cycloalkyl groups, halogen groups,- ^{_{NO 2, -CN, -Ar 1,}} - (CO) R 10, - (CO) OR 11, - (CO) NR 12 R 13, -O (CO) R 10, -O (CO) OR 11, - O (CO) NR ¹² R ¹³ , —NR ⁹ (CO) R ¹⁰ , —NR ⁹ (CO) OR ¹¹ , —OR ¹¹ , —NR ¹² R ¹³ , —SR ⁹ , —SOR ¹⁰ , —SO ₂ R ¹⁰ , and at least a benzoyl group substituted with one of _{^{-OSO 2 R 10; NO 2;}} S (O) p C 1 ~C 18 alkyl _{group, S (O) p -C 6} ~C 12 aryl group, SO ₂ O—C ₁ -C ₁₈ alkyl group, SO ₂ O—C ₆ -C ₁₀ aryl group, and Or a diphenyl-phosphinoyl group.

A ¹ represents a direct bond, a C _{1 to} C ₁₈ alkylene group, —O—, —S—, —NR ⁹ —, —O (CO) —, —S (CO) —, —NR ⁹ (CO) —. _{, -SO -, - SO 2 -} , and -OSO ₂ - represents either.
A ² represents a direct bond; C ₁ -C ₁₈ alkylene; one or more C ₃ -C ₃₀ cycloalkylene groups, and —O—, —S—, —NR ⁹ —, — (CO) —, — C ₂ interrupted by any of O (CO) —, —S (CO) —, —NR ²³ (CO) —, —SO—, —SO ₂ —, —OSO ₂ —, and —Ar ² —. -C ₁₈ alkylene group, either; C ₃ -C ₃₀ cycloalkylene group; a phenylene group, and one of naphthylene group; represents any of.

The p represents an integer of 1 or 2.
Said X is -O (CO) R < ¹⁴ >, -O (CO) OR < ¹¹ >, -O (CO) NR < ¹² > R < ¹³ >, -NR < ⁹ > (CO) R < ¹⁴ >, -NR < ⁹ > (CO) OR < ¹¹ >, -OR. ¹¹ , —NR ¹² R ¹³ , the following formula:
^{, -SR 9, -SOR 10, -SO} 2 R 10, and represents one of -OSO ₂ R ^10.
X ′ is represented by the following formula:
Represents.
X ¹ and X ² are, independently of each other, —O (CO) —, —O (CO) O—, —O (CO) NR ⁹ —, —NR ⁹ (CO) —, —NR ⁹ (CO ^{) O -, - O -,} - NR 9 -, - S -, - SO -, - SO 2 -, and -OSO ₂ - represents either. X ¹ and X ² are direct bonds, provided that both X ¹ and X ² are not direct bonds at the same time.
Wherein ^{A 3} is a phenylene group, a naphthylene group of the following formula:
, Diphenylene group, oxydiphenylene group, and the following formula:
Any of the following: direct bond and the following formula:
Any one of;

R ² has ^one of the meanings indicated for R ¹ ; a C ₂ -C ₁₈ alkanoyl group; one or more C ₁ -C ₁₈ alkyl groups, a C ₁ -C ₈ haloalkyl group, C ₃ -C ₃₀ cycloalkyl group, a halogen _{^{group, -NO 2, -CN, -Ar 1}} , - (CO) R 10, - (CO) OR 11, - (CO) NR 12 R 13, -O (CO ) R ¹⁰ , —O (CO) OR ¹¹ , —O (CO) NR ¹² R ¹³ , —NR ⁹ (CO) R ¹⁰ , —NR ⁹ (CO) OR ¹¹ , —OR ¹¹ , —NR ¹² R ¹³ , _{^{-SR 9, -SOR 10, -SO 2}} R 10, and -OSO ₂ may benzoyl group optionally substituted with one of _{^{R 10; NO 2; S (}} O) p C 1 ~C 18 alkyl group, S (O) _p -C ₆ ~C ₁₂ aryl _{group, SO 2 O-C 1 ~C} 18 alkyl group, S Any one of an O ₂ O—C ₆ -C ₁₀ aryl group and a diphenyl-phosphinoyl group; R ¹ and R ² may be combined to form a 5-membered, 6-membered or 7-membered ring.
R ³ and R ⁴ each independently represent hydrogen, a C ₁ -C ₁₈ alkyl group, a C ₁ -C ₈ haloalkyl group, a C ₃ -C ₃₀ cycloalkyl group, and one or more —O—, ^{-S -, - NR 9 -,} - O (CO) - and ^-NR 9 (CO) - C ₃ interrupted by either -C ₃₀ cycloalkyl group, one of a halogen group, -NO ₂ , —CN, —Ar ¹ , — (CO) R ¹⁰ , — (CO) OR ¹¹ , — (CO) NR ¹² R ¹³ , —O (CO) R ¹⁰ , —O (CO) OR ¹¹ , —O ( ^{CO) NR 12 R 13, -NR} 9 (CO) R 10, -NR 9 (CO) oR 11, -OR 11, -NR 12 R 13, -SR 9, -SOR 10, -SO 2 R 10 , and -OSO ₂ R ¹⁰ is represented. R ³ and R ⁴ together represent —C (R ¹⁵ ) ═C (R ¹⁶ ) —C (R ¹⁷ ) = C (R ¹⁸ ) — and — (CO) NR ⁹ (CO) Any of-may be represented.

The G represents any of —S—, —O—, —NR ⁹ —, and a group represented by any one of the following formulas Z ¹ , Z ² , Z ³ and Z ⁴ .

R ¹⁹ and R ²⁰ may have, independently of each other, one of the meanings indicated by R ³ , or R ¹⁹ and R ²⁰ together represent —CO One of -NR < ⁹ > CO- and -C (R < ¹⁵ >) = C (R < ¹⁶ >)-C (R < ¹⁷ >) = C (R < ¹⁸ >)-may be represented.
R ³⁰ , R ³¹ , R ³² and R ³³ are each independently hydrogen, halogen, C ₁ -C ₁₈ alkyl group, C ₁ -C ₁₈ alkoxy group, C ₁ -C ₈ haloalkyl group, CN, NO ₂ , C ₂ -C ₁₈ alkanoyl group, benzoyl group, phenyl group, —S-phenyl group, OR ¹¹ , SR ⁹ , NR ¹² R ¹³ , C ₂ -C ₆ alkoxycarbonyl group, phenoxycarbonyl group, S (O) _p C ₁ -C ₁₈ alkyl group, C ₁ -C ₁₈ optionally substituted with an alkyl group _{S (O) p -C 6 ~C} 12 aryl _{group, SO 2 O-C 1 ~C} 18 alkyl group, SO ₂ O—C ₆ -C ₁₀ aryl and any one of NHCONH ₂ are represented.
Ar ¹ is any ^one of a phenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a heteroaryl group.
R ¹⁰ represents a phenyl group, a naphthyl group, a C _{3 to} C ₃₀ cycloalkyl group, a C _{1 to} C ₁₈ alkyl group, a C _{1 to} C ₈ haloalkyl group, a C _{2 to} C ₁₂ alkenyl group, or a C _{4 to} C ₃₀ cyclo. Any of the alkenyl groups; one or more —O— interrupted C ₂ -C ₁₈ alkyl groups; one or more —O—, —S—, —NR ⁹ —, —O (CO) —, And a C ₃ -C ₃₀ cycloalkyl group interrupted by any of —NR ⁹ (CO) — (all of which are optionally one or more Ar ¹ , OH, C ₁ -C ₁₈ alkyl groups, C ₁ -C ₈ haloalkyl group, C ₃ -C ₃₀ cycloalkyl group, a halogen _{group, -NO 2, -CN, C 1} ~C 12 alkoxy group, a phenoxy group, a phenoxycarbonyl group, a phenylthio group, phenylthio group, -NR ¹² R ¹³ , C ₁ -C ₁₂ alkylthio group , C ₂ -C ₁₂ alkoxycarbonyl group, C ₂ -C ₈ haloalkanoyl group, halobenzoyl group, C ₁ -C ₁₂ alkylsulfonyl group, phenylsulfonyl group, (4-methylphenyl) sulfonyl group, C ₁ -C ₁₂ alkylsulfonyloxy group, a phenylsulfonyloxy group, substituted (4-methylphenyl) sulfonyloxy group, C ₂ -C ₁₂ alkanoyl group, C ₂ -C ₁₂ alkanoyloxy group, benzoyl, and at least one of benzoyloxy group Or hydrogen.
R ¹¹ is a phenyl group, a naphthyl group, a C _{3 to} C ₃₀ cycloalkyl group, a C _{1 to} C ₁₈ alkyl group, a C _{1 to} C ₈ haloalkyl group, a C _{2 to} C ₁₂ alkenyl group, or a C _{4 to} C ₃₀ cyclo. Any of the alkenyl groups; one or more —O— interrupted C ₂ -C ₁₈ alkyl groups; one or more —O—, —S—, —NR ⁹ —, —O (CO) —, And a C ₃ -C ₃₀ cycloalkyl group interrupted by any one of —NR ⁹ (CO) —; C ₂ -C ₁₈ alkanoyl group; benzoyl group; C ₁ -C ₁₈ alkylsulfonyl group; hydrogen, phenylsulfonyl group , A (4-methylphenyl) sulfonyl group, a naphthylsulfonyl group, an anthracylsulfonyl group, and a phenanthrylsulfonyl group.
R ¹² , R ¹³ and R ⁹ are each independently a phenyl group, a naphthyl group, a C ₃ -C ₃₀ cycloalkyl group, a C ₁ -C ₁₈ alkyl group, a C ₁ -C ₈ haloalkyl group, a C _2- Any one of a C ₁₂ alkenyl group and a C ₄ -C ₃₀ cycloalkenyl group; a C ₂ -C ₁₈ alkyl group interrupted by one or more —O—; one or more —O—, —S—, ^{-NR 9 -, - O (CO} ) -, and ^-NR 9 (CO) - C ₃ interrupted by either -C ₃₀ cycloalkyl group; C ₂ -C ₁₈ alkanoyl group, a benzoyl group, and a C Any of _{1 to} C ₁₈ alkylsulfonyl groups; independently of each other, any of hydrogen, phenylsulfonyl group, (4-methylphenyl) sulfonyl group, naphthylsulfonyl group, anthracylsulfonyl group, and phenanthrylsulfonyl group; Any of Represents R ¹² and R ¹³ together with the nitrogen atom to which they are attached are optionally 5-membered, 6-membered and 7-membered rings interrupted by either —O— or —NR ⁹ —. Any of these may be formed.
R ¹⁴ is any one of a phenyl group, a naphthyl group, a C _{3 to} C ₃₀ cycloalkyl group, a C _{1 to} C ₁₈ alkyl group, a C _{1 to} C ₈ haloalkyl group, and a C _{4 to} C ₃₀ cycloalkenyl group; C ₂ -C ₁₈ alkyl radical which is interrupted by more than five -O-; 1 or more ^{-O -, - S -, -} NR 9 -, - O (CO) -, and ^-NR 9 (CO) - C ₃ -C ₃₀ cycloalkyl radical which is interrupted by one of; represents any of; hydrogen. R ⁹ and R ¹⁴ may form any of a 5-membered, 6-membered and 7-membered ring together with the N atom to which they are bonded.
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently hydrogen, halogen, C ₁ -C ₁₈ alkyl group, C ₁ -C ₁₈ alkoxy group, C ₁ -C ₈ haloalkyl group, CN, NO ₂ , C _{2 to} C ₁₈ alkanoyl group, benzoyl group, phenyl group, —S-phenyl group, OR ¹¹ , SR ⁹ , NR ¹² R ¹³ , C _{2 to} C ₆ alkoxycarbonyl group, phenoxycarbonyl group, S (O) pC ₁ -C ₁₈ alkyl group, S (O) p-C ₆ -C ₁₂ aryl group optionally substituted with C ₁ -C ₁₈ alkyl group, SO ₂ O—C ₁ -C ₁₈ alkyl group, SO ₂ It represents any of O—C ₆ -C ₁₀ aryl and NHCONH ₂ .
The Q ¹ represents any of —CR ²⁰ — and —N—, and the Q ² represents any of —CH ₂ —, —S—, —O—, and —NR ⁹ —.

  Specific examples of the photoacid generator represented by the general formula (II-1) to the general formula (II-4) include compounds represented by the following names and structural formulas: B-1 to B- 9 is mentioned.

[B-1]
5- {2- (methanesulfonyl) -ethanesulfoxy} -imino-5H-thiophen-2-ylidene-o-tolyl-acetonitrile absorption maximum wavelength: 410 nm

[B-2]
5- {2- (p-toluenesulfonyl) -ethanesulfoxy} -imino-5H-thiophen-2-ylidene-o-tolyl-acetonitrile absorption maximum wavelength: 408 nm

[B-3 (CGI1397)]
5- (3-propanesulfoxy) -imino-5H-thiophen-2-ylidene-o-tolyl acetonitrile absorption maximum wavelength: 405 nm

[B-4 (CGI1397)]
5- (8-octanesulfoxy) -imino-5H-thiophen-2-ylidene-o-tolyl acetonitrile absorption maximum wavelength: 405 nm

[B-5 (CGI 1380)]
5- (Camphorsulfoxy) -imino-5H-thiophen-2-ylidene-o-tolyl acetonitrile absorption maximum wavelength: 405 nm

[B-6 (CGI1311)]
5- (p-toluenesulfoxy) -imino-5H-thiophen-2-ylidene-o-tolyl acetonitrile absorption maximum wavelength: 410 nm

[B-7 (PAG103)]
3- (3-propanesulfoxy) -imino-2H-thiophene-3-ylidene-o-tolyl acetonitrile absorption maximum wavelength: 408 nm

[B-8 (PAG108)]
3- (8-Octanesulfoxy) -imino-2H-thiophene-3-ylidene-o-tolyl acetonitrile absorption maximum wavelength: 405 nm

[B-9 (PAG121)]
3- (p-Toluenesulfoxy) -imino-2H-thiophene-3-ylidene-o-tolyl acetonitrile absorption maximum wavelength: 405 nm

  As content of the said photo-acid generator B, 0.1-40 mass% is preferable with respect to solid content of the whole composition in the said positive photosensitive composition, and 0.2-20 mass% is more preferable. 1-10 mass% is especially preferable. When the content is less than 0.1% by mass, the sensitivity may be low. When the content exceeds 40% by mass, profile deterioration and process margin (especially baking process such as post-exposure heating process) may be narrowed. is there.

-(C) (other ingredients)-
The chemical amplification type positive photosensitive composition used in the present invention further has two or more phenolic OH groups that promote solubility in a surfactant, a spectral sensitizer, and a developer, if necessary. A compound, an organic solvent, a quencher, an adhesion promoter, and the like can be contained.

--Surfactant--
Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol. Ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate Sorb, fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, poly Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as xylethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, Ftop EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F173, F176, F189, R08 (manufactured by Dainippon Ink and Chemicals), Florad FC430, FC431 (Sumitomo 3M) Manufactured by Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 ( Yue Chemical Industries, Ltd.) and acrylic or methacrylic acid-based (co) polymer Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), and the like. Among these, fluorine-based surfactants and silicon-based surfactants are more preferable from the viewpoints of coatability and development defect reduction. These surfactants may be used alone or in combination of two or more.
As content of the said surfactant, 0.01-2 mass% is preferable normally with respect to solid content of the whole composition in the said positive photosensitive composition, and 0.01-1 mass% is more preferable.

  Further, for the purpose of improving the coating property, defoaming property, leveling property and the like of the positive photosensitive composition, examples of the surfactant include various anionic, cationic and nonionic active agents. For example, BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183 (manufactured by Dainippon Ink & Chemicals), Florard FC-135, FC-170C, FC-430, FC-431 (Sumitomo 3M Co., Ltd.), Surflon S-112, S-113, S-131, S-141, S-145 (Asahi Glass Co., Ltd.), Fluorosurfactants commercially available under names such as SH-28PA, -190, -193, SZ-6032, and SF-8428 (manufactured by Toray Silicone Co., Ltd.) can be used. The amount of these surfactants used is preferably 5 parts by mass or less with respect to 100 parts by mass of the acid-decomposable resin A.

--- Spectral sensitizer-
The spectral sensitizer sensitizes the chemically amplified positive photosensitive composition used in the present invention to i-line or It is added from the viewpoint of giving sensitivity to g-line.
Specific examples of the spectral sensitizer include benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, and anthracene. , Pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro -4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-t rt-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis ( (5,7-dimethoxycarbonylcoumarin), coronene, and the like are preferable, but not limited thereto.

--Compound having two or more phenolic OH groups--
The compound having two or more phenolic OH groups is added from the viewpoint of promoting solubility in a developer.
Examples of the compound having two or more phenolic OH groups include polyhydroxy compounds, which include phenols, resorcin, phloroglucin, phloroglucid, 2,3,4-trihydroxybenzophenone, 2 , 3,4,4′-tetrahydroxybenzophenone, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, tris (4-hydroxyphenyl) methane, tris (4 -Hydroxyphenyl) ethane, 1,1'-bis (4-hydroxyphenyl) cyclohexane.

-Organic solvent-
The organic solvent can be appropriately used for adjusting the viscosity of the photosensitive composition of the present invention. Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monophenyl ether, Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3- Ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3- Methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone , Diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy 2-methyl, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, ethyl-3-propoxypropionate, propyl-3-methoxypropionate, Isopropyl-3-methoxypropionate, ethyl ethoxy acetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, acetic acid Soamyl, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, benzyl methyl ether, benzyl ethyl ether, dihexyl ether, acetic acid Examples include benzyl, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, benzene, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin. . These may be used alone or in combination of two or more.

  As the content of the organic solvent, in order to obtain a thickness of 20 μm or more from the obtained positive photosensitive composition using a spin coating method, the solid content concentration of the positive photosensitive composition is 65% by mass or less. A range of is preferred. When the solid content concentration exceeds 65% by mass, the fluidity of the positive photosensitive composition is remarkably deteriorated and is difficult to handle, and it is difficult to obtain a uniform positive photosensitive layer by the spin coating method. Sometimes.

--Quencher--
There is no restriction | limiting in particular as said quencher, According to the objective, it can select suitably, For example, secondary or tertiary amines, such as a triethylamine, a tributylamine, a dibutylamine, a triethanolamine, etc. are mentioned.

-Adhesion promoter-
The adhesion promoter (hereinafter sometimes referred to as an adhesion assistant) is added for the purpose of improving the adhesion between the positive photosensitive layer and the substrate.
Suitable examples of the adhesion assistant include functional silane coupling agents. Here, the functional silane coupling agent means a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and specifically, for example, trimethoxysilyl. Benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. It is done.
The content of the adhesion assistant is preferably 20 parts by mass or less with respect to 100 parts by mass of the acid-decomposable resin A.

In addition, from the viewpoint of finely adjusting the solubility in an alkaline developer, the photosensitive composition of the present invention includes acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso-valeric acid, Monocarboxylic acids such as benzoic acid and cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid Hydroxy monocarboxylic acids such as acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, Isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, trimelli Polycarboxylic acids such as toic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, anhydrous Dodecenyl succinic acid, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4, -butanetetracarboxylic acid, cyclopentanetetracarboxylic dianhydride, Acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitic anhydride, and glycerin tris anhydrous trimellitate can also be added.
Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. It is also possible to add a high boiling point solvent.
The content of the compound for finely adjusting the solubility in the alkali developer can be adjusted according to the use and application method, and is not particularly limited as long as the composition can be mixed uniformly. However, it is preferably 60% by mass or less, more preferably 40% by mass or less, based on the total solid content of the obtained positive photosensitive composition.

If necessary, the positive photosensitive composition can further contain a filler, a colorant, a viscosity modifier and the like.
Examples of the filler include silica, alumina, talc, bentonite, zirconium silicate, and powdered glass.
Examples of the colorant include extender pigments such as alumina white, clay, barium carbonate, barium sulfate; zinc white, lead white, yellow lead, red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, carbon black, and the like. Inorganic pigments; Brilliant Carmine 6B, Permanent Red 6B, Permanent Red R, Organic Pigments such as Benzidine Yellow, Phthalocyanine Blue, and Phthalocyanine Green; Basic Dyes such as Magenta and Rhodamine; Direct Dyes such as Direct Scarlet and Direct Orange; Roserine, Meta Examples include acid dyes such as nil yellow. Examples of the viscosity modifier include bentonite, silica gel, aluminum powder, and the like.
The content thereof is preferably 50% by mass or less based on the total solid content of the obtained positive photosensitive composition in a range not impairing the essential characteristics of the positive photosensitive composition.

Moreover, an antifoamer and other additives can be added to the positive photosensitive composition as necessary.
Examples of the antifoaming agent include various silicone-based and fluorine-based antifoaming agents.

  The positive photosensitive composition solution used in the present invention may be prepared by mixing and stirring in the usual manner when no filler or pigment is added, and when a filler or pigment is added, a dissolver is used. , Using a disperser such as a homogenizer or a three-roll mill. Moreover, you may further filter using a mesh, a membrane filter, etc. as needed.

  The positive photosensitive layer is formed by a well-known coating method such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, and the like. It can form by apply | coating a composition coating liquid.

In addition, the said positive photosensitive composition can be used as a resist at the time of the etching of various board | substrates, such as a copper, chromium, iron, a glass substrate, and a resist for semiconductor manufacture as mentioned later.
The thickness of the positive photosensitive layer when the composition of the present invention is used as a photoresist film is preferably 0.1 to 10 μm, more preferably 0.5 to 7 μm, and more preferably 1 to 3 μm. When the thickness is less than 0.1 μm, the etching resistance may be inferior, and when it exceeds 10 μm, the resolution may be deteriorated.

<Base material>
There is no restriction | limiting in particular as the said base material used at the said positive photosensitive layer formation process, According to the objective, it selects suitably from what has a highly smooth surface to what has an uneven surface from well-known materials. However, a plate-like base material (substrate) is preferable. Specifically, a glass plate (for example, a soda glass plate, a glass plate sputtered with silicon oxide, a quartz glass plate, etc.), a synthetic resin film, Examples include paper and metal plates.
After cleaning the substrate having the preceding pattern or thin film, the substrate surface is treated with a solvent such as HMDS (hexamethylphosphoramide) to remove moisture on the substrate surface. The positive photosensitive composition is applied and dried using a spin coater. The drying temperature is preferably 100 to 150 ° C.

[Protective film formation process]
The protective film forming step is a step of forming a protective film containing at least polyvinyl alcohol having a mass average molecular weight of 8,000 to 100,000 on the surface of the positive photosensitive layer.
As the method for forming the protective film, for example, one or more of the protective film forming materials described later are dissolved in water or a mixture of water-miscible solvents to form an aqueous solution, It can be formed by applying an aqueous solution on the positive photosensitive layer and drying it.

As the protective film, the protective group decomposition reaction by the acid of the positive photosensitive layer is not hindered by the influence of a basic substance in the air or the environment during exposure, and the sensitivity of the positive photosensitive layer is kept high. If possible, the material, shape, structure, etc. are not particularly limited and can be appropriately selected according to the purpose. However, the air permeability is low and the transmission of light used for exposure is not substantially hindered. It is preferable.
Further, it is preferable that the protective film adheres or adheres more strongly to the photosensitive layer than the support.
Further, the protective film preferably has a small surface tack property from the viewpoint of handling properties and prevention of defects due to dust adhesion.

The protective film forming material is not particularly limited as long as it contains at least the above-mentioned polyvinyl alcohol having a weight average molecular weight of 8,000 to 100,000, and can be appropriately selected according to the purpose. It is preferably soluble, and more preferably soluble in a weak alkaline aqueous solution as a developer.
The protective film forming material preferably further contains a water-soluble resin in addition to the polyvinyl alcohol. Examples of the water-soluble resin include polyvinyl alcohol, polyvinyl pyrrolidone, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy Celluloses such as water-soluble salts of propylmethylcellulose, carboxyethylcellulose, carboxypropylcellulose, carboxyethylcellulose, carboxyalkylcellulose, water-soluble salts of acidic cellulose, carboxyalkyl starch, polyacrylamides, water-soluble polyamide, water-soluble polyacrylic acid Salt, polyvinyl ether / maleic anhydride polymer, ethylene oxide polymer, styrene / maleic acid copolymer, maleate resin, gelatin , Gum arabic. Among these, the combined use of polyvinyl alcohol and polyvinyl pyrrolidone is preferable from the viewpoint of improving the adhesion to the photosensitive layer.
Moreover, as said protective film, 1 type may be used individually among these, and 2 or more types may be used together.

The polyvinyl alcohol is required to have a mass average molecular weight of 8,000 to 100,000, particularly preferably 15,000 to 45,000. The polyvinyl alcohol preferably has a saponification rate of 75 to 95 mol%, particularly preferably 85 to 90 mol%.
If the mass average molecular weight is less than 8,000, an undesirable tackiness of the protective film is likely to occur, and the protective ability of the protective film may be reduced. Adhesion with the layer may be inferior.
Further, when the saponification rate is less than 75 mol%, the protective ability of the protective film may be reduced. There is.

Specifically as said polyvinyl alcohol, PVA-202, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-217EE, PVA-217E, PVA220E, PVA -403, PVA-405, PVA-420, PVA-613, PVA-617, PVA-706, PVA-CS, PVA-CST (all are trade names manufactured by Kuraray Co., Ltd.) and the like are preferable.
In the case of polyvinyl alcohol and polyvinylpyrrolidone, which is a suitable combination in the protective film forming material, the content of the polyvinyl alcohol is not particularly limited and can be appropriately selected according to the purpose. On the other hand, 50-90 mass% is preferable and 60-80 mass% is more preferable. When the content of the polyvinyl alcohol is less than 50% by mass, the ability to prevent contamination may be insufficient, and when the content exceeds 90% by mass, the adhesion to the positive photosensitive layer may be increased. May be inferior.
Moreover, there is no restriction | limiting in particular as content of the said polyvinylpyrrolidone in this case, Although it can select suitably according to the objective, 10-50 mass% is preferable with respect to the protective film whole quantity, and 20-40 mass % Is more preferable. When the content of the polyvinyl pyrrolidone is less than 10% by mass, the adhesion to the positive photosensitive layer may be insufficient, and when the content exceeds 50% by mass, the protective ability is deteriorated. Sometimes.

A surfactant may be further added to the protective film forming material for the purpose of improving the coating property of the protective film and improving the adhesion between the positive photosensitive layer and the protective film.
As the surfactant, for example, amphoteric surfactants such as alkylcarboxybetaines and perfluoroalkylbetaines described in JP-A-61-285444 can be used.
As content of this surfactant in the case of adding the said surfactant, 1-20 mass% of protective-film solid content is preferable, 1-10 mass% is more preferable, 1-5 mass% is especially preferable.

Examples of the water-miscible solvent used for dissolving the protective film forming material include methanol, ethanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and the like.
As content in the solvent total amount of the said water-miscible solvent, 1-80 mass% is preferable, 2-70 mass% is more preferable, 5-60 mass% is especially preferable.
The mixing ratio of water and solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, water: solvent is preferably 100: 0 to 80:20, more preferably 70:30. 60:40 is particularly preferred.
When the protective film is formed of an aqueous solution containing the protective film forming material, the solid content concentration in the aqueous solution of the protective film forming material is preferably 0.5 to 30% by mass, and 1 to 20%. % By mass is more preferable, and 2 to 10% by mass is particularly preferable.
When the solid content concentration is less than 0.5% by mass or exceeds 30% by mass, the thickness of the protective film may not be a predetermined thickness after drying.

  There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, Specifically, 0.1-3.0 micrometers is preferable and 0.2-2.5 micrometers is more preferable. 0.5 to 2.0 μm is particularly preferable. If the thickness of the protective film is less than 0.1 μm, the air permeability is too high and the protective ability may be reduced. If the thickness exceeds 3.0 μm, light scattering or refraction by the protective film may occur. Due to the influence, a blurred image may be formed on the image formed on the positive photosensitive layer, high resolution may not be obtained, and further development and resist peeling may take time.

[Intermediate layer forming step]
The intermediate layer forming step is a step of forming an intermediate layer on the positive photosensitive layer.
The intermediate layer is provided between the positive photosensitive layer and the protective layer. In forming the positive photosensitive layer and the protective layer, an organic solvent is used. Therefore, the intermediate layer is located between the layers, thereby preventing the two layers from being mixed with each other.

The intermediate layer is preferably dispersed or dissolved in water or an aqueous alkali solution.
As the material for the intermediate layer, known materials can be used. For example, polyvinyl ether / maleic anhydride polymer, carboxyalkyl described in JP-A No. 46-2121 and JP-B No. 56-40824 Water-soluble salt of cellulose, water-soluble cellulose ether, water-soluble salt of carboxyalkyl starch, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, water-soluble polyamide, water-soluble salt of polyacrylic acid, gelatin, ethylene oxide polymer, various Water soluble salts of the group consisting of starch and the like, styrene / maleic acid copolymers, maleate resins, and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use a hydrophilic polymer, and among these hydrophilic polymers, it is preferable to use at least polyvinyl alcohol, and a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

There is no restriction | limiting in particular as said polyvinyl alcohol, Although it can select suitably according to the objective, The saponification rate has preferable 80% or more.
When using the said polyvinyl pyrrolidone, as content, 1-75 mass% is preferable with respect to solid content of this intermediate | middle layer, 1-60 mass% is more preferable, 10-50 mass% is especially preferable.
When the content is less than 1% by mass, sufficient adhesion to the photosensitive layer may not be obtained, and when it exceeds 75% by mass, the oxygen blocking ability may be lowered, which is not preferable.

  The intermediate layer preferably has a low oxygen permeability. When the oxygen permeability of the intermediate layer is large and the oxygen blocking ability is low, it may be necessary to increase the amount of light at the time of exposure to the positive photosensitive layer, or it may be necessary to lengthen the exposure time, and the resolution may also be increased. May fall.

There is no restriction | limiting in particular as thickness of the said intermediate | middle layer, According to the objective, it can select suitably, 0.1-5 micrometers is preferable and 0.5-2 micrometers is more preferable.
If the thickness is less than 0.1 μm, oxygen permeability may be too high, and if it exceeds 5 μm, it takes a long time for development or removal of the intermediate layer, which is not preferable.

[Other layer formation process]
There is no restriction | limiting in particular as said other layer formation process, According to the objective, it can select suitably, For example, formation processes, such as a light absorption layer and a surface protective layer, are mentioned.
There is no restriction | limiting in particular as said other layer formation method, According to the objective, it can select suitably, For example, the method of apply | coating on the said positive photosensitive layer etc. are mentioned.

[Exposure process]
The exposure step is a step of exposing the positive photosensitive layer from the protective film side.
The exposure process is preferably an exposure process using an exposure method (maskless pattern exposure) in which a two-dimensional image is formed by performing relative scanning while exposing light while modulating light based on image data.

  Maskless pattern exposure is an exposure method in which two-dimensional images are formed by using two-dimensional spatial light modulation devices and performing relative scanning while modulating light based on image data.

  More specifically, an object called a “mask” in which an image (exposure pattern; hereinafter also referred to as a pattern) is formed of a material that does not transmit or weakens and transmits exposure light is disposed in the optical path of exposure light. Exposure method in which a photosensitive layer is exposed in a pattern without using the "mask", compared to a conventional mask exposure method (also referred to as mask exposure) in which a photosensitive layer is exposed in a pattern corresponding to the image That's it.

In maskless pattern exposure, an ultra-high pressure mercury lamp or a laser is used as a light source.
An ultra-high pressure mercury lamp is a discharge lamp in which mercury is enclosed in a quartz glass tube, etc., and has a high mercury vapor pressure to increase luminous efficiency (the mercury vapor pressure during lighting is approximately 5 MPa) W. Ellenbaas: Light Sources, Philips Technical Library 148-150). Of the bright line spectrum, a single exposure wavelength of 405 nm ± 40 nm is used, and h-line (405 nm) can be mainly used.

  Laser is an acronym for Light Amplification by Stimulated Emission of Radiation. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplifying and oscillating light waves, utilizing the phenomenon of stimulated emission that occurs in materials with an inverted distribution. Excitation media include crystals, glass, liquids, dyes, gases, etc. From these media, solid lasers (YAG lasers), liquid lasers, gas lasers (argon lasers, He-Ne lasers, carbon dioxide lasers, excimer lasers), semiconductor lasers A known laser such as can be used in the wavelength region.

  The semiconductor laser uses a light emitting diode that induces and emits coherent light at the pn junction when electrons and holes flow out to the junction due to carrier injection, excitation by an electron beam, ionization by collision, optical excitation, and the like. It is a laser. The wavelength of the emitted coherent light is determined by the semiconductor compound. The laser wavelength is a single exposure wavelength of 405 nm ± 40 nm.

  In the present invention, the single exposure wavelength means the dominant wavelength when using a laser, and when using an ultra-high pressure mercury lamp, the emission wavelength other than 405 nm is cut with an ND filter to a wavelength larger than 365 nm or 405 nm. This means one wavelength only.

A method of performing relative scanning while modulating light will be described.
One typical method is a two-dimensional micromirror such as DMD (digital micromirror device, for example, an optical semiconductor developed in 1987 by Dr. Larry Hornbeck et al., Texas Instruments, USA). This is a method of using spatial modulation elements arranged in line.
In this case, the light from the light source is irradiated onto the DMD by an appropriate optical system, and the reflected light from each mirror arranged two-dimensionally on the DMD passes through another optical system on the photosensitive layer in a two-dimensional manner. An image of light spots arranged in a row is formed. If the light spot is not exposed between the light spots, the image of the light spots arranged in two dimensions is moved in a direction slightly inclined with respect to the two-dimensional arrangement direction. The entire surface of the photosensitive layer can be exposed in such a manner that the light spots in the rear row are exposed between the light spots. An image pattern can be formed by controlling the angle of each mirror of the DMD and turning the light spot on and off. By aligning and using exposure heads having such DMDs, it is possible to deal with substrates of various widths.
In the DMD, the brightness of the light spot has only two gradations, ON or OFF, but exposure with 256 gradations can be performed by using a mirror gradation spatial modulation element.

  On the other hand, another representative method of relative scanning while modulating light according to the present invention is a method using a polygon mirror. A polygon mirror is a rotating member having a series of planar reflecting surfaces around it. The light from the light source is reflected and irradiated onto the photosensitive layer, and the light spot of the reflected light is scanned by the rotation of the plane mirror. By moving the substrate at right angles to the scanning direction, the entire surface of the photosensitive layer on the substrate can be exposed. An image pattern can be formed by controlling the intensity of light from the light source to ON-OFF or halftone by an appropriate method. By using a plurality of light from the light source, the scanning time can be shortened.

As a method of performing relative scanning while modulating light of the present invention, for example, the following method can also be applied.
An example of drawing using a polygon mirror described in JP-A-5-150175, an apparatus using a polygon mirror by visually acquiring a part of an image of a lower layer described in JP-T-2004-523101 (WO2002 / 039793) In this example, exposure is performed with the position of the upper layer aligned with the position of the lower layer, an example of exposure with DMD described in JP-A-2004-56080, an exposure apparatus equipped with a polygon mirror described in JP-T-2002-523905, and JP-A-2001-255661 An exposure apparatus including a polygon mirror described in JP-A-2003-50469, an example of a combination of DMD, LD, and multiple exposure described in JP-A-2003-50469, an example of an exposure method that changes an exposure amount depending on a part of a substrate described in JP-A-2003-156893 This is an example of an exposure method for performing misalignment adjustment described in Japanese Patent Application Laid-Open No. 2005-43576.

Hereinafter, the relative scanning exposure will be described in detail.
-Relative scanning exposure-
The exposure method of the present invention includes a method using an ultra high pressure mercury lamp and a method using a laser, but the latter is preferred. As the laser in the present invention, a laser having a single exposure wavelength of 405 nm ± 40 nm can be used, and specifically, a known laser such as a semiconductor laser (GaN-based) can be used.

In the patterning step, the light to be irradiated is not particularly limited and can be appropriately selected depending on the purpose. For example, the electromagnetic wave that activates the photopolymerization initiator and the sensitizer, ultraviolet to visible light, electrons X-rays, X-rays, laser light, and the like. Among these, laser light that can perform on / off control of light in a short time and easily control light interference is preferable.
The wavelength of the “ultraviolet to visible light” is not particularly limited and may be appropriately selected depending on the intended purpose. However, in order to shorten the exposure time of the photosensitive composition, 330 to 650 nm is preferable, 365 to 445 nm is more preferable, and 405 nm is particularly preferable.

  The light irradiation method is not particularly limited and can be appropriately selected depending on the purpose. For example, a high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a cold cathode tube for a copying machine, an LED, a semiconductor laser, etc. The method of irradiating with the well-known light source of this is mentioned. Further, it is preferable to synthesize and irradiate two or more lights from these light sources, and to irradiate a laser beam (hereinafter sometimes referred to as “combined laser beam”) that combines the two or more lights. Is particularly preferred.

  There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this several laser light source There is a method of forming and irradiating a combined laser beam with a collective optical system that collects light and couples it to the multimode optical fiber.

The beam diameter of the laser is not particularly limited, but among them, from the viewpoint of the resolution of the dark color separation barrier, the 1 / e ² value of the Gaussian beam is preferably 5 to 30 μm, and more preferably 7 to 20 μm.
The energy amount of the laser beam is not particularly limited, but in particular, from the viewpoint of exposure time and resolution, 1 to 100 mJ / cm ² is preferable, and 5 to 20 mJ / cm ² is more preferable.
In the present invention, it is necessary to spatially modulate laser light according to image data. For this purpose, it is preferable to use a digital micro device which is a spatial light modulation element.

  As the exposure apparatus, for example, the following apparatus can be used. Hereinafter, although an example of the three-dimensional exposure apparatus using a laser beam is shown, the exposure apparatus in the present invention is not limited to this.

  As shown in FIG. 1, the exposure unit includes a flat stage 152 that holds the glass substrate 150 by adsorbing the glass substrate 150 to the surface. Two guides 158 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 156 supported by the four legs 154. The stage 152 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by a guide 158 so as to be reciprocally movable. The exposure apparatus is provided with a drive device (not shown) for driving the stage 152 along the guide 158.

  A U-shaped gate 160 is provided at the center of the installation table 156 so as to straddle the movement path of the stage 152. Each of the ends of the U-shaped gate 160 is fixed to both side surfaces of the installation table 156. A scanner 162 is provided on one side of the gate 160, and a plurality of (for example, two) detection sensors 164 for detecting the front and rear ends of the photosensitive material 150 are provided on the other side. The scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152. The scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.

As shown in FIGS. 2 and 3B, the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in an approximately matrix of m rows and n columns (for example, 3 rows and 5 columns). ing. In this example, four exposure heads 166 are arranged in the third row in relation to the width of the photosensitive material 150. In addition, when showing each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure head 166 _mn .

An exposure area 168 by the exposure head 166 has a rectangular shape with a short side in the sub-scanning direction. Therefore, as the stage 152 moves, a strip-shaped exposed area 170 is formed for each exposure head 166 in the photosensitive material 150. In addition, when showing the exposure area by each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure area 168 _mn .

Further, as shown in FIGS. 3A and 3B, each of the exposure heads in each row arranged in a line so that the strip-shaped exposed areas 170 are arranged without gaps in the direction orthogonal to the sub-scanning direction. In the arrangement direction, they are shifted by a predetermined interval (a natural number times the long side of the exposure area, twice here). Therefore, can not be exposed portion between the exposure area _{168 11} in the first row and the exposure area _{168 12,} it can be exposed by the second row of the exposure area _{168 21} and the exposure area _{168 31} in the third row.

Each of the exposure heads 166 _{11 to} 166 _mn is a spatial light modulation element that modulates an incident light beam for each pixel according to image data, as shown in FIGS. 4, 5 (A) and (B). A digital micromirror device (DMD) 50 is provided. The DMD 50 is connected to a controller (not shown) including a data processing unit and a mirror drive control unit. The data processing unit of this controller generates a control signal for driving and controlling each micromirror in the region to be controlled by the DMD 50 for each exposure head 166 based on the input image data. The area to be controlled will be described later. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the image data processing unit. The control of the angle of the reflecting surface will be described later.

  On the light incident side of the DMD 50, a fiber array light source 66 including a laser emitting portion in which an emitting end portion (light emitting point) of an optical fiber is arranged in a line along a direction corresponding to the long side direction of the exposure area 168, a fiber A lens system 67 for correcting the laser light emitted from the array light source 66 and condensing it on the DMD, and a mirror 69 for reflecting the laser light transmitted through the lens system 67 toward the DMD 50 are arranged in this order.

  The lens system 67 includes a pair of combination lenses 71 that collimate the laser light emitted from the fiber array light source 66 and a pair of combination lenses that correct the light quantity distribution of the collimated laser light to be uniform. 73 and a condensing lens 75 that condenses the laser light whose light intensity distribution is corrected on the DMD. With respect to the arrangement direction of the laser emitting end, the combination lens 73 spreads the light beam at a portion close to the optical axis of the lens and contracts the light beam at a portion away from the optical axis, and with respect to a direction orthogonal to the arrangement direction. Has a function of allowing light to pass through as it is, and corrects the laser light so that the light quantity distribution is uniform.

  Further, on the light reflection side of the DMD 50, lens systems 54 and 58 that form an image of the laser light reflected by the DMD 50 on the scanning surface (exposed surface) 56 of the photosensitive material 150 are arranged. The lens systems 54 and 58 are arranged so that the DMD 50 and the exposed surface 56 are in a conjugate relationship.

  As shown in FIG. 6, the DMD 50 is configured such that a micromirror 62 is supported by a support column on an SRAM cell (memory cell) 60, and a large number of (pixels) (pixels) are formed. For example, the mirror device is configured by arranging 600 × 800 micromirrors in a lattice pattern. Each pixel is provided with a micromirror 62 supported by a support column at the top, and a material having a high reflectance such as aluminum is deposited on the surface of the micromirror 62. The reflectance of the micromirror 62 is 90% or more. A silicon gate CMOS SRAM cell 60 manufactured in a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke, and is entirely monolithic (integrated type). ).

  When a digital signal is written in the SRAM cell 60 of the DMD 50, the micromirror 62 supported by the support is inclined within a range of ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 50 is disposed with the diagonal line as the center. It is done. FIG. 7A shows a state in which the micromirror 62 is tilted to + α degrees in the on state, and FIG. 7B shows a state in which the micromirror 62 is tilted to −α degrees in the off state. Therefore, by controlling the inclination of the micromirror 62 in each pixel of the DMD 50 as shown in FIG. 6 according to the image signal, the light incident on the DMD 50 is reflected in the inclination direction of each micromirror 62. .

  FIG. 6 shows an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled to + α degrees or −α degrees. On / off control of each micromirror 62 is performed by a controller (not shown) connected to the DMD 50. A light absorber (not shown) is arranged in the direction in which the light beam is reflected by the micromirror 62 in the off state.

  Further, it is preferable that the DMD 50 be arranged with a slight inclination so that the short side thereof forms a predetermined angle θ (for example, 1 ° to 5 °) with the sub-scanning direction. 8A shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not tilted, and FIG. 8B shows the scanning trajectory of the exposure beam 53 when the DMD 50 is tilted. Show.

In the DMD 50, a number of micromirror arrays in which a large number (for example, 800) of micromirrors are arranged in the longitudinal direction are arranged in a large number (for example, 600 sets) in the short direction. as shown, by tilting the DMD 50, the pitch P ₁ of the scanning locus of the exposure beams 53 from each micromirror (scan line), it becomes narrower than the pitch P ₂ of the scanning lines in the case of not tilting the DMD 50, significant resolution Can be improved. On the other hand, the inclination angle of the DMD 50 is small, the scanning width _{W 2} in the case of tilting the DMD 50, which is substantially equal to the scanning width _{W 1} when not inclined DMD 50.

  Further, the same scanning line is overlapped and exposed (multiple exposure) by different micromirror rows. In this way, by performing multiple exposure, it is possible to control a minute amount of the exposure position and to realize high-definition exposure. Further, joints between a plurality of exposure heads arranged in the main scanning direction can be connected without a step by controlling a very small amount of exposure position.

  Note that the same effect can be obtained by arranging the micromirror rows in a staggered manner by shifting the micromirror rows by a predetermined interval in a direction orthogonal to the sub-scanning direction instead of inclining the DMD 50.

  As shown in FIG. 9A, the fiber array light source 66 includes a plurality of (for example, six) laser modules 64, and one end of the multimode optical fiber 30 is coupled to each laser module 64. Yes. The other end of the multimode optical fiber 30 is coupled with an optical fiber 31 having the same core diameter as the multimode optical fiber 30 and a cladding diameter smaller than the multimode optical fiber 30, as shown in FIG. A laser emission portion 68 is configured by arranging emission ends (light emission points) of the optical fiber 31 in a line along a main scanning direction orthogonal to the sub-scanning direction. As shown in FIG. 9D, the light emitting points can be arranged in two rows along the main scanning direction.

  As shown in FIG. 9B, the emission end of the optical fiber 31 is sandwiched and fixed between two support plates 65 having a flat surface. Further, a transparent protective plate 63 such as glass is disposed on the light emitting side of the optical fiber 31 in order to protect the end face of the optical fiber 31. The protective plate 63 may be disposed in close contact with the end surface of the optical fiber 31 or may be disposed so that the end surface of the optical fiber 31 is sealed. The light emitting end portion of the optical fiber 31 has a high light density and is likely to collect dust and easily deteriorate. However, by disposing the protective plate 63, it is possible to prevent the dust from adhering to the end face and to delay the deterioration.

  Here, in order to arrange the output ends of the optical fibers 31 with a small cladding diameter in a line without any gaps, the multi-mode optical fibers 30 are stacked between two adjacent multi-mode optical fibers 30 at a portion with a large cladding diameter. The exit ends of the optical fibers 31 coupled to the stacked multi-mode optical fibers 30 are the two exit ends of the optical fibers 31 coupled to the two adjacent multi-mode optical fibers 30 in the portion where the cladding diameter is large. They are arranged so that they are sandwiched between them.

  For example, as shown in FIG. 10, an optical fiber 31 having a length of 1 to 30 cm and having a small cladding diameter is coaxially connected to the tip of the multimode optical fiber 30 having a large cladding diameter on the laser light emission side. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 31 is fused and joined to the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 31 a of the optical fiber 31 is the same as the diameter of the core 30 a of the multimode optical fiber 30.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused to an optical fiber having a short cladding diameter and a large cladding diameter may be coupled to the output end of the multimode optical fiber 30 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 31 may be referred to as an emission end portion of the multimode optical fiber 30.

  The multimode optical fiber 30 and the optical fiber 31 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used. Here, the multimode optical fiber 30 and the optical fiber 31 are step index optical fibers, and the multimode optical fiber 30 has a cladding diameter = 125 μm, a core diameter = 25 μm, NA = 0.2, and transmission of the incident end face coating. The ratio is 99.5% or more, and the optical fiber 31 has a cladding diameter = 60 μm, a core diameter = 25 μm, and NA = 0.2.

  In general, in laser light in the infrared region, propagation loss increases as the cladding diameter of the optical fiber is reduced. For this reason, a suitable cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, the cladding thickness {(cladding diameter−core diameter) / 2} is set to infrared light having a wavelength band of 800 nm. The propagation loss hardly increases even if it is about ½ of the case of propagating infrared light and about ¼ of the case of propagating infrared light in the 1.5 μm wavelength band for communication. Therefore, the cladding diameter can be reduced to 60 μm.

  However, the cladding diameter of the optical fiber 31 is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber light source is 125 μm, but the depth of focus becomes deeper as the clad diameter becomes smaller. Therefore, the clad diameter of the multimode optical fiber is preferably 80 μm or less, more preferably 60 μm or less. Preferably, it is 40 μm or less. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 31 is preferably 10 μm or more.

  The laser module 64 includes a combined laser light source (fiber light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6, which are arrayed and fixed on the heat block 10. And LD7, collimator lenses 11, 12, 13, 14, 15, 16, and 17 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 20, and one multi-lens. Mode optical fiber 30. The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a clad diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

  The GaN-based semiconductor lasers LD1 to LD7 all have a common oscillation wavelength (for example, 405 nm), and all the maximum outputs are also common (for example, 100 mW for a multimode laser and 30 mW for a single mode laser). As the GaN-based semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above-described 405 nm in a wavelength range of 365 nm to 445 nm may be used.

  As shown in FIGS. 12 and 13, the above-described combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements. The package 40 includes a package lid 41 created so as to close the opening thereof. After the deaeration process, a sealing gas is introduced, and the package 40 and the package lid 41 are closed by closing the opening of the package 40 with the package lid 41. 41. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by 41.

  A base plate 42 is fixed to the bottom surface of the package 40, and the heat block 10, a condensing lens holder 45 that holds the condensing lens 20, and the multimode optical fiber 30 are disposed on the top surface of the base plate 42. A fiber holder 46 that holds the incident end is attached. The exit end of the multimode optical fiber 30 is drawn out of the package from an opening formed in the wall surface of the package 40.

  Further, a collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held. An opening is formed in the lateral wall surface of the package 40, and a wiring 47 for supplying a driving current to the GaN-based semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 13, in order to avoid complication of the drawing, only the GaN semiconductor laser LD7 is numbered among the plurality of GaN semiconductor lasers, and only the collimator lens 17 is numbered among the plurality of collimator lenses. is doing.

  FIG. 14 shows the front shape of the attachment part of the collimator lenses 11-17. Each of the collimator lenses 11 to 17 is formed in a shape obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the length direction is orthogonal to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 14).

  On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having a light emission width of 2 μm, and each of the laser beams B1 in a direction parallel to the active layer and a divergence angle in a direction perpendicular to the active layer. A laser emitting ~ B7 is used. These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.

Accordingly, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the divergence angle is small with respect to the elongated collimator lenses 11 to 17 as described above. Incident light is incident in a state where the direction coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses 11 to 17 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2. 6 mm. In addition, each of the collimator lenses 11 to 17 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 20 is obtained by cutting an area including the optical axis of a circular lens having an aspheric surface into a long and narrow shape in parallel planes, and is long in the arrangement direction of the collimator lenses 11 to 17, that is, in the horizontal direction and short in the direction perpendicular thereto. Is formed. This condenser lens 20 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 20 is also formed by molding resin or optical glass, for example.

Next, the operation of the exposure apparatus will be described.
In each exposure head 166 of the scanner 162, laser beams B1, B2, B3, B4, B5, B6 emitted in a divergent light state from each of the GaN-based semiconductor lasers LD1 to LD7 constituting the combined laser light source of the fiber array light source 66. , And B7 are collimated by corresponding collimator lenses 11-17. The collimated laser beams B <b> 1 to B <b> 7 are collected by the condenser lens 20 and converge on the incident end face of the core 30 a of the multimode optical fiber 30.

  Here, a condensing optical system is configured by the collimator lenses 11 to 17 and the condensing lens 20, and a multiplexing optical system is configured by the condensing optical system and the multimode optical fiber 30. That is, the laser beams B1 to B7 condensed as described above by the condenser lens 20 are incident on the core 30a of the multimode optical fiber 30 and propagate through the optical fiber to be combined with one laser beam B. The light is emitted from the optical fiber 31 coupled to the output end of the multimode optical fiber 30.

  In each laser module, when the coupling efficiency of the laser beams B1 to B7 to the multimode optical fiber 30 is 0.85 and each output of the GaN-based semiconductor lasers LD1 to LD7 is 30 mW, the light arranged in an array For each of the fibers 31, a combined laser beam B with an output of 180 mW (= 30 mW × 0.85 × 7) can be obtained. Therefore, the output from the laser emitting unit 68 in which the six optical fibers 31 are arranged in an array is about 1 W (= 180 mW × 6).

  In the laser emitting portion 68 of the fiber array light source 66, light emission points with high luminance are arranged in a line along the main scanning direction as described above. A conventional fiber light source that couples laser light from a single semiconductor laser to a single optical fiber has low output, so a desired output cannot be obtained unless multiple rows are arranged. Since the light source has a high output, a desired output can be obtained even with a small number of columns, for example, one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled one-on-one, a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser, and the core diameter is 50 μm and the cladding diameter is 125 μm. Since a multimode optical fiber having a numerical aperture (NA) of 0.2 is used, if an output of about 1 W (watt) is to be obtained, 48 multimode optical fibers (8 × 6) must be bundled. Since the area of the light emitting region is 0.62 mm ² (0.675 mm × 0.925 mm), the luminance at the laser emitting portion 68 is 1.6 × 10 ⁶ (W / m ² ) and one optical fiber is used. The luminance per hit is 3.2 × 10 ⁶ (W / m ² ).

On the other hand, as described above, an output of about 1 W can be obtained with the six multimode optical fibers, and the area of the light emitting region at the laser emitting unit 68 is 0.0081 mm ² (0.325 mm × 0.025 mm). Therefore, the luminance at the laser emitting portion 68 is 123 × 10 ⁶ (W / m ² ), and the luminance can be increased about 80 times as compared with the conventional case. Further, the luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 28 times compared to the conventional one.

  Here, with reference to FIGS. 15A and 15B, the difference in the depth of focus by the exposure head will be described. In FIG. 15A, the diameter of the light emission region of the bundled fiber light source of the exposure head in the sub-scanning direction is 0.675 mm. In FIG. 15B, the light emission region of the fiber array light source of the exposure head in the sub-scanning direction. The diameter is 0.025 mm. As shown in FIG. 15A, in this exposure head, since the light emitting area of the light source (bundle-shaped fiber light source) 1 is large, the angle of the light beam incident on the DMD 3 increases, and as a result, the light beam incident on the scanning surface 5. The angle becomes larger. For this reason, the beam diameter tends to increase with respect to the light condensing direction (shift in the focus direction).

  On the other hand, as shown in FIG. 15B, in this exposure head, since the diameter of the light emitting region of the fiber array light source 66 is small in the sub-scanning direction, the angle of the light beam that passes through the lens system 67 and enters the DMD 50 is small. As a result, the angle of the light beam incident on the scanning surface 56 is reduced. That is, the depth of focus becomes deep. In this example, the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus substantially corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot. This effect on the depth of focus is more prominent and effective as the required light quantity of the exposure head is larger. In this example, the size of one pixel projected on the exposure surface is 10 μm × 10 μm. DMD is a reflective spatial modulation element, but FIGS. 15A and 15B are developed views for explaining the optical relationship.

  Image data corresponding to the exposure pattern is input to a controller (not shown) connected to the DMD 50 and temporarily stored in a frame memory in the controller. This image data is data representing the density of each pixel constituting the image by binary values (whether or not dots are recorded).

  The stage 152 that has adsorbed the photosensitive material 150 to the surface is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device (not shown). When the leading edge of the photosensitive material 150 is detected by the detection sensor 164 attached to the gate 160 when the stage 152 passes under the gate 160, the image data stored in the frame memory is sequentially read out for a plurality of lines. A control signal is generated for each exposure head 166 based on the image data read by the data processing unit. Then, each of the micromirrors of the DMD 50 is controlled on and off for each exposure head 166 based on the generated control signal by the mirror drive control unit.

  When the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the micro mirror of the DMD 50 is in an on state forms an image on the exposed surface 56 of the photosensitive material 150 by the lens systems 54 and 58. Is done. In this way, the laser light emitted from the fiber array light source 66 is turned on and off for each pixel, and the photosensitive material 150 is exposed in pixel units (exposure area 168) that is approximately the same number as the number of pixels used in the DMD 50. Further, when the photosensitive material 150 is moved at a constant speed together with the stage 152, the photosensitive material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region 170 is formed for each exposure head 166. It is formed.

  As shown in FIGS. 16A and 16B, in the DMD 50, 600 sets of micromirror rows in which 800 micromirrors are arranged in the main scanning direction are arranged in the sub-scanning direction. Thus, only a part of the micro mirror rows (for example, 800 × 100 rows) is controlled to be driven.

  As shown in FIG. 16A, a micromirror array arranged at the center of the DMD 50 may be used, and as shown in FIG. 16B, the micromirror array arranged at the end of the DMD 50 is used. May be used. In addition, when a defect occurs in some of the micromirrors, the micromirror array to be used may be appropriately changed depending on the situation, such as using a micromirror array in which no defect has occurred.

  Since the data processing speed of the DMD 50 is limited and the modulation speed per line is determined in proportion to the number of pixels used, the modulation speed per line can be increased by using only a part of the micromirror rows. Get faster. On the other hand, in the case of an exposure method in which the exposure head is continuously moved relative to the exposure surface, it is not necessary to use all the pixels in the sub-scanning direction.

  For example, when only 300 sets are used in 600 micromirror rows, modulation can be performed twice as fast per line as compared to the case of using all 600 sets. Further, when only 200 sets of 600 micromirror arrays are used, modulation can be performed three times faster per line than when all 600 sets are used. That is, an area of 500 mm in the sub-scanning direction can be exposed in 17 seconds. Further, when only 100 sets are used, modulation can be performed 6 times faster per line. That is, an area of 500 mm in the sub-scanning direction can be exposed in 9 seconds.

  The number of micromirror rows to be used, that is, the number of micromirrors arranged in the sub-scanning direction is preferably 10 or more and 200 or less, and more preferably 10 or more and 100 or less. Since the area per micromirror corresponding to one pixel is 15 μm × 15 μm, when converted to the use area of DMD50, an area of 12 mm × 150 μm or more and 12 mm × 3 mm or less is preferable, and 12 mm × 150 μm or more and 12 mm A region of × 1.5 mm or less is more preferable.

  If the number of micromirror rows to be used is within the above range, as shown in FIGS. 17A and 17B, the laser light emitted from the fiber array light source 66 is made into substantially parallel light by the lens system 67, and the DMD 50 Can be irradiated. It is preferable that the irradiation area where the laser beam is irradiated by the DMD 50 coincides with the use area of the DMD 50. When the irradiation area is wider than the use area, the utilization efficiency of the laser light is lowered.

  On the other hand, the diameter of the light beam condensed on the DMD 50 in the sub-scanning direction needs to be reduced according to the number of micromirrors arranged in the sub-scanning direction by the lens system 67, but the number of micromirror rows to be used. Is less than 10, it is not preferable because the angle of the light beam incident on the DMD 50 increases and the depth of focus of the light beam on the scanning surface 56 becomes shallow. Further, the number of micromirror rows to be used is preferably 200 or less from the viewpoint of modulation speed. DMD is a reflective spatial modulation element, but FIGS. 17A and 17B are developed views for explaining the optical relationship.

  When the sub scanning of the photosensitive material 150 by the scanner 162 is completed and the rear end of the photosensitive material 150 is detected by the detection sensor 164, the stage 152 is moved along the guide 158 by the driving device (not shown) on the most upstream side of the gate 160. Returned to the origin at the point, and again moved along the guide 158 from the upstream side to the downstream side of the gate 160 at a constant speed.

  As described above, the exposure unit (exposure apparatus) includes a DMD in which 600 micromirror arrays in which 800 micromirrors are arranged in the main scanning direction are arranged in 600 sets in the subscanning direction. Since the control is performed so that only the micromirror array is driven, the modulation speed per line becomes faster than when all the micromirror arrays are driven. This enables high-speed exposure.

[Development process]
The developing step includes a step of developing the photosensitive layer by exposing the photosensitive layer by the exposing step and removing an unexposed portion.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.
In the present invention, the number of steps in the manufacturing process of the TFT array substrate is combined with the intensity-modulated exposure in the exposure step by performing development using two or more types of developers having different development intensities in the development step. Reduction is possible.

There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, A weak alkaline aqueous solution (henceforth an alkali developing solution) is preferable.
Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, sodium metasilicate, and aqueous ammonia; first examples such as ethylamine and n-propylamine. Amines; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; amides such as formamide and acetamide; tetra Methylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide, tetraethanolammonium hydroxide, Quaternary ammonium salts such as tiltriethanolammonium hydroxide, benzylmethyldiethanolammonium hydroxide, benzyldimethylethanolammonium hydroxide, benzyltriethanolammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide; pyrrole, piperidine And an aqueous solution of an alkali such as a cyclic amine.
The concentration of the alkaline substance in the alkaline developer is preferably 0.1 to 10% by mass.
The temperature of the developer can be appropriately selected according to the developability of the positive photosensitive layer, and is preferably about 25 ° C. to 40 ° C., for example.

There is no restriction | limiting in particular as said image development system, According to the objective, it can select suitably, For example, paddle image development, shower image development, shower & spin image development, dip image development, etc. are mentioned.
The shower development will be described. The uncured portion can be removed by spraying a developer onto the positive photosensitive layer after exposure. Prior to development, it is preferable to spray an alkaline solution having a low solubility of the positive photosensitive layer with a shower or the like to remove the intermediate layer and the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.

[Post-exposure heating process]
The post-exposure heating step is a step of performing heat treatment (post-exposure bake, PEB) on the positive photosensitive layer after the exposure step.
Examples of the PEB method include proximity baking that provides a gap between the hot plate and the substrate, direct baking that does not provide a gap, and the like. In order to obtain, the method of performing direct baking after performing proximity baking is preferable.
As heating temperature in the said PEB, 90-150 degreeC is preferable and 100-140 degreeC is more preferable. When the heating temperature is less than 90 ° C., the reactivity of the decomposition reaction of the acid-decomposable resin is inferior and the sensitivity and resolution may not be improved. When the heating temperature exceeds 150 ° C., the positive photosensitive composition The resin inside may be decomposed and the film quality may be weak and brittle.
As heating time in the said whole surface heating, 5-300 seconds are preferable and 10-100 seconds are more preferable.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

[Heating process after development]
The post-development heating step is a step of performing a heat treatment on the positive photosensitive layer in the formed pattern after the development step.
Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the pattern is formed after the developing step. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
As heating time in the said whole surface heating, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

[Other processes]
There is no restriction | limiting in particular as said other process, Although it selects suitably from the processes in well-known pattern formation, For example, an etching process, a resist peeling process, etc. are mentioned. These may be used alone or in combination of two or more.

-Etching process-
The etching step can be performed by a method appropriately selected from known etching methods, and is performed to remove a base portion not covered with a resist pattern to obtain a thin film pattern.
Either a treatment with an etching solution (wet etching) or a reaction by gas discharge under reduced pressure to form a gas (dry etching) is performed.
When performing the wet etching, it is desirable to perform post-baking in order to prevent undercut due to the penetration of the etchant. Usually, these post-baking is performed at about 110 ° C. to 140 ° C., but is not necessarily limited thereto. As etchants used, many etchants have been developed and used, with ferric chloride / hydrochloric acid system, hydrochloric acid / nitric acid system, hydrobromic acid system and the like as representative examples. Cerium ammonium nitrate solution for Cr, diluted hydrofluoric acid for Ti and Ta, hydrogen peroxide solution for Mo, phosphorous nitric acid for MoW, Al, diluted aqua regia, ferric chloride solution for ITO, hydrogen iodide solution, buffered hydrofluoric acid is SiNx or SiO _2, a-Si, the n + a-Si is used, respectively hydrofluoric nitric acid.

In the positive photosensitive composition used in the present invention, the dry etching resistance of the resist pattern can be improved by adding a thermal crosslinking agent to the positive photosensitive layer and performing post-baking.
As an etchant gas used in the dry etching, an etchant gas suitable for each film type is used. Carbon tetrafluoride (chlorine) + oxygen, carbon tetrafluoride (sulfur hexafluoride) + hydrogen chloride (chlorine) for a-Si / n ⁺ and s-Si, carbon tetrafluoride for a-SiNx + Oxygen, carbon tetrafluoride + oxygen for a-SiOx, carbon trifluoride + oxygen, carbon tetrafluoride (sulfur hexafluoride) + oxygen for Ta, carbon tetrafluoride for MoTa / MoW Examples include + oxygen, chlorine + oxygen for Cr, boron trichloride + chlorine for Al, and methane, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide, etc. for ITO.

-Resist stripping process-
Finally, remove the resist used for pattern formation with a stripping solution (wet stripping), or remove it by oxidizing it with oxygen gas discharge under reduced pressure (dry stripping / ashing). Alternatively, the resist is removed by several peeling methods such as oxidation with ozone and UV light to remove it in a gaseous state (dry peeling / UV ashing). As the stripping solution, an aqueous solution system such as an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution and an organic solvent system such as a mixture of an amine and dimethyl sulfoxide or N-methylpyrrolidone are generally known. As an example of the latter, a monoethanolamine / dimethyl sulfoxide mixture (mass mixing ratio = 7/3) is well known.

  The pattern forming method of the present invention uses a positive photosensitive composition that is highly sensitive to blue-violet laser exposure, and protects the positive photosensitive layer made of the photosensitive composition with a protective layer. The acid catalyst generated in the exposed area of the positive photosensitive layer is shielded from catalyst deactivation factors such as trace contaminants in the atmosphere, and the PED phenomenon can be prevented well and easily at low cost, with high resolution and high Since a fine pattern can be formed, it can be suitably used for forming various patterns that require high-definition exposure, and particularly suitable for forming a large-area TFT array substrate. .

(TFT array substrate)
The TFT array substrate can be formed by the pattern forming method of the present invention. That is, a positive photosensitive layer made of the positive photosensitive composition of the present invention is formed on a TFT (thin film transistor) active matrix substrate (TFT array substrate), exposed, baked and developed to form the same TFT array substrate. A plurality of pixel electrodes are formed thereon.
In this case, the formation, exposure, development, baking, etching and the like of the positive photosensitive layer are the same as in the pattern forming method of the present invention.

  An example of a manufacturing process of a TFT array substrate used in a general active matrix type liquid crystal display device will be described with reference to FIGS. 19 is a plan view of a unit pixel of the TFT array substrate constituting the liquid crystal display device, and FIGS. 20 to 25 are cross-sectional views taken along line AA of FIG.

  As shown in FIG. 19, the TFT array substrate 40 of the liquid crystal display device has a planar structure in which TFTs 60 and display electrodes 45 whose potentials are controlled by the TFTs 60 are arranged at intersections of a plurality of drain buses 58 and gate buses 49. The TFT 60 is controlled by controlling the potential of the drain bus 58 and the gate bus 49. As a result, the potential of the display electrode 45 connected to the source electrode 57s of the TFT 60 is controlled. The orientation of the liquid crystal filled between the TFT array substrate 40 and the counter substrate is controlled in units of pixels by the potential difference between the display electrode 45 and the electrode of the counter substrate (not shown), and light transmitted through the liquid crystal display device. The polarization direction is changed and display is performed.

  Hereinafter, the manufacturing process of the TFT array substrate 40 will be described with reference to FIGS. The numerical values to be introduced are those of a typical TFT array substrate. First, as shown in FIG. 20, an ITO film 42 having a thickness of 1,000 mm is formed on the entire surface of a glass substrate 41 by sputtering, and a positive photosensitive composition and a protective film are formed on the ITO film 42 using a spin coater. The forming material is sequentially applied to form a positive photosensitive layer 43 having a protective film on the upper surface. Then, after opening the positive photosensitive layer 43 into a predetermined shape, the ITO film 42 is etched into a predetermined shape with an ITO etchant made of hydrochloric acid, ferric chloride, and pure water using this as a mask. 42 is formed. The auxiliary capacitance electrode 42 forms a capacitance with the display electrode 45 and contributes to improving contrast and preventing flicker. The positive photosensitive layer 43 is then peeled off.

Next, as shown in FIG. 21, a SiNx film 44 or SiO ₂ film having a thickness of 4,000 mm and an ITO film 45 having a thickness of 1,000 mm are sequentially formed on the entire surface of the glass substrate 41 by low pressure CVD and sputtering. On the ITO film 45, a positive photosensitive composition and a protective film forming material are sequentially applied to form a positive photosensitive layer 46 having a protective film on the upper surface. Then, after opening the positive photosensitive layer 46 in a predetermined shape, the display electrode 45 is formed by etching the ITO film 45 into a predetermined shape with the above-described ITO etchant using the positive photosensitive layer 46 as a mask. The positive photosensitive layer 46 is then peeled off.

Next, as shown in FIG. 22, a SiNx film 47 or SiO ₂ film having a thickness of 1,000 mm and a chromium layer 48 having a thickness of 1,000 mm are sequentially formed on the entire surface by low pressure CVD and sputtering. A positive photosensitive composition and a protective film-forming material are sequentially applied onto 48 to form a positive photosensitive layer 50 having a protective film on the upper surface. Then, after opening the positive photosensitive layer 50 in a predetermined shape, the chromium layer 48 is etched into a predetermined shape by using a chromium etchant made of nitric acid / secondary cerium / ammonium, perchloric acid and pure water using the positive photosensitive layer 50 as a mask. Thus, the gate electrode 48 and the gate bus 49 (see FIG. 8) are formed. The SiNx film 47 prevents the display electrode 45 from being etched by a subsequent etching process. The positive photosensitive layer 50 is then peeled off.

Next, as shown in FIG. 23, a SiNx film 51 or SiO ₂ film having a thickness of 4,000 mm is grown and formed by the low pressure CVD method, whereby the gate insulating film 51 is formed on the entire surface. Similarly, the thickness is 1,000 mm. The amorphous silicon layer 52 and the SiNx layer 53 having a thickness of 1,000 mm are sequentially formed on the entire surface. Then, a positive photosensitive composition and a protective film forming material are sequentially applied on the SiNx layer 53 to form a positive photosensitive layer 54 having a protective film on the upper surface, and the positive photosensitive layer 54 has a predetermined shape. The passivation layer 53 is formed by etching the SiNx layer 53 into a predetermined shape using a SiNx etchant made of hydrofluoric acid, ammonium fluoride, and acetic acid. The amorphous silicon layer 52 is etched into a predetermined pattern in a later step to become a semiconductor active layer. The positive photosensitive layer 54 is then peeled off.

  Next, as shown in FIG. 24, an amorphous silicon layer 55 having a thickness of 500 mm doped with phosphorus (P) at a high concentration is formed on the entire surface by low pressure CVD, and a positive photosensitive property is formed on the amorphous silicon layer 55. The composition and the protective film forming material are sequentially applied to form a positive photosensitive layer 56 having a protective film on the upper surface. Then, using the positive photosensitive layer 56 as a mask, the amorphous silicon layer 55 and the non-doped amorphous silicon layer 52 are simultaneously etched with an amorphous silicon etchant made of hydrofluoric acid, nitric acid, and acetic acid, so that the semiconductor active layer 52 is etched. The contact layers 55 are respectively formed. The positive photosensitive layer 56 is then peeled off.

  Next, as shown in FIG. 25, after opening the SiNx film 47 and the SiNx film 51 at predetermined positions on the display electrode 45 by etching, aluminum (Al) having a thickness of 7,000 mm is formed on the entire surface by sputtering. A positive photosensitive composition and a protective film forming material are sequentially applied onto the layer, and a positive photosensitive layer 59 having a protective film on the upper surface is formed. Then, using the positive photosensitive layer 59 as a mask, the aluminum layer is etched with an aluminum etchant made of phosphoric acid, nitric acid, acetic acid, and pure water to form a drain electrode 57d and a source electrode 57s. In this etching step, as shown in FIG. 19, the drain bus 58 is also formed continuously with the drain electrode 57d. The passivation layer 53 is exposed by the etching process of the amorphous silicon layer 55. At this time, the passivation layer 53 functions as an etching stopper to prevent the semiconductor active layer 52 from being etched. Thereafter, a thermosetting resin such as a polyimide resin is rubbed to form an alignment film, a polarizing plate is formed on the other main surface of the glass substrate 41, and the TFT array substrate 40 is completed.

(Liquid crystal display element)
The liquid crystal display element of the present invention includes the TFT array substrate of the present invention manufactured by the pattern forming method of the present invention described above, and further includes other members as necessary.

  The basic configuration of the liquid crystal display element is as follows: (1) TFT array substrate of the present invention in which drive elements such as thin film transistors (hereinafter referred to as “TFTs”) and pixel electrodes (conductive layers) are arrayed. (Drive-side substrate) and a color filter-side substrate provided with a color filter and a counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap portion, (2 ) A color filter-integrated TFT array substrate in which a color filter is directly formed on the TFT array substrate of the present invention and a counter substrate having a counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and in the gap portion Examples include a liquid crystal material encapsulated.

Examples of the conductive layer include an ITO film; a metal film such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; and a metal oxide film such as SiO _2. Is preferable, and an ITO film is particularly preferable.
The TFT array substrate, the color filter side substrate, and the counter substrate of the present invention have, as their base materials, for example, a known glass plate such as a soda glass plate, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, or a plastic. It is configured using a film or the like.
In addition, as a specific method for manufacturing the liquid crystal element, for example, a method described in JP-A-6-67204 can be mentioned. By doing so, a high-quality and inexpensive product can be obtained.

  Since the liquid crystal display element of the present invention uses a TFT array substrate in which fine TFTs formed by the pattern forming method of the present invention are densely formed without defects, a large-screen LCD of about 1 m square or more can be produced with high quality. Yes, and can be provided at low cost.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

(Synthesis Example 1)
-Synthesis of acid-decomposable resin A1-
Into a 500 ml four-necked flask purged with nitrogen inside, 25 g of poly (p-vinylphenol) having a weight average molecular weight (Mw) of 14,700 and a polydispersity (Mw / Mn) of 2.48 (p-vinylphenol unit) 208 mmol) and p-toluenesulfonic acid 0.021 (0.109 mmol) were added and dissolved in 250 g of 1,4-dioxane. To this solution, 4.34 (60 mmol) of ethyl vinyl ether was added dropwise and then reacted at 25 ° C. for 5 hours. This reaction solution was dropped into 1,500 ml of ion-exchanged water, and then filtered to obtain a white wet cake. This wet cake was dissolved again in 200 g of 1,4-dioxane, and then dropped into 1,500 ml of ion-exchanged water, followed by filtration. The obtained wet cake was stirred and washed in 600 g of ion exchange water, filtered to take out the wet cake, and this washing operation with ion exchange water was repeated twice.
The obtained white wet cake was dried under reduced pressure to obtain an acid-decomposable resin A1 (the following structural formula (1)) in which the hydroxyl group of poly (p-vinylphenol) was partially converted to 1-ethoxyethyl ether. . When this resin was analyzed by ¹ H-NMR, 29 mol% of the hydroxyl groups were protected with 1-ethoxyethyl groups. The acid-decomposable resin A1 had a weight average molecular weight of 17,200 and a polydispersity of 2.54.

(Synthesis Example 2)
-Synthesis of acid-decomposable resin A2-
A novolak resin obtained by condensing a mixed cresol having a mixed molar ratio of m-cresol / p-cresol of 70/30 by a conventional method using formaldehyde as a condensing agent and an oxalic acid catalyst is usually combined with ethyl vinyl ether. The acid-decomposable resin A2 represented by the following structural formula (2) was synthesized by acetalization by the method.

(Synthesis Example 3)
-Synthesis of acid-decomposable resin A3-
Into a 500 ml four-necked flask purged with nitrogen inside, 25 g of poly (p-vinylphenol) having a weight average molecular weight (Mw) of 14,700 and a polydispersity (Mw / Mn) of 2.48 (p-vinylphenol unit) 208 mmol) and p-toluenesulfonic acid 0.021 (0.109 mmol) were added and dissolved in 250 g of 1,4-dioxane. To this solution, 9.24 g (60 mmol) of 2-cyclohexylethyl vinyl ether was added dropwise, and then reacted at 25 ° C. for 5 hours. 1,500 ml of this reaction solution was added dropwise, and then filtered to obtain a white wet cake. This wet cake was dissolved again in 200 g of 1,4-dioxane, and then dropped into 1,500 ml of ion-exchanged water, followed by filtration. The obtained wet cake was stirred and washed in 600 g of ion exchange water, filtered to take out the wet cake, and this washing operation with ion exchange water was repeated twice. The obtained white wet cake was dried under reduced pressure, and acid-decomposable resin A3 in which the hydroxyl group of poly (p-vinylphenol) was partially converted to 1- (2-cyclohexylethoxy) ethyl ether (the following structural formula (3 )). When this resin was analyzed by ¹ H-NMR, 29 mol% of the hydroxyl groups were protected with 1- (2-cyclohexylethoxy) ethyl group. The acid-decomposable resin A3 had a weight average molecular weight of 25,100 and a polydispersity of 2.56.

(Synthesis Example 4)
-Synthesis of acid-decomposable resin A4-
30 g of polyhydroxystyrene was dissolved in tetrahydrofuran, 10 g of potassium tert-butoxide was added, 75 g of di-t-butyl carbonate was added dropwise at 0 ° C. with stirring, and reacted for 6 hours. After completion of the reaction, this solution was dropped into water, and the precipitated polymer was dried overnight at 50 ° C. in a vacuum dryer to obtain an acid-decomposable resin A4 (the following structural formula (4)). When this resin was analyzed by ¹ H-NMR, 63 mol% of the hydrogen of the phenolic hydroxyl group was protected with a tert-butoxycarbonyl group. The acid-decomposable resin A4 had a weight average molecular weight of 30,000 and a polydispersity of 1.60.

(Synthesis Example 5)
-Synthesis of polyvinyl alcohol (PVA-1)-
After taking 2,400 parts by weight of vinyl acetate, 580 parts by weight of methanol, and 1.5 parts by weight of thiol acetic acid in the reaction vessel and thoroughly replacing the inside with nitrogen, the outside temperature was raised to 65 ° C. and the inside temperature was 60 ° C. Was reached, 20 parts by mass of methanol containing 0.868 parts by mass of 2,2′-azobisisobutyronitrile was added. Immediately, 60 parts by mass of a methanol solution containing 26.1 parts by mass of thiolacetic acid was uniformly added dropwise over 5 hours. The polymerization rate after 5 hours was 51%. The container was cooled, and the operation of driving the remaining vinyl acetate out of the system together with methanol was performed while adding methanol to obtain a methanol solution of polyvinyl acetate (concentration 65%). A part of this methanol solution was taken, a methanol solution of sodium hydroxide was added so that the concentration of polyvinyl acetate was 50% by mass and [NaOH] / [vinyl acetate units] (molar ratio) = 0.04, and 40 ° C. Was then saponified to synthesize polyvinyl alcohol (PVA-1).
The polyvinyl alcohol had a weight average molecular weight of 4,500 and a saponification degree of 88 mol%.

Example 1
<Positive photosensitive layer forming step>
An ITO thin film having a thickness of 1,000 mm (100 nm) was formed on a 100 mm × 100 mm glass substrate (Corning # 7059) using a sputtering DC magnetron sputtering apparatus under the following conditions.
Substrate temperature: room temperature to 300 ° C
Target board distance: 40mm
Gas pressure: 2.6 × 10 ⁻³ Torr (0.35 Pa)
Sputtering gas: Argon Input current: 0.1A
Target substrate: 3 inches in diameter x 5 mm in thickness
On the ITO layer of the glass substrate on which the ITO thin film has been formed, a chemically amplified positive photosensitive composition having the following composition was applied for 30 seconds at 500 rpm using a spin coater, and in an oven at 100 ° C. for 2 minutes. By drying, a chemically amplified positive photosensitive layer (photoresist film) having a thickness of 1.5 μm was formed.

-Composition of positive photosensitive composition (solution)-
Acid-decomposable resin A1 represented by the structural formula (1) 31.3 parts by mass B-3 represented by the following structural formula: CGI1397 (a photoacid generator manufactured by Ciba Specialty Chemicals, 5- (3-propanesulfoxy) -imino-5H-thiophen-2-ylidene-o-tolylacetonitrile)... 0.43 parts by mass. F780F (fluorine-based surfactant manufactured by DIC). 025 parts by mass / propylene glycol methyl ether acetate) 166 parts by mass

<Formation of protective film>
A solution having the following composition (solid content concentration: 3.0% by mass, viscosity: 10 mPa · s) was filtered through a 0.2 μm microfilter to prepare a protective film coating solution. The resulting protective film coating solution was applied onto the positive photosensitive layer at 2,500 rpm using a spin coater (Mark 8 manufactured by Tokyo Electron), dried at 100 ° C. for 120 seconds, and a thickness of 0.8 μm. A protective film was formed.
-Composition of coating solution for protective film-
PVA-205 (trade name, manufactured by Kuraray Co., Ltd .: polyvinyl alcohol, degree of saponification = 88 mol%, mass average molecular weight = 22,000), 6.2 parts by mass, K-30 (manufactured by GAF Corporation: polyvinyl pyrrolidone, (Mass average molecular weight = 40,000)... 2.8 parts by mass, ion-exchanged water ... 160 parts by mass, methanol ... 131 parts by mass On the base material, a positive photosensitive layer and a protective film are obtained by the above process. The photosensitive laminated body which has these in this order was produced.

<Exposure process>
Next, with respect to the positive photosensitive layer on the glass substrate, using a pattern forming apparatus described below, the positive photosensitive layer and the exposure head are moved relative to each other while the wavelength is 405 nm and 10 to 100 mJ / cm ^2. The light corresponding to the resist pattern while generating various line (space) width patterns with line / space = 1/1 (hereinafter abbreviated as L / S = 1/1) by changing the exposure amount in the range of Was irradiated.
-Pattern forming device-
As the light irradiating means, the combined laser light source shown in FIGS. 9 to 14 and 600 pairs of micromirror arrays in which 800 micromirrors are arranged in the main scanning direction shown in FIG. Among the arrayed light modulation means, the DMD 50 controlled to drive only 800 × the number of columns in the use area, the microlens array 472 in which the microlenses shown in FIG. 18 are arrayed, and the microlens A pattern forming apparatus having optical systems 480 and 482 for forming an image of light passing through the array on the photosensitive resin layer was used. In addition, the aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is disposed so that only light that has passed through the corresponding microlens 55a is incident on each aperture 59a.

<Post-exposure heating step (PEB treatment)>
Two hours after the completion of the exposure process, the resist pattern irradiated glass substrate was heated on a hot plate at 110 ° C. for 90 seconds. At this time, the glass substrate was kept 100 μm above the hot plate.

<Development process>
The glass substrate was cooled to room temperature, developed with 2.38 mass% TMAH aqueous solution at 25 ° C. for 80 seconds, washed with ultrapure water for 1 minute, and spin-dried to obtain a resist pattern.

<Etching process>
The ITO layer not covered with the resist pattern was removed with an ITO etchant composed of hydrochloric acid, ferric chloride, and pure water to form an ITO electrode pattern.

<Resist stripping process>
As a stripping treatment of the resist pattern, a glass substrate was immersed in a monoethanolamine / N-methylpyrrolidone (volume ratio = 30/70) mixed stripping solution at 80 ° C. for 3 minutes. It was able to peel without being done.

<Evaluation of adhesion of protective film>
With respect to the protective film on the glass substrate, 100 grids are made with a cutter, Mylar tape is stuck on this, and the number of grids remaining when peeled off from the end of the tape, the following evaluation criteria The adhesion of the protective film was evaluated.
○: 100/100 pieces Δ: 50/100 pieces to 99/100 pieces ×: 0/100 pieces to 49/100 pieces

<Evaluation of sensitivity>
The positive photosensitive layer is subjected to an exposure process by changing the exposure amount of the L / S = 1/1 pattern as described above, and after the exposure process, after being left for 2 hours as described above, a heating process is performed. After the heating step, the resist pattern obtained by carrying out the development step was observed with a microscope, and the exposure amount when the L / S = 10 μm / 10 μm exposed area was completely developed was defined as sensitivity.

<Evaluation of resolution>
In the same manner as described above, the positive type photosensitive layer was exposed by changing the exposure amount of the L / S = 1/1 pattern, and after the heating step after being left for 2 hours as described above, the above development was performed. The resist pattern obtained by performing the process was observed with a microscope, and the resolved minimum pattern width was defined as the resolution.

<Evaluation of average line width>
In the various patterns formed above, the line width of the remaining image portion of the resist pattern of L / S = 5 μm / 5 μm was measured at five points, and the average value was taken as the average line width.

<Evaluation of line width variation>
The variation in data measured in the evaluation of the average line width was defined as the variation in line width.
The evaluation results are shown in Table 1.

(Example 2)
In Example 1, B-7: PAG103 (manufactured by Ciba Specialty Chemicals, 3- (3) represented by the following structural formula, instead of B-3 which is a photoacid generator in the positive photosensitive composition -Propanesulfoxy) -imino-2H-thiophen-3-ylidene-o-tolylacetonitrile) was used in the same manner as in Example 1 to prepare a photosensitive laminate having a positive photosensitive layer and a protective layer. Then, a resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 3
In Example 1, instead of B-3 which is a photoacid generator in the positive photosensitive composition, B-4: CGI1325 represented by the following structural formula (manufactured by Ciba Specialty Chemicals, 5- (8 -Octanesulfoxy) -imino-5H-thiophen-2-ylidene-o-tolylacetonitrile) was used in the same manner as in Example 1 to prepare a photosensitive laminate having a positive photosensitive layer and a protective layer. Then, a resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 4
In Example 1, instead of B-3 which is a photoacid generator in the positive photosensitive composition, B-8 represented by the following structural formula: PAG108 (manufactured by Ciba Specialty Chemicals, 3- (8 -Octanesulfoxy) -imino-2H-thiophen-3-ylidene-o-tolylacetonitrile) was used in the same manner as in Example 1 to prepare a photosensitive laminate having a positive photosensitive layer and a protective layer. Then, a resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 5)
In Example 1, instead of B-3 which is a photoacid generator in the positive photosensitive composition, B-5: CGI1380 represented by the following structural formula (manufactured by Ciba Specialty Chemicals, 5- (Camphor) Except for using sulfoxy) -imino-5H-thiophen-2-ylidene-o-tolylacetonitrile), a photosensitive laminate having a positive photosensitive layer and a protective layer was formed in the same manner as in Example 1. A resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 6)
In Example 1, instead of B-3 which is a photoacid generator in the positive photosensitive composition, B-9: PAG121 represented by the following structural formula (manufactured by Ciba Specialty Chemicals, 3- (p -Toluenesulfoxy) -imino-2H-thiophene-3-ylidene-o-tolylacetonitrile) was used in the same manner as in Example 1 to prepare a photosensitive laminate having a positive photosensitive layer and a protective layer. Then, a resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 7)
In Example 1, in place of the acid-decomposable resin A1 in the positive photosensitive composition, the acid-decomposable resin A2 synthesized in Synthesis Example 2 was used in the same manner as in Example 1, A photosensitive laminate having a positive photosensitive layer and a protective layer was formed to obtain a resist pattern, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 8)
In Example 1, in place of the acid-decomposable resin A1 in the positive photosensitive composition, the acid-decomposable resin A3 synthesized in Synthesis Example 3 was used in the same manner as in Example 1, A photosensitive laminate having a positive photosensitive layer and a protective layer was formed to obtain a resist pattern, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 9
In Example 1, in the same manner as in Example 1 except that the acid-decomposable resin A4 synthesized in Synthesis Example 4 was used instead of the acid-decomposable resin A1 in the positive photosensitive composition, A photosensitive laminate having a positive photosensitive layer and a protective layer was formed to obtain a resist pattern, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 10)
In Example 1, PVA-217 (manufactured by Kuraray Co., Ltd .: polyvinyl alcohol, saponification degree = 88 mol%, mass average molecular weight = 74,800) was used in place of PVA-205 as the polyvinyl alcohol of the protective film. In the same manner as in Example 1, a photosensitive laminate having a positive photosensitive layer and a protective layer was formed, a resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 11)
In Example 1, PVA-203 (manufactured by Kuraray Co., Ltd .: polyvinyl alcohol, degree of saponification = 88 mol%, mass average molecular weight = 13,200) was used instead of PVA-205 as the polyvinyl alcohol of the protective film. In the same manner as in Example 1, a photosensitive laminate having a positive photosensitive layer and a protective layer was formed, a resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 12)
In Example 1, PVA-210 (manufactured by Kuraray Co., Ltd .: polyvinyl alcohol, saponification degree = 88 mol%, mass average molecular weight = 44,000) was used in place of PVA-205 as the polyvinyl alcohol of the protective film. In the same manner as in Example 1, a photosensitive laminate having a positive photosensitive layer and a protective layer was formed, a resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 13)
In Example 1, PVA-405 (manufactured by Kuraray Co., Ltd .: polyvinyl alcohol, saponification degree = 82 mol%, mass average molecular weight = 22,000) was used instead of PVA-205 as the polyvinyl alcohol of the protective film. In the same manner as in Example 1, a photosensitive laminate having a positive photosensitive layer and a protective layer was formed, a resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 14)
In Example 1, PVA-706 (manufactured by Kuraray Co., Ltd .: polyvinyl alcohol, saponification degree = 92 mol%, mass average molecular weight = 26,400) was used in place of PVA-205 as the polyvinyl alcohol of the protective film. In the same manner as in Example 1, a photosensitive laminate having a positive photosensitive layer and a protective layer was formed, a resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 15)
As shown in Table 1, in Example 1, as a polyvinyl alcohol of the protective film, instead of PVA-205, PVA-105 (trade name, manufactured by Kuraray Co., Ltd .: polyvinyl alcohol, saponification degree = 99 mol%, mass average molecular weight = 22,000) is used in the same manner as in Example 1 to form a photosensitive laminate having a positive photosensitive layer and a protective layer to obtain a resist pattern, and in the same manner as in Example 1, Each said evaluation was performed. The evaluation results are shown in Table 1.

(Example 16)
As shown in Table 1, in Example 1, as a polyvinyl alcohol of the protective film, instead of PVA-205, PVA-505 (trade name manufactured by Kuraray Co., Ltd .: polyvinyl alcohol, saponification degree = 73 mol%, mass average molecular weight = 22,000) is used in the same manner as in Example 1 to form a photosensitive laminate having a positive photosensitive layer and a protective layer to obtain a resist pattern, and in the same manner as in Example 1, Each said evaluation was performed. The evaluation results are shown in Table 1.

(Example 17)
In Example 1, instead of 6.2 parts by mass of PVA-205 as a protective film and 2.8 parts by mass of polyvinylpyrrolidone K-30 (mixing mass ratio 6.2 / 2.8), 2.8 of PVA-205 was used. A photosensitive laminate having a positive photosensitive layer and a protective layer was formed in the same manner as in Example 1 except that 6.2 parts by mass of polyvinyl pyrrolidone K-30 was obtained, and a resist pattern was obtained. Each of the above evaluations was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 18)
In Example 1, 6.2 parts by mass of PVA-205 as a protective film and 2.8 parts by mass of polyvinylpyrrolidone K-30 (mixing mass ratio 6.2 / 2.8) were combined with 5.0 parts by mass of PVA-205. A photosensitive laminate having a positive-type photosensitive layer and a protective layer was formed in the same manner as in Example 1 except that 4.0 parts by mass of polyvinylpyrrolidone K-30 (same ratio: 5.0 / 4.0) was formed. A resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 19)
In Example 1, 6.2 parts by mass of PVA-205 as a protective film and 2.8 parts by mass of polyvinylpyrrolidone K-30 (mixing mass ratio 6.2 / 2.8) were combined with 8.1 parts by mass of PVA-205. Polyvinylpyrrolidone K-30 A photosensitive laminate having a positive photosensitive layer and a protective layer was formed in the same manner as in Example 1 except that 0.9 parts by mass (the same ratio of 8.1 / 0.9) was formed. A resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 20)
In Example 1, 6.2 parts by mass of PVA-205 as a protective film and 2.8 parts by mass of polyvinylpyrrolidone K-30 (mixing mass ratio 6.2 / 2.8) were combined with 8.5 parts by mass of PVA-205. A photosensitive laminate having a positive photosensitive layer and a protective layer was formed in the same manner as in Example 1 except that 0.5 parts by mass of polyvinylpyrrolidone K-30 (same ratio was 8.5 / 0.5), A resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 21)
In Example 1, instead of 6.2 parts by mass of PVA-205 and 2.8 parts by mass of polyvinylpyrrolidone K-30 (mixing mass ratio 6.2 / 2.8) of the protective film, 9.0 parts by mass of PVA-205 Except for using only the part, a photosensitive laminate having a positive photosensitive layer and a protective layer was formed in the same manner as in Example 1 to obtain a resist pattern. Evaluation was performed. The evaluation results are shown in Table 1.

(Example 22)
In Example 1, the positive photosensitive layer and the positive photosensitive layer were prepared in the same manner as in Example 1 except that the amount of B-3, which is a photoacid generator in the positive photosensitive composition, was 0.22 parts by mass. The photosensitive laminated body which has a protective layer was formed, the resist pattern was obtained, and each said evaluation was performed like Example 1. FIG. The evaluation results are shown in Table 1.

(Example 23)
In Example 1, the positive photosensitive layer and the positive photosensitive layer were prepared in the same manner as in Example 1 except that the addition amount of B-3 as the photoacid generator in the positive photosensitive composition was 0.64 parts by mass. The photosensitive laminated body which has a protective layer was formed, the resist pattern was obtained, and each said evaluation was performed like Example 1. FIG. The evaluation results are shown in Table 1.

(Example 24)
In Example 1, except that the thickness of the protective film was 0.3 μm, a photosensitive laminate having a positive photosensitive layer and a protective layer was formed in the same manner as in Example 1, to obtain a resist pattern, Each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 25)
In Example 1, a photosensitive laminate having a positive photosensitive layer and a protective layer was formed in the same manner as in Example 1 except that the thickness of the protective film was 1.6 μm, and a resist pattern was obtained. Each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 1)
In Example 1, except that the protective film was not provided, a photosensitive laminate having a positive photosensitive layer was formed in the same manner as in Example 1, a resist pattern was obtained, and in the same manner as in Example 1. Each of the above evaluations was performed. The evaluation results are shown in Table 1.

(Comparative Example 2)
As shown in Table 1, in Example 1, as a polyvinyl alcohol of the protective film, instead of PVA-205, PVA-1 (polyvinyl alcohol obtained in Synthesis Example 5 above, saponification degree = 88 mol%, mass average molecular weight) = 4,500), except that a photosensitive laminate having a positive photosensitive layer and a protective layer was formed in the same manner as in Example 1, and a resist pattern was obtained. Each of the above evaluations was performed. The evaluation results are shown in Table 1.

(Comparative Example 3)
As shown in Table 1, in Example 1, as polyvinyl alcohol of the protective film, instead of PVA-205, PVA-224 (Kuraray Co., Ltd. trade name: polyvinyl alcohol, saponification degree = 88 mol%, mass average molecular weight = 105, 600) except that the photosensitive laminated body having the positive photosensitive layer and the protective layer was formed in the same manner as in Example 1 to obtain a resist pattern. Each said evaluation was performed. The evaluation results are shown in Table 1.

(Comparative Example 4)
In Example 1, in the positive photosensitive composition, N-cyclohexyl-N ′-(2-morpholinoethyl) thiourea (a compound represented by the following structural formula (3) as a quencher, hereinafter referred to as Q-1 0.03 parts by mass) and a protective laminate was not provided, and a photosensitive laminate having a positive photosensitive layer was formed in the same manner as in Example 1 to obtain a resist pattern, Each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 5)
In Example 1, instead of CGI1397 as a photoacid generator in the positive photosensitive composition, PAG203 represented by the following structural formula (manufactured by Ciba Specialty Chemicals, 1,3-bis [4- { 2,2,2-trifluoro-1- (3-propanesulfoxy) iminoethyl} phenoxy] propane) except that a positive photosensitive layer and a protective layer are used. A laminate was formed, a resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.
The PAG 203 is a photoacid generator that does not absorb light with a wavelength of 405 nm.

(Comparative Example 6)
In Example 1, instead of 6.2 parts by mass of PVA-205 as a protective film and 2.8 parts by mass of polyvinylpyrrolidone K-30 (mixing mass ratio 6.2 / 2.8), L-3266 (Nippon Synthetic Chemical) Except for using 6.5 parts by mass of Kogyo Co., Ltd., sulfonic acid-modified polyvinyl alcohol, sulfonic acid modification degree 0.4 mol%, saponification degree 88 mol%, and weight average molecular weight 16,000). Then, a photosensitive laminate having a positive photosensitive layer and a protective layer was formed, a resist pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 7)
-Synthesis of alkali-soluble resin (a1)-
For the mixed phenols of m-cresol / p-cresol = 30/70, formaldehyde is used as a condensing agent, and a novolak resin obtained by a condensation reaction by a conventional method using an oxalic acid catalyst is used as a water-methanol mixed solvent. The novolak resin having a Mw of 5,000 obtained by the separation treatment was used as an alkali-soluble resin (a1).
-Synthesis of alkali-soluble resin (a1)-
For a mixed phenol of m-cresol / p-cresol = 30/70, formaldehyde is used as a condensing agent, and a novolak resin obtained by a condensation reaction by a conventional method using an oxalic acid catalyst is used as a water-methanol mixed solvent. The novolak resin having a Mw of 6,300 obtained by performing the separation treatment was used as an alkali-soluble resin (a2).
For a mixed phenol of m-cresol / p-cresol = 60/40, formaldehyde is used as a condensing agent, and a novolak resin obtained by a condensation reaction by a conventional method using an oxalic acid catalyst is used as a water-methanol mixed solvent. Thus, the novolak resin having Mw of 11,000 obtained by the fractionation treatment was used as the alkali-soluble resin (a3).

-Composition of photosensitive composition-
Alkali-soluble novolac resin: a mixture of the alkali-soluble resins (a1) to (a3) synthesized above at a mass ratio of 2: 3: 5: 100 parts by mass. Phenolic hydroxyl group-containing compound (C1: below) Compound represented by structural formula (4)) ... 10 parts by mass / naphthoquinonediazide group-containing compound: 1 mol of phenolic hydroxyl group-containing compound represented by the following structural formula (5) and 1,2-naphthoquinonediazide-5 -Esterification reaction product with 2.34 mol of sulfonyl chloride (hereinafter referred to as N1) ... 29.7 parts by mass · Propylene glycol monomethyl ether acetate · 430 parts by mass · BYK-310 (silicone manufactured by BYK Chemie) -Based surfactants) ... 0.07 parts by mass 2- (2-hydroxyethyl) pyridine ... 0.25 parts by mass

After the above components were uniformly dissolved, this was filtered using a membrane filter having a pore size of 0.2 μm to prepare a positive photosensitive composition of Comparative Example 7.
The positive photosensitive composition solution is applied and dried on the glass substrate described in Example 1 to form a positive photosensitive layer, and a photosensitive laminate is formed without providing a protective film on the positive photosensitive layer. Then, a pattern was obtained, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 8)
In Example 1, a protective film was not provided, and the addition amount of the photoacid generator B-22 was further increased 1.5 times to 0.64 parts by mass, as in Example 1, A photosensitive laminate having a positive photosensitive layer was formed to obtain a resist pattern, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 9)
In Example 1, PVA-1 (polyvinyl alcohol obtained in Synthesis Example 5, saponification degree = 88 mol%, mass average molecular weight = 4,500) was used instead of PVA-205 as the polyvinyl alcohol of the protective film. Further, a photosensitive laminate having a positive photosensitive layer and a protective layer was formed in the same manner as in Example 1 except that the thickness of the protective film was 1.6 μm, and a resist pattern was obtained. Each evaluation was performed in the same manner as described above. The evaluation results are shown in Table 1.

(Comparative Example 10)
In Example 1, PVA-1 (polyvinyl alcohol obtained in Synthesis Example 5, saponification degree = 88 mol%, mass average molecular weight = 4,500) was used instead of PVA-205 as the polyvinyl alcohol of the protective film. Further, a positive type was formed in the same manner as in Example 1 except that the thickness of the protective film was 1.6 μm and the addition amount of B-22, which is a photoacid generator in the photosensitive layer, was 0.64 parts by mass. The photosensitive laminated body which has a photosensitive layer and a protective layer was formed, the resist pattern was obtained, and each said evaluation was performed like Example 1. FIG. The evaluation results are shown in Table 1.

From the results shown in Table 1, a positive photosensitive composition comprising at least a resin that exhibits alkali solubility by the action of an acid and a photoacid generator that generates an acid that absorbs at least light having a wavelength of 405 nm. The present invention was developed by exposing and developing a positive photosensitive layer using a product provided with a protective film containing at least a polyvinyl alcohol (water-soluble resin) having a weight average molecular weight of 8,000 to 100,000. In Examples 1 to 25 in which the resist pattern was formed by the pattern forming method, the resist was highly sensitive, excellent in adhesion between the protective film and the positive photosensitive layer, high resolution, and no line width variation. It was found that a pattern was obtained and the effect of preventing the PED phenomenon was excellent.
In particular, an oxime sulfonate photoacid generator is used as a photoacid generator, the content thereof is 0.1 to 40% by mass, and polyvinyl alcohol and polyvinylpyrrolidone are used in combination as a protective film material, In Examples 1 to 20, 22, and 24 to 25 in which the thickness of the protective film was 0.1 to 3 μm, it was found that the effect of preventing the PED phenomenon was extremely excellent with high resolution.

(Example 26)
<Production and evaluation of TFT array substrate>
A TFT array substrate was produced according to a method for producing a TFT array substrate having the steps shown in FIGS.
First, as shown in FIG. 20, an ITO film 42 having a thickness of 1,000 mm is formed on the entire surface of a glass substrate 41 by sputtering, and the positive photosensitive composition of Example 1 is formed on the ITO film 42 using a spin coater. Then, a positive photosensitive layer 43 having a protective film on the upper surface was formed. Then, after opening the positive photosensitive layer 43 into a predetermined shape, the ITO film 42 is etched into a predetermined shape with an ITO etchant made of hydrochloric acid, ferric chloride, and pure water using the positive photosensitive layer 43 as a mask. 42 was formed. The auxiliary capacitance electrode 42 forms a capacitance with the display electrode 45 and contributes to improving contrast and preventing flicker. The positive photosensitive layer 43 was then peeled off.

Next, as shown in FIG. 21, a SiNx film 44 or SiO ₂ film having a thickness of 4,000 mm and an ITO film 45 having a thickness of 1,000 mm were sequentially formed on the entire surface of the glass substrate 41 by low pressure CVD and sputtering. On the ITO film 45, the positive photosensitive composition of Example 1 and the protective film forming coating solution were sequentially applied to form a positive photosensitive layer 46 having a protective film on the top surface. Then, after opening the positive photosensitive layer 46 in a predetermined shape, the display film 45 was formed by etching the ITO film 45 into a predetermined shape with the above-described ITO etchant using this as a mask. The positive photosensitive layer 46 was then peeled off.

Next, as shown in FIG. 22, a SiNx film 47 or SiO ₂ film having a thickness of 1,000 mm and a chromium layer 48 having a thickness of 1,000 mm are sequentially formed on the entire surface by low pressure CVD and sputtering. The positive photosensitive composition of Example 1 and a protective film coating solution were sequentially applied onto 48 to form a positive photosensitive layer 50 having a protective film on the upper surface. Then, after opening the positive photosensitive layer 50 in a predetermined shape, the chromium layer 48 is etched into a predetermined shape by using a chromium etchant made of nitric acid / secondary cerium / ammonium, perchloric acid and pure water using the positive photosensitive layer 50 as a mask. Thus, the gate electrode 48 and the gate bus 49 (see FIG. 8) were formed. The SiNx film 47 prevents the display electrode 45 from being etched by a subsequent etching process. The positive photosensitive layer 50 was then peeled off.

Next, as shown in FIG. 23, a SiNx film 51 or SiO ₂ film having a thickness of 4,000 mm is grown and formed by a low pressure CVD method to form a gate insulating film 51 on the entire surface. Similarly, the thickness is 1,000 mm. The amorphous silicon layer 52 and the SiNx layer 53 having a thickness of 1,000 mm were sequentially formed on the entire surface. Then, on the SiNx layer 53, the positive photosensitive composition and the protective film coating solution of Example 1 are sequentially applied to form the positive photosensitive layer 54 having the protective film on the upper surface, and the positive photosensitive film is formed. The passivation layer 53 was formed by opening the layer 54 in a predetermined shape and etching the SiNx layer 53 into a predetermined shape with a SiNx etchant made of hydrofluoric acid, ammonium fluoride, and acetic acid using the layer 54 as a mask. The amorphous silicon layer 52 is etched into a predetermined pattern in a later step to become a semiconductor active layer. The positive photosensitive layer 54 was then peeled off.

  Next, as shown in FIG. 24, an amorphous silicon layer 55 having a thickness of 500 mm doped with phosphorus (P) at a high concentration is formed on the entire surface by low pressure CVD, and the amorphous silicon layer 55 of Example 1 is formed on the amorphous silicon layer 55. A positive photosensitive composition and a protective film coating solution were sequentially applied to form a positive photosensitive layer 56 having a protective film on the upper surface. Then, using the positive photosensitive layer 56 as a mask, the amorphous silicon layer 55 and the non-doped amorphous silicon layer 52 are simultaneously etched with an amorphous silicon etchant made of hydrofluoric acid, nitric acid, and acetic acid, so that the semiconductor active layer 52 is etched. Each contact layer 55 was formed. The positive photosensitive layer 56 was then peeled off.

  Next, as shown in FIG. 25, after opening the SiNx film 47 and the SiNx film 51 at predetermined positions on the display electrode 45 by etching, aluminum (Al) having a thickness of 7,000 mm is formed on the entire surface by sputtering. On the layer, the positive photosensitive composition of Example 1 and the protective film coating solution were sequentially applied to form a positive photosensitive layer 59 having a protective film on the upper surface. Then, using this positive photosensitive layer 59 as a mask, the aluminum layer was etched with an aluminum etchant made of phosphoric acid, nitric acid, acetic acid, and pure water to form a drain electrode 57d and a source electrode 57s. In this etching step, as shown in FIG. 19, the drain bus 58 is also formed continuously with the drain electrode 57d. The passivation layer 53 is exposed by the etching process of the amorphous silicon layer 55. At this time, the passivation layer 53 functions as an etching stopper to prevent the semiconductor active layer 52 from being etched. Thereafter, a thermosetting resin such as polyimide resin was rubbed to form an alignment film, a polarizing plate was formed on the other main surface of the glass substrate 41, and the TFT array substrate 40 was formed.

  When the TFT array substrate 100 was processed and the TFT chip on the substrate was evaluated, there was one substrate having one or more defective TFTs on the same substrate. The incidence was 1%.

(Comparative Example 11)
In Example 26, a TFT array substrate was formed in the same manner as in Example 26 except that the protective film was not provided on the positive photosensitive layer.
When 100 TFT array substrates were processed and the TFT chip on the substrate was evaluated, there were 80 substrates having one or more defective TFTs on the same substrate. The incidence was 80%.

(Example 27 and Comparative Example 12)
[Production and Evaluation of Liquid Crystal Display]
Using the TFT array substrate of Example 26 and Comparative Example 11 to produce a liquid crystal panel by a known method (Japanese Patent Laid-Open No. 6-67204) and evaluating the display performance, the liquid crystal display device was compared with the liquid crystal display device of Comparative Example 12. Thus, it was confirmed that the liquid crystal display device of Example 27 exhibited good display characteristics.

  The pattern forming method of the present invention uses a positive photosensitive composition that is highly sensitive to blue-violet laser exposure, and protects the positive photosensitive layer made of the photosensitive composition with a protective layer. TFT array substrates and plasma display (PDP) electrode plates that require high-definition exposure because the PED phenomenon can be satisfactorily and easily prevented at low cost, and high-definition and high-definition patterns can be formed. The TFT array substrate manufactured by the pattern forming method of the present invention is suitable for large liquid crystal display devices (LCD) such as notebook computers and TV monitors, PALC (plasma address liquid crystal), plasma display (PDP). It is preferably used as an application.

FIG. 1 is a perspective view showing an appearance of an exposure unit according to the present invention. FIG. 2 is a perspective view showing the configuration of the scanner of the exposure unit according to the present invention. FIG. 3A is a plan view showing an exposed region formed on the photosensitive material, and FIG. 3B is a diagram showing an arrangement of exposure areas by each exposure head. FIG. 4 is a perspective view showing a schematic configuration of the exposure head according to the present invention. 5A is a cross-sectional view in the sub-scanning direction along the optical axis showing the configuration of the exposure head shown in FIG. 4, and FIG. 5B is a side view of FIG. FIG. 6 is a partially enlarged view showing a configuration of a digital micromirror device (DMD). 7A and 7B are explanatory diagrams for explaining the operation of the DMD. FIGS. 8A and 8B are plan views showing exposure beam arrangements and scanning lines in a case where the DMD is not inclined and in a case where the DMD is not inclined. FIG. 9A is a perspective view showing the configuration of the fiber array light source, FIG. 9B is a partially enlarged view of FIG. 9A, and FIGS. It is a top view which shows the arrangement | sequence of a light emission point. FIG. 10 is a diagram illustrating a configuration of a multimode optical fiber. FIG. 11 is a plan view showing the configuration of the combined laser light source. FIG. 12 is a plan view showing the configuration of the laser module. FIG. 13 is a side view showing the configuration of the laser module shown in FIG. FIG. 14 is a partial side view showing the configuration of the laser module shown in FIG. 15A and 15B are cross-sectional views showing the depth of focus in the exposure apparatus. FIGS. 16A and 16B are diagrams illustrating examples of DMD usage areas. FIG. 17A is a side view when the DMD usage region is appropriate, and FIG. 17B is a cross-sectional view in the sub-scanning direction along the optical axis of FIG. FIG. 18A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system, and FIG. 18B shows an object to be exposed when a microlens array or the like is not used. FIG. 18C is an example of a plan view showing a light image projected on the surface to be exposed when a microlens array or the like is used. FIG. 19 is a plan view showing an example of an LCD TFT array substrate. FIG. 20 is a cross-sectional view showing the manufacturing process (No. 1) of the TFT array substrate for LCD. FIG. 21 is a cross-sectional view showing a manufacturing process (No. 2) of the TFT array substrate for LCD. FIG. 22 is a cross-sectional view showing a manufacturing process (No. 3) of the TFT array substrate for LCD. FIG. 23 is a cross-sectional view showing the manufacturing process (No. 4) of the TFT array substrate for LCD. FIG. 24 is a cross-sectional view showing a manufacturing process (No. 5) of the TFT array substrate for LCD. FIG. 25 is a cross-sectional view showing a completed TFT array substrate for LCD.

Explanation of symbols

50 ... Digital micromirror device (DMD)
54... Lens system 66... Fiber array light source 166 ..Exposure head (exposure unit according to the present invention)

Claims (9)

A base material using a positive photosensitive composition comprising at least a resin that exhibits alkali solubility by the action of an acid, and a photoacid generator that generates an acid that absorbs at least light having a wavelength of 405 nm A positive photosensitive layer forming step of forming at least a positive photosensitive layer on the surface of
A protective film forming step of forming a protective film containing at least polyvinyl alcohol having a mass average molecular weight of 8,000 to 100,000 on the surface of the positive photosensitive layer;
An exposure step of exposing the positive photosensitive layer from the protective film side;
And a development step of developing the positive photosensitive layer exposed in the exposure step.   The pattern forming method according to claim 1, wherein the resin that exhibits alkali solubility by the action of an acid includes a resin having a phenolic hydroxyl group in which a part of the phenolic hydroxyl group is protected.   The pattern forming method according to claim 2, wherein the protecting group for the phenolic hydroxyl group is any one of an acetal group, a ketal group, and a sterically hindered ester group.   The pattern formation method according to claim 1, wherein the photoacid generator includes an oxime sulfonate photoacid generator.   5. The pattern forming method according to claim 1, further comprising an intermediate layer forming step of forming an intermediate layer on the positive photosensitive layer.   The pattern forming method according to claim 1, wherein the exposure is performed using laser light having a wavelength of 400 to 410 nm.   The pattern forming method according to claim 1, further comprising a post-exposure heating step of performing a heat treatment on the exposed positive photosensitive layer before development.   A TFT array substrate formed by the pattern forming method according to claim 1. A liquid crystal display element using the TFT array substrate according to claim 8.