TW200832067A - Chemically amplified positive resist composition for thermal lithography and method for forming resist pattern - Google Patents

Abstract

A chemically amplified positive resist composition for thermal lithography to form a resist film which is used for the thermal lithography, wherein the resist film formed by using the chemically amplified positive resist composition for thermal lithography has an absorbance of 0.08 or greater per a film thickness of 100 nm at a wavelength of an exposure light source used in the thermal lithography.

Description

200832067 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a reinforced chemical type positive photoresist composition for thermal micro-etching, and a light for reinforced chemically-type positive resist composition using the thermal micro-etching The formation method of the resistance pattern. The present invention claims priority based on Japanese Patent Application No. 2006-283967, filed on Jan. 18,,,,,,,,,,,,,,,,,,,,,, In the manufacture of fine structures, the lithography technique is often used. In the lithography technique, conventionally, a photosensitive organic material called photoresi is used. For the photoresist, for example, a substance which changes solubility (alkali solubility) to an alkali developer by irradiation of a short-wavelength light such as a fluorescent ultraviolet light or a radiation such as an electron beam (exposure) is generally used. When the photoresist is exposed to light, a part of the structure can be decomposed to form cross-linking or the like to change the alkali solubility. Therefore, a difference in alkali solubility between the exposed portion and the unexposed portion is generated, and a resist pattern can be formed based on the difference. That is, when the photoresist is selectively exposed, the alkali solubility of the photoresist may be partially changed to form a portion having a higher alkali solubility and a lower solubility in alkali. Graphic type. Subsequently, when the photoresist is subjected to alkali development, a portion having a higher alkali solubility can be dissolved and removed to form a photoresist pattern. -4- 200832067 Photoresist, a negative type of alkali solubility of a positive light portion which increases the alkali solubility of an exposed portion. A photoresist having a high sensitivity to a short-wavelength exposure light source, such as a photochemical acid composition containing acid generated by the action of radiation, and a strong chemical type photoresist composition which changes alkali solubility based on the action of the acid (for example, Patent Literature) 1~2) In the optical ROM (Read Only Memory) disc, in the near future, the lithography technique for achieving ultra-high-density recording of at least 10 〇 nm or less is as described above, and has been developed so far. The method of using the light source, or the method of using an electronic wire, and the like. However, the narrowing of the wavelength of the light source used for the exposure is not a difficult exposure machine which is caused by optical causes such as a light source, and the wavelength of the light source is shortened, which tends to be expensive, and when an electron beam is used, it is generated. The need for high voltage conditions, chambers, etc. requires a significant increase in many devices. The foregoing problems will also increase the manufacturing cost of products such as discs. One of the technologies recently developed is the direct use of light by thermal micro-etching, and the feeding of the heat distribution generated by the light can be finely depicted below the spot diameter of the light, or formed at a high speed and low cost. It has also become possible. Previously reported thermal lithography uranium engraving methods, such as inorganic materials that cause rapid changes in properties above temperature, and data on the increase in the composition of known substrate (PAG) substrates However, I am very much looking forward to the problem of using a shorter wavelength to shorten. For example, a gridded, large-sized electronic harness, etc., will result in a CD-ROM. This technique is not a method. Thermal lithography allows the use of fine patterns to achieve specific materials. Example -5-200832067 As disclosed in Non-Patent Document 1, for example, a method of laminating a laminate of a ZnS-Si 2 layer, a TbFeCo layer, and a ZnS-SiO 2 layer on a substrate is described. The method 'is a thermal lithography uranium engraving using a change in volume based on heat. In this method, the TbFeCo layer absorbs laser light and generates heat. When the temperature exceeds 200 ° C, the volume begins to increase, and as a result, the laser light is irradiated. Part of the film thickness is increased to form a pattern. Further, as the inorganic material, for example, a method using platinum oxide (for example, Non-Patent Document 2) is also available. This method is a method in which the property of explosive evaporation occurs when platinum oxide is used at a certain temperature or higher, and the uranium oxide applied to the surface of the substrate is heated by blue laser light to remove the necessary portion for processing. Method of serving. In these methods, it is possible to form a fine pattern of 10 〇〇 nm or less using blue laser light (wavelength 405 nm). Further, for example, Non-Patent Document 3 discloses a method of laminating a composition obtained by sequentially depositing a Ge2Sb2Te5 layer, a ZnS-SiO2 layer, and a photoresist film on a substrate made of carbonate. In this method, first, when an infrared laser is irradiated from the lower side of the substrate, the laser light is absorbed by Ge2Sb2Te5, and Ge2Sb2Te5 is heated. When the heat is conducted to the photoresist film (negative type) of the upper layer, the photoresist film is changed to alkali insolubility by the action of the heat. Thus, when developed by alkali, a photoresist pattern can be formed. [Patent Document 1] Japanese Patent Publication No. 288 1 969 [Patent Document 2] JP-A-2003-24 1 3 85 [Non-Patent Document 1] Jpn·J·Appl· Phys·Vol· 43, No. 8B (2004) Ρρ. L 1 045-L 1047 [Non-Patent Document 2] The 53rd Applied Physics Physics Joint Lecture, -6- 200832067 Presentation to the Manuscript, 1051 (Spring 2006), 22a-D-9 [Non-patent Document 3] Jpn·J. Appl· Phys· Vol· 41, No. 9A/B (2002) pp. L 1 022-L 1024 [Summary of the Invention] The thermal micro-etching technique proposed so far, regardless of any technique They are all inorganic materials that absorb light and convert their energy. However, these inorganic materials are often expensive materials, and after the formation of the photoresist pattern, problems such as deterioration in workability such as substrate etching occur. One of the methods for solving the above problems is a method of performing thermal photolithography etching only on an organic material. However, so far, no technique has been proposed which does not use inorganic materials, and only thermal lithography using organic materials has been proposed. The present invention has been made in view of the above circumstances, and has been proposed to form a resistive pattern type thermochemical lithography enhanced chemical type positive photoresist composition capable of forming a photoresist pattern via thermal lithography, and to use the enhanced chemistry for thermal microlithography etching. A method of forming a photoresist pattern of a positive resist composition is for the purpose. As a result of intensive investigation, the present inventors have found that an enhanced chemical type positive resist composition having a specific absorbance of light of a wavelength higher than that of a light source used for exposure of the formed photoresist film is a specific time or more. When the above problems are solved, the present invention has been completed. That is, the first aspect of the present invention is a reinforced chemical type positive photoresist composition for thermal lithography etching, which is a thermal lithography etching for thermal lithography engraving to form a photoresist film. The reinforced chemical type positive photoresist composition is characterized in that: 200832067 is used in the thermal lithography uranium engraving using the photolithography film formed by the thermal lithography engraving enhanced chemical type positive photoresist composition. The wavelength of the exposure light source has an absorbance of 0.08 or more for each film thickness l 〇〇 nm. A second aspect of the present invention is a method for forming a photoresist pattern, which comprises the use of the first aspect of the thermal lithography lithography enhanced chemical type positive photoresist composition on the support. a step of forming a photoresist film, using the step of selectively exposing light having a wavelength of 100 nm or more for each film thickness of the photoresist film of 0.08 or more, and developing the photoresist film type The step of the photoresist pattern. A third aspect of the present invention is a reinforced chemical type positive photoresist composition for thermal lithography etching, which is an enhanced chemical type positive type for thermal lithography etching for thermal lithography etching to form a photoresist film. A photoresist composition characterized by comprising a substrate component (A) which increases alkali solubility via an action of an acid, an acid generator component (B) which generates an acid based on a heat action, and absorbs the aforementioned heat micro The dye (C) having a wavelength of 35 5 Onm or more of the exposure light source used for the uranium engraving, and the addition amount of the dye (C) is 8 to 65 mass% with respect to the component (A). A fourth aspect of the present invention is a method for forming a photoresist pattern, characterized by comprising the use of the third aspect of the thermal lithography to enhance the chemical type positive photoresist composition on the support. a step of forming a photoresist film, a step of selectively exposing the photoresist film using light having a wavelength of 350 nm or more, and a step of developing the photoresist film to form a photoresist pattern. In addition, in the scope of this specification and the patent application, "exposure" includes the illuminating effect of the full illumination of -8 - 200832067 rays. The "alkyl group" is a monovalent saturated hydrocarbon group containing a linear chain, a branched chain, and a ring, unless otherwise specified. The "lower alkyl group" means an alkyl group having 1 to 5 carbon atoms. The "alkylene group" is a divalent saturated hydrocarbon group containing a linear chain, a branched chain, and a ring, unless otherwise specified. "Structural unit" means the monomer unit (monomer unit) constituting the resin (polymer). The invention provides a reinforced chemical type positive photoresist composition for thermal lithography etching which can form a photoresist pattern for thermal lithography, and a reinforced chemical type positive photoresist composition for thermal lithography etching Method for forming photoresist pattern of heat lithography engraving enhanced chemical type positive photoresist composition. The reinforced chemical type positive photoresist composition for thermal lithography etching of the present invention uses the thermal micro-touch The photoresist film formed by the enhanced chemical type positive photoresist composition is required to have an absorbance of 0.08 or more per wavelength of 10 Onm in the wavelength of the exposure light source used in the thermal lithography uranium engraving. When the above absorbance has 〇 8 or more, a resist pattern can be formed by thermal lithography. That is, the reinforced chemical type positive resist composition generally contains a substrate component (A) which increases alkali solubility via an action of an acid, and an acid generator component (B) which generates an acid based on an acid action as a necessity. Ingredients. The acid generator component (B) used to enhance the chemical type positive resist composition is usually heated to a temperature higher than a certain temperature, and is the same as that at the time of exposure, and acidity can occur in -9-200832067. Therefore, when the absorbance of the photoresist film formed by the enhanced chemical type positive resist composition is 0.08 or more, in the thermal lithography, when the photoresist film is exposed, the photoresist film can be obtained. The acid generator component ( _ B ) is capable of generating heat at a sufficient temperature of the acid. Therefore, in the formation of the photoresist pattern, when the photoresist film is selectively exposed, the acid generator component (B) is acidized in the exposed portion, and the substrate component is increased based on the action of the acid ( The alkali solubility of A) is the same as that of the unexposed portion, and the alkali-insoluble φ is not changed. Therefore, when the photoresist film is alkali-developed, a photoresist pattern can be formed. The upper limit of the absorbance is not particularly limited. However, when considering the influence of thermal diffraction, lithography characteristics such as sensitivity, etc., each film thickness l〇0 nm is preferably 〇·5 or less. 5 or less is more preferable, and 〇·4 or less is the best 〇. The lower limit of the absorbance is 値, for each film thickness of lOOnm, preferably 0.08 or more, more preferably 0.10 or more, and most preferably 0. . # The above absorbance can be adjusted by adding to the enhanced chemical type positive resist group, and the type or amount of the components of the composition can be adjusted. For example, as described later, the above-mentioned 鮝 absorbance can be adjusted by adding a dye (C) that absorbs light of a wavelength of an exposure light source, and the higher the content of the dye (C), or the higher the light absorption energy of the dye (c) The aforementioned absorbance is greater. Further, as will be described later, each of the substrate components (A) is the same as the dye (C), and absorbs light of a wavelength used as an exposure light source for thermal lithography (hereinafter, simply referred to as "having light absorption"). In the case of the compound, the absorbance can be adjusted in such a manner that the kind or amount of the substrate component (A) can be adjusted. -10- 200832067 In the specification and the patent application, the aforementioned absorbance is a thermochemical lithography engraving chemical-type positive photoresist composition in a quartz-based photoresist film, and the wavelength of the exposure light source is measured for the photoresist film. The absorption was determined by the measurement of the film thickness of the photoresist film at a density of 10 nm from the film thickness of the photoresist film. The film formation of the photoresist film is carried out by coating the substrate with a spin coater using an organic solvent solution for enhancing the chemical photoresist composition for thermal lithography. The baking temperature is not particularly limited, and it can be set in accordance with the reinforced chemical type positive resist composition used. The absorbance of the photoresist film can be measured, for example, using a commercially available spectrophotometric. The reinforced chemical type positive photoresist group for thermal lithography etching of the present invention is also preferably in the case of a positive-type photoresist composition which is only referred to as the present invention, and contains an alkali-soluble property by the action of an acid. a base (A) (hereinafter, also referred to as (A) component), and an acid generator component (B) based on an acid generating acid (hereinafter, also referred to as (B), and light having a wavelength of absorbing the aforementioned exposure light source a positive photoresist composition of the dye (C) (also referred to as (C) component), etc. In the resist pattern, when the photoresist film formed using the positive photoresist composition is exposed, it is possible to C) The component absorbs the main light to generate heat, and acts on the component (B) to cause acid, and the acid is further used for (a) to increase the solubility of the alkali. The thick positive type is limited to the quartz and the appropriate component is used to carry out the composition of the product ( ). The hot component is not particularly limited as the component (2008) of 200832067 <(A) component> (A), and may be any of the components of the substrate component which has been proposed as a reinforcing chemical positive resist composition. The choice to use. The base component is generally a component having an acid dissociable dissolution inhibiting group. The base component is alkali-insoluble before exposure, and when an acid is generated via the component (B) after exposure, the acid dissociable dissolution inhibiting group is dissociated based on the action of the acid, and the alkali solubility is changed. Here, the "substrate component" means an organic compound having a film forming ability, and an organic compound having a molecular weight of 500 or more is preferably used. When the molecular weight of the organic compound is 500 or more, the film formation energy can be improved, and the pattern of the degree of nanometer can be easily formed. The organic compound having a molecular weight of 500 or more can be roughly classified into a low molecular weight organic compound having a molecular weight of 500 or more and 2000 or less (hereinafter also referred to as a low molecular compound), and a high molecular weight resin (polymer) having a molecular weight of more than 2,000. The aforementioned low molecular compound is usually used for non-polymer. In the case of a resin (polymer), the "molecular weight" is a mass average molecular weight in terms of polystyrene obtained by GPC (gel permeation chromatography). Hereinafter, the term "resin" alone means a resin having a molecular weight of more than 2,000. The component (A) may be a low molecular compound which increases alkali solubility by the action of an acid, or may be a resin which increases alkali solubility via an action of an acid, or a mixture thereof. The component (A), in addition to the acid dissociable dissolution inhibiting group, preferably has a hydrophilic group. When the hydrophilic group is provided, the hydrophilicity of the entire component (A) -12-200832067 can be improved, and the affinity with the developer can be improved, and the alkali solubility can be improved in the exposed portion, and the resolution can be improved. The hydrophilic group is selected, for example, from a group consisting of a hydroxyl group, a carboxyl group, a carbonyl group (-C(0)-), an ester group (ester bond; -C(0)-0-), an amine group, and an amidino group. One or more of them are preferred. Among them, a hydroxyl group (particularly an alcoholic hydroxyl group or a phenolic hydroxyl group), a carboxyl group or an ester group is more preferable. Among them, a carboxyl group, an alcoholic hydroxyl group, or a phenolic hydroxyl group is preferably a fine pattern which can form a line edge roughness of the side of the pattern. The hydrophilic group may have both an acid dissociable dissolution inhibiting group. The component (A) of the positive resist composition of the present invention is preferably the following (A-1) component and/or (A-2) component. • (A-1) component: a resin having a structural unit of an acid dissociable dissolution inhibiting group. • (A-2) Ingredients: Low molecular compounds with acid dissociative dissolution inhibitory groups. Hereinafter, the preferred aspects of the (A-1) component and the (A-2) component will be specifically described. [(A-1) component] The component (A-1) is a resin having a structural unit of an acid dissociable dissolution inhibiting group. In the component (A-1), the ratio of the structural unit having the acid dissociable dissolution inhibiting group is preferably 20 to 80 mol% based on the total amount of the total structural unit constituting the component (A-1). Take 20~70%% for more -13-200832067, and 30~60% for the best. Further, the component (A-1) is a hydrophilic group in addition to the structural unit having an acid dissociable solubility, and the structural unit having a hydrophilic group is, for example, the same as described above. Preferably, the structural unit having a hydrophilic group is a structural unit of a base, an alcoholic hydroxyl group or a phenolic hydroxyl group, and more preferably an (α-lower alkyl) propylene hydroxyl group having a methacrylic acid or an alcoholic hydroxyl group. A structural unit derived from styrene. In the component (A-1), the structural unit having the hydrophilic group is preferably 20 to 80 mol%, and 20 to 70 mol%, based on the total structural unit constituting the (A-1) component. % is better, 60% is the best. (A-1) component, more specifically, a knot derived from a phenolic resin containing a solubilization inhibiting group, a hydroxystyrene resin lower alkyl acrylate resin, or a hydroxystyrene, and (α-lower A resin or the like of a structural unit derived from an alkyl group acrylate is preferred. Further, in the present specification, "(α-lower alkyl) acrylic acid acrylic acid (CH2=CH-COOH) and α-lower alkylacrylic acid are both meanings. α-lower alkylacrylic acid means a bond group in acrylic acid The hydrogen atom to which the carbon atom (the carbon atom in the alpha position) is bonded is low-substituted. "(α-Lower alkyl) acrylate" is an ester derivative of (α-lower acrylic acid), which means acrylate and The α-lower alkane inhibits the base. The carboxylic acid acrylate has a ratio of 20 to 1 dissociation ^ (a · unit copolymerization) means one or a carbonyl alkylalkyl group-based propylene -14- 200832067 One or both of the acid esters. "Structural unit derived from (α-lower alkyl) acrylate" means the bi-symmetric double bond of (α-lower alkyl) acrylate The structural unit formed by cracking, hereinafter also referred to as (α-lower courtyard) acrylate structural unit. "(α-Lower alkyl) acrylate" means one of acrylate and α-lower alkyl acrylate or The meaning of both. "The knot derived from hydroxystyrene "Unit" means a structural unit formed by the cracking of an ethylenic double bond of hydroxystyrene or α-lower alkyl hydroxystyrene, hereinafter also referred to as a hydroxystyrene unit. ^ ^ -Lower alkyl hydroxystyrene It is meant that the carbon atom bonded to the phenyl group is bonded to the lower alkyl group, the structural unit derived from the α-lower alkyl acrylate, and the structural unit derived from the α-lower alkyl hydroxystyrene. The lower alkyl group bonded to the α-position is an alkyl group having 1 to 5 carbon atoms, and preferably a linear or branched alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or η-butyl group. Base, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The methyl group is preferred in the industry. Among the components (A-1), the preferred resin component is not particularly limited, for example, And having a unit having a phenolic hydroxyl group such as the following structural unit (a 1 ), and at least one selected from the group consisting of the following structural unit (a2) and the following structural unit (a3) having acid dissociable dissolution a structural unit of the inhibiting group 5 and, if necessary, a resin having an alkali-insoluble unit as in (a4) (hereinafter, also referred to as (A-11) component), etc. Among the components (A-11), the action of the acid generator -15-200832067 based on exposure causes the structural unit (a2) and/or Cracking occurs in the structural unit (a3), so that the alkali solubility of the resin which is insoluble to the alkali developer can be increased. As a result, a positive pattern of the enhanced chemical form can be formed by exposure and development. • Structural unit (al) The structural unit (a 1 ) is a unit having a phenolic hydroxyl group, preferably a unit derived from a hydroxystyrene represented by the following formula (Γ).

(I,) wherein R is a hydrogen atom or a lower alkyl group, and R is a hydrogen atom or a lower alkyl group. The lower alkyl group is, for example, the same as the lower alkyl group bonded to the above-mentioned α-position, and particularly preferably a hydrogen atom or a methyl group. The description of R is the same as the following. The bonding position of the benzene ring is not particularly limited, and the position (alignment) of 4 described in the formula is preferred. The structural unit (al) is preferably contained in the () component of 40 to 80. If it is 40 mol% or more, the Mox% of the shape of the pattern can be obtained, and it is preferable to contain 50 to 75 mol%, which can improve the solubility to the alkali developing solution, and the effect is also good. . When it is less than 80%, it can be balanced. • Structural unit (a2) The structural unit (a2) has an acid dissociable position, which is represented by the following formula (II,). Structure sheet of the flat structure of other structural units

(wherein R is a hydrogen atom or a lower alkyl group, an inhibiting group), and the acid dissociable dissolution inhibiting group X is a tertiary carbon atom having three such tertiary alkyl groups bonded to an ester g acid-releasing inhibiting group, Tetrahydropyranyl, four dust base, and the like. Among the groups used for the acid dissociable dissolution inhibiting group X, for example, the 丨-type photoresist composition, the above-mentioned oxime structural unit (a2) is preferably exemplified by the following formula. X is an acid-dissociable solution: an alkyl group of a carbon atom, a compound of the formula [-C(0) 0-], a cyclic acetal such as a furyl group, which can be used as a basis for enhancing the chemical form (ΙΙΓ). The person indicated is -17- 200832067

...(I I r )

In the formula, R is a hydrogen atom or a lower alkyl group, and each of R11, R12 and R13 is independently an alkyl group (either straight chain or branched chain, preferably a lower alkyl group having 1 to 5 carbon atoms). Or, among R11, R12 and R13, R11 is a lower alkyl group, and R12 and R13 are bonded to each other to form a monocyclic or polycyclic aliphatic cyclic group. The carbon number of the aliphatic cyclic group is preferably from 5 to 12%. Here, "aliphatic" means that the group or compound does not have aromatic meaning, and "aliphatic cyclic group" means a monocyclic group or a polycyclic group which does not have an aromatic group. R11, R12 and R13 are those which do not have an aliphatic cyclic group. For example, any of R11, R12 and R13 is preferably a methyl group. In the case where any of R11, R1 2, and R13 is an aliphatic cyclic group in the case where the aliphatic group is a monocyclic aliphatic ring group, the structural unit (a2) has, for example, a ring. Amyl, cyclohexyl and the like are preferred. When the aliphatic cyclic group is a polycyclic alicyclic group, the structural unit (a2) is less preferred, for example, represented by the following formula (IV). -18 - 200832067

(IV, • [wherein R is a hydrogen atom or a lower alkyl group, and R14 is an alkyl group (any of a straight chain or a branched chain may be used. Preferably, it is a low-grade base having a carbon number of 1 to 5)] The group having an acid dissociable dissolution inhibiting group containing a polycyclic aliphatic cyclic group is preferably, for example, represented by the following formula (V').

R

(V, wherein R is a hydrogen atom or a lower alkyl group, and R15 and R16 are each independently an alkyl group (may be either a straight chain or a branched chain. Preferably, the carbon number is -19-200832067 1 ～5的lower alkyl)] The structural unit (a2) is present in the (A-1 1 ) component in an amount of 5 to 50 mol%, preferably 1 〇 to 4 〇 mol%, more preferably 1 0 to 3 5 % of the molar % • Structural unit (a3) The structural unit (a3 ) is a structural unit having an acid dissociable dissolution inhibiting group, which is represented by the following general formula (VI').

(VI * ) (wherein R is a hydrogen atom or a lower alkyl group, and X ' is an acid dissociable dissolution inhibiting group). The acid dissociable dissolution inhibiting group X ' is tert-butyloxycarbonyl, tert-pentyl a tertiary alkoxycarbonyl group such as an oxocarbonyl group; a tertiary alkyl oxycarbonylalkyl group such as tert-butyloxycarbonylmethyl or tert-butyloxycarbonylethyl; tert-butyl, tert-pentyl The second courtyard of the temple; the ring-shaped awake base such as tetrachloropyranyl and tetrachloropyranyl; the oxyhydrazine group such as ethoxyethyl and methoxypropyl. Among them, tert-butyloxycarbonyl, tert-butyloxycarbonylmethyl, tert-butyl, tetrahydropyranyl or ethoxyethyl is preferred. -20- 200832067 The acid dissociable dissolution inhibiting group X ', for example, in the group used for the positive-type resist composition of the enhanced chemical type, any of the above-mentioned groups can be used arbitrarily. In the formula (VI'), the bonding position of the group bonded to the benzene ring (-OX') is not particularly limited, but the position (alignment) of 4 shown by the formula is preferable. The structural unit (a3), in the component (A-1 1 ), preferably 5 to 50 mol% is preferably 1 to 10 mol%, and 10 to 3 mol%. The range is the best. • Structural unit (a4) The structural unit (a4), which is a unit of alkali insolubility, is represented by the following general formula (VII').

(wherein R is a hydrogen atom or a lower alkyl group, R4' is an alkyl group, n is an anthracene or an integer of 1 to 3) Further, an alkyl group of R4' may be a straight chain or a branched chain. Good M A lower alkyl group having a carbon number of 1 to 5. η' is an integer of 0 or 1 to 3, and is preferably 〇. The structural unit (a4) is 1 to 4 〇mol 0/〇 -21 - 200832067 in the composition of (Α-11), preferably 5 to 25 mol%. For 1 mole. /. In the above case, the effect of improving the shape of the height (especially, the film reduction) is 4 〇 mol% or less, and the balance with other structural units can be obtained. • In (A-11), the above structural unit (al), and at least one selected from the group consisting of structural unit (a2) and structural unit (a3), are optional and may contain any (a4). ). Further, a copolymer having all of the above units may be used, or a mixture obtained by mixing one or more of the units of the Lu polymer may be used. Further, it may be used in combination. Further, the component (A-11) may optionally contain any of the structural units (al) to (a4), but the ratio of the structural units (al) to (a4) is 80% or more. Preferably, it is preferably more than 90% by mole (1% of the molar % is optimal). In particular, "any of the copolymers having the above structural units (al) and (a3), or a mixture of two or more of the copolymers" or "having structural units (al), (" Any of the copolymers of a2) and (a4): or a mixture of two or more of the copolymers is preferred, and the effect can be easily obtained. Further, it is also preferable from the viewpoint of improving heat resistance and the like. In particular, a mixture of polyhydroxystyrene which is protected by a tertiary alkoxycarbonyl group and polyhydroxystyrene protected by an alkoxyalkyl group is preferred. When mixing, 'mixing ratio (mass ratio) of each polymer (polyhydroxy styrene protected by a polyhydroxy styrene/1-alkoxyalkyl group protected by a tertiary alkoxycarbonyl group), for example, 1/9 ~9/1, preferably 2/8~8/2, more preferably -22-200832067 2/8~5/5. In addition to the above (A-11) component, it is more suitable as a resin component of the component (A-1), and in particular, a viewpoint of forming a pattern having lower etching resistance, and the like (α-lower alkyl) acrylate is used. The resin component of the resin ((α-lower alkyl) acrylate resin) is preferred, and the resin component obtained from the (α-lower alkyl) acrylate resin is more preferable. (α-lower alkyl) acrylate resin (hereinafter, also referred to as (Α-φ 1 2 ) component), a structure derived from (α-lower alkyl) acrylate having an acid-dissociable dissolution inhibiting group The resin of the unit (a5) is preferred. The α-lower alkyl group (lower alkyl group bonded to the α-position) is, for example, the same as described above. The acid dissociation-dissolving system of the structural unit (a5) is a base-dissolving property, and has an alkali-insoluble inhibition property of the entire resin component before exposure, and is dissociated by the action of an acid generated by the component (B) after exposure. The entire component (A-1 2 ) is changed to an alkali-soluble base. • Acid dissociative dissolution inhibitory group, for example, light which can be irradiated by ArF excimer. The resin used for the resistive composition is appropriately selected from the contents of most proposals. In general, it is known that, for example, a carboxyl group of a cyclic or chain tertiary alkyl ester may be formed with a carboxyl group of (α-lower alkyl)acrylic acid, or a cyclic or chain-like amphoteric group. Here, the "group forming a tertiary alkyl ester" means that a hydrogen atom of a carboxyl group of acrylic acid is substituted to form an ester group. Namely, the oxygen atom at the terminal of the carbonyloxy group [-C(0)-0-] of the acrylate has a structure in which a tertiary carbon atom of a chain or a cyclic tertiary alkyl group is bonded. In the tertiary alkyl ester, when the acid is produced by -23-200832067, the bond between the oxygen atom and the tertiary carbon atom can be cut off. Further, the tertiary alkyl group means an alkyl group having a tertiary carbon atom. A group of a chain tertiary alkyl ester such as tert-butyl, tert-pentyl or the like is formed. The group forming the cyclic tertiary alkyl ester is, for example, the same as the content exemplified as the "acid-dissociable dissolution inhibiting group containing an alicyclic group" which will be described later. φ "A cyclic or chain alkoxyalkyl group" may form an ester by substituting a hydrogen atom of a carboxyl group. Namely, a structure obtained by bonding an oxygen atom at the terminal of the acrylate carbonyloxy group [-C ( 0) -0-] to the alkoxyalkyl group can be formed. In this configuration, the bond between the oxygen atom and the alkoxyalkyl group can be interrupted by the action of an acid. The cyclic or chain alkoxyalkyl group, for example, 1-methoxymethyl, 1-ethoxyethyl, 1-isopropoxyethyl, 1-cyclohexyloxyethyl, 2-adamantaneoxy Base, 1-methyladamantyloxymethyl, 4-oxo-2-adamantanyloxymethyl, 1-adamantanyloxyethyl, 2-adamantanyloxyethyl, and the like. • The structural unit (a5) is preferably a structural unit containing a cyclic group, particularly an aliphatic ring-containing dissolution group. Among them, "aliphatic" and "aliphatic ring-based" are as defined above.

The content of V meaning. The aliphatic cyclic group may be a monocyclic ring or a polycyclic ring, for example, among ArF photoresists and the like, and may be appropriately selected from most of the proposed groups. From the viewpoint of etching resistance, a polycyclic alicyclic group is preferred. Further, the alicyclic group is preferably a hydrocarbon group, and particularly preferably a saturated hydrocarbon group (alicyclic group). A monocyclic alicyclic group, for example, a cycloalkane obtained by removing one hydrogen atom, and a base of -24-200832067. The polycyclic alicyclic group is, for example, a group obtained by removing one hydrogen atom from a bicycloalkane or a tetracycloalkane or the like. Specifically, a monocyclic alicyclic group such as a cyclopentyl group. A polycyclic alicyclic group such as a polycycloalkane such as adamantane, protopane, isodecane or tetracyclododecane removes one hydrogen atom or the like. Wherein, the original spinachene obtained by removing one hydrogen atom from adamantane to remove one hydrogen atom, the tricyclic fluorenyl group obtained by removing three hydrogen atoms, and the tetracyclododecane are removed by four The cyclododecyl group or the like is industrially preferable. More specifically, the structural unit (a5) is preferably at least one selected from the group consisting of the following (III). Further, the ester moiety derived from the (α-lower alkyl) acrylate has the above cyclic group. a unit of an alkoxyalkyl group, specifically having a 2-adamantyloxymethyl group, a 1-methyladamantaneoxymethyladamantaneoxymethyl group, a 1-adamantanyloxyethyl group, a 2-adamantanyloxy group A polycyclic alkoxy lower alkyl group (at least one selected from the group derived from an α-lower alkyl ester) is preferred. [Chemical 8] A fund obtained from a spine or a tricyclic ring such as a tricycloalkane or a cyclohexyl group. A unit of the formula (I") in which a hydrogen atom is removed by a straight alkyl group or a decane, and, for example, a substituent such as a 4-oxoethyl group)

(I , , ) -25- 200832067 [In the formula (I"), R is a hydrogen atom or a lower alkyl group, and R1 is a lower alkyl group]

[化9]〇^〇

[In the formula (II"), R is a hydrogen atom or a lower alkyl group, and R2 and R3 are each independently a lower alkyl group]

[化1 0] R

In the formula (III", R is a hydrogen atom or a lower alkyl group, and R4 is a tertiary -26 - 200832067 alkyl group. In the formula (I") to (III"), a hydrogen atom or a lower alkyl group of R is a The description is the same as the above description of the hydrogen atom or the lower alkyl group bonded to the α-position of the acrylate. The lower alkyl group of R is an alkyl group having 1 to 5 carbon atoms, and is a linear or branched alkyl group. The base is preferably, for example, methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. Preferably, a lower alkyl group of φ R1 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group or a η-butyl group. Isobutyl, pentyl, isopentyl, neopentyl, etc. Among them, a methyl group and an ethyl group are preferably industrially easy to obtain. The lower alkyl groups of R2 and R3 are each independently carbon. A linear or branched alkyl group of 1 to 5 is preferred, and in the case where both R2 and R3 are simultaneously a methyl group, it is industrially preferable. Specifically, for example, 2-(1-adamantyl)-2 -propyl acrylate Derived structural units, etc. • R4 is a chain of a tertiary alkyl group or a cyclic tertiary alkyl group, and preferably a carbon atom, the number of 4 to 20 is preferred. The bond-like secondary courtyard base 'e tert- Butyl or tert-pentyl% 'is also industrially preferred as tert-butyl. Further, the tertiary intermediate is an alkyl group having a tertiary carbon atom. A cyclic tertiary alkyl group is as described above. The contents exemplified in the "acid-dissociable dissolution inhibiting group containing an aliphatic cyclic group" are the same contents 'for example, 2-methyl-2-goldenamine base, ethyl-2-golden base, 2-(1- King Kong Institute base-2-propyl, 1-ethylcyclohexyl, ethylethylcyclopentyl, 1-methylcyclohexyl-27-200832067, i-methylcyclopentyl and the like. The alkyl propylene 8 or the thio-COOR 4 may be bonded to the position of the 4 or 4 of the tetracyclic 12 shown in the formula without a specific bonding position. Further, the carboxyl group residue of the I acid ester structural unit may be bonded to the same position as shown in the formula. The structural unit (a5) may be used alone or in combination of two or more. (A -1 2 ) The ratio of the 'structural unit (a 5 ) in the composition, relative to the total structure of the constituents of the (A-12) component, preferably 20 to 60 mol%, to 30 to 50 mol The ear % is better, and the best is 35 to 45 mol%. When 20 mol% or more, the pattern can be obtained, and when it is 60 mol% or less, the balance with other structural units can be obtained. The component (A-12) is preferably a structural unit (a6) derived from an acrylate having a lactone ring in addition to the above structural unit (a5). The structural unit (a6) can improve the adhesion of the photoresist film to the substrate, and can effectively improve the hydrophilicity with the developer. # Structural unit (a6), which is bonded to the carbon atom of the alpha position, is a lower alkyl group or a hydrogen atom. The lower alkyl group bonded to the carbon atom at the α-position is, for example, the same as the lower alkyl group of the structural unit (a5), and is preferably a methyl group. The structural unit (a6), for example, an ester branch of an acrylate, is bonded to a structural unit derived from a monocyclic group formed by a lactone ring or a cyclic group having a polycyclic ring of a lactone ring. Further, the lactone ring at this time means a ring containing a structure of -o-c ( 〇 )- and is counted as one ring. Therefore, the case where only the lactone ring is a monocyclic group and the other ring structure -28-200832067 is called a polycyclic group regardless of its configuration. The structural unit (a6) is, for example, a monocyclic group obtained by removing one of r-butyrolactone or a polycyclic group obtained by removing one atom of a bicycloalkane containing a lactone ring. The structural unit (a6), more specifically, for example, the following formula (~VII)) is preferably at least one selected. [Chemical 1 1] Hydrogen Original hydrogen IV"

, R6 Φ [In the formula (IV"), R is a hydrogen atom or a lower alkyl group, and R: each independently S: is a hydrogen atom or a lower alkyl group]

R

[Chemical 1 2] -29- (V,,) 200832067 [In the formula (v"), R is a hydrogen atom or a lower-grade yard, m is 0 or 1

[In the formula (VI"), R is a hydrogen atom or a lower alkyl group] [Chemical Formula 1]

R

[In the formula (VII"), R is a hydrogen atom or a lower alkyl group] -30- 200832067 In the formula (IV") to (VII"), a hydrogen atom or a lower alkyl group of R, for example, the above formula ( The description of the hydrogen atom or the lower alkyl group of R in I") to (III,,) is the same. In the formula (IV"), R5 and R6 each independently represent a hydrogen atom or a lower alkyl group, preferably a hydrogen atom. Among R5 and R6, the lower alkyl group is preferably a linear or branched alkane having a carbon number of 1 to 5. a group such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. φ is industrially preferred. In the structural unit represented by the general formulae (IV") to (VII"), the structural unit represented by (IV") is inexpensive and is suitable for industrial use, and the structural unit represented by (IV") Wherein R is a methyl group, R5 and R6 are a hydrogen atom, and the ester bonding position of the methacrylate to the r-butyrolactone is the α-methylpropenyloxy-7 of the α-position on the lactone ring. The lactone is the most preferable. The structural unit (a6) may be used alone or in combination of two or more. In the component (A-1 2 ), the ratio of the structural unit (a6) is relative to the constituent φ (A·12 ). The total of the total structural units is preferably 20 to 60 mol%, more preferably 20 to 50 mol%, and most preferably 3 to 4 mol%. Can improve the lithography characteristics of 6 When the molar percentage is 5% or less, a balance with other structural units can be obtained. The component (A-12) is further contained in addition to the structural unit (a5) or the structural unit (a5) and (&6). The structural unit (a7) derived from the polycyclic group-containing acrylate having a polar group is preferred. The structural unit (a7) can improve the hydrophilicity of the entire component (A-12) and improve the affinity with the developer and improve the affinity. The alkali solubility of the exposed portion, and further, -31 - 200832067 can improve the resolution. In the structural unit (a7), the carbon atom bonded to the α-position is a lower alkyl group or a hydrogen atom. The carbon atom bonded to the α-position is bonded. The lower alkyl group is the same as the lower alkyl group of the structural unit (a5), and is preferably a methyl group. A polar group such as a hydroxyl group, a cyano group, a carboxyl group, an amine group or the like, particularly preferably a hydroxyl group. The cyclic group may be, for example, an aliphatic ring group exemplified by the "aliphatic cyclic group-containing acid dissociable dissolution inhibiting group" of the above (a5) unit, and appropriately selected from the contents of the polycyclic ring. . The structural unit (a7) is preferably at least one selected from the group consisting of the following general formulae (VIII") to (IX, ?).

(〇H)n [In the formula (VIII"), 'R is a hydrogen atom or a lower alkyl group, and η is an integer of 1 to 3; R in the formula (VIII)) and the above formula (I)) to (() R in III") is the same content. -32- 200832067 In the formula (VIII"), it is preferred that η is 1 and the hydroxyl group is bonded to the adamantyl group.

(CN)k [In the formula (IX"), & is a hydrogen atom or a lower alkyl group, and ^ is an integer of 1 to 3] R in the formula (IX") and the above formula (I") R in (ΙΠ) is the same content. In the general formula (IX"), it is preferred that k is one. Further, it is preferred that the cyano group is bonded to the 5- or 6-position of the original spinnyl group. One or two kinds of structural units (a7) can be used. The combination of the above. (A-12) The ratio of the structural unit (a7) to the total structural unit constituting the component (A-12) is preferably 1 〇 to 5 〇 mol%, and 15 〜40mol% is better, and 2〇~35mol% is the best. When it is more than 1%, it can improve the lithography characteristics of lithography. When it is 50% or less, it can be obtained with other The balance of structural units. In the composition of (A-12), the above-mentioned structural unit (a5) to (u) is the sum of 200832067's relative to the total structural unit constituting the (A-1 2) component, to 70~100 The ear % is preferably 80 to 100 mol%. The (Ad2) component may contain structural units other than the above structural units (a5) to (a7) (a 8 ). The structural unit (a8), as long as it is not When it is classified into other structural units of the above structural units (a5) to (a7), it is not particularly limited. For example, it contains a polycyclic aliphatic hydrocarbon group and is derived from (α-lower alkyl) acrylate. The polyvalent aliphatic hydrocarbon group is, for example, an aliphatic cyclic group exemplified by the above-mentioned "aliphatic cyclic group-containing acid dissociable dissolution inhibiting group", which is composed of a polycyclic group. Use the appropriate choice. In particular, when at least one selected from the group consisting of a tricyclic fluorenyl group, an adamantyl group, a tetracyclododecyl group, a raw spintenyl group, and an isobornyl group is preferable, it is preferably industrially easy to obtain. The structural unit (a8) is preferably a non-acid dissociable group. The structural unit (a8)' specifically has, for example, a structural unit having a structure of the following general formula (X") to (X11"). [化1 7] Η

(X") -34- 200832067

(wherein R is a hydrogen atom or a lower alkyl group) [Chem. 1 8] R

(wherein R is a hydrogen atom or a lower alkyl group)

R

(wherein R is a hydrogen atom or a lower alkyl group) In the formula (X") to (XII"), a hydrogen atom or a lower alkyl group of R5, for example, and the above formula (I") to (III") The description of the hydrogen atom or lower alkyl group of R is the same. In the case of the structural unit (aS), the ratio of the structural unit -35-200832067 (a8) in the component (A-12) is 1 to 25 m per unit of the total structural unit constituting the component (A-12). % is better, preferably 5 to 20 mol%. The component (A-12) is preferably a copolymer having at least structural units (a5) (a6) and (a7). The copolymer is, for example, a copolymer composed of the above structural units (a5), (a6) and (a7), a copolymer composed of the above structural units (a5), (a6), (a7) and (a8), and the like. . The component (A-1) can be obtained, for example, by polymerization of a monomer of the above structural unit by a known method of φ. For example, a monomer of each structural unit is obtained by, for example, polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN) by a known radical polymerization reaction or the like. (A-1) The mass average molecular weight of the component (the polystyrene-converted mass average molecular weight of the gel permeation chromatography method is the same as the following) is preferably 30,000 or less, more preferably 20,000 or less, and most preferably 12,000 or less. good. The lower limit 値 is more than 2,000, and is preferably 4,000 or more, and more preferably 5,000 or more, from the viewpoint of suppressing pattern collapse and improving resolution. [(A-2) component] (A-2) component having a molecular weight of 500 or more and 2000 or less and having a low acid dissociation inhibition group X or X' exemplified by the above (A-1) component description Molecular compounds are preferred. Specifically, among the hydroxyl groups of the compound having a plurality of phenolic frameworks, a part or all of a hydrogen atom is partially or completely substituted by the above-mentioned acid dissociable dissolution inhibiting group X or X'. (A-2) component, for example, a part of a hydrogen atom in a hydroxyl group of a low molecular weight phenol compound-36-200832067 which is a non-reinforced chemical type g-line or i-line photoresist which is a sensitizer or a heat-resistant enhancer. It is preferred that all or part of the acid dissociable dissolution inhibiting group is substituted, and if it is the above component, it can be optionally used. The low molecular weight hydrazine compound is, for example, a compound which is not described below. Bis(4-hydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-( 2,3,4-trihydroxyphenyl)-2-(2,3,4,3-trihydroxyphenyl)propane, tris(4-hydroxyphenyl)methane, bis(4-hydroxy·3,5 -Dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-di Methylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-trans-based) 3-methylphenyl)-3,4 - _*-p-phenylene, bis(3-cyclohexyl-4 hydroxy-6-methylphenyl)· 4 hydroxyphenylmethane, double (3 -cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1, a 2, 3, 4 nucleus of a hydrazine formal water condensate such as (4-hydroxyphenyl)ethyl]benzene, phenol, m-cresol, P-cresol or xylenol. Of course, it is not limited to this. Further, the acid dissociable dissolution inhibiting group is not particularly limited, and examples thereof include the above. In the present invention, the component (A) may be a component having light absorbability or a component having no light absorbability. In order to enhance the effect of the present invention, the component (A) is preferably one having light absorbability. That is, when the component (A) has light absorbability, the amount of the component (C) added to achieve the desired absorbance can be reduced. Therefore, it is possible to reduce defects which may occur due to the addition of the (C) component, such as sublimation due to heating at the time of film formation, or the deterioration of the yield caused by the -37-200832067, precipitation as a solution, etc. . For example, among the above-exemplified organic compounds, there is a compound having a molecular structure for absorbing light of a wavelength of an exposure light source in thermal micro-etching, which has light absorbability. (A) The component may be used singly or in combination of two or more kinds of < (B) component > (B) component, which is an acid component based on the action of heat. Here, "the acid is generated by the action of heat" means that acid is generated by heating at 80 ° C or more and 200 ° C or less. The component (B) can be appropriately selected from any of the known compounds which have been conventionally used as an acid generator for enhancing chemical resist. As such acid generators, for example, a gun salt acid generator such as an iodine salt or a phosphonium salt, an oxime sulfonate acid generator, a dialkyl group or a bisarylsulfonium diazomethane, A diazomethane acid generator such as a bisacesulfonyl diazomethane, a nitrobenzyl sulfonate acid generator, an imiline sulfonate acid generator, a diterpene acid generator, and the like substance. Further, as the acid generator, generally, for example, there is a function of a thermal acid generator (TAG) which generates an acid based on the action of heat based on an acid photoacid generator (PAG) which is exposed to heat. Therefore, the '(B) component can be a specific example of a PAG key acid generator used in conventional photolithography etching, for example, diphenyl iodide trifluoromethanesulfonate, (4-methoxyphenyl). Phenyl iodide trifluoromethanesulfonate, bis(-38-200832067 p-tert-butylphenyl) iodine trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, (4-A Oxyphenyl)diphenylphosphonium trifluoromethanesulfonate, (4-methylphenyl)diphenylphosphonium hexafluorobutanesulfonate, (p-tert-butylphenyl)diphenylphosphonium Fluoromethanesulfonate, diphenyl iodide nonafluorobutane sulfonate, bis(p-tert-butylphenyl) iodine hexafluorobutane sulfonate, triphenyl* mirror nonafluorobutane sulfonate Acid esters, etc. Among them, a fluorinated alkylsulfonic acid ion is preferably used as the key salt of the anion. Examples of the φ oxime sulfonate compound, such as α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonyloxyimido)-fluorene-methoxyphenylacetonitrile, (trifluoromethylsulfonyloxyimido)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-fluorene-methoxyphenylacetonitrile, α·(ethylsulfonyloxy) Imino)-fluorene-methoxyphenylacetonitrile, α-(propylsulfonyloxyimido)-fluorene-methylphenylacetonitrile, α-(methylsulfonyloxyimino)-hydrazine- Bromophenyl acetonitrile and the like. Among them, α-(methylsulfonyloxyimino)- ρ-methoxyphenyl b. • Specific examples of diazomethane acid generators, bis(isopropylsulfonyl)diazomethane, bis(indolyl-toluenesulfonyl)diazide, bis(1,1-dimethylethyl) Sulfhydryl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and the like. The (Β) component may be used singly or in combination of two or more. In the positive resist composition of the present invention, the content of the (Β) component is 1 to 2 parts by mass, preferably 2 to 10 parts by mass, per part by mass of the component (A). When it is at least the lower limit of the above range, it can be formed in a sufficient form of Fig. 39-200832067, and when it is less than or equal to the upper limit of the above range, uniformity is easily obtained, and good storage stability is obtained. < (c) Component> (C) component, as long as it is an organic compound capable of absorbing the light of the wavelength of the light source of the lithography, the wavelength of the exposure light source used is not particularly matched, and is commercially available. Dyes are used. The dye may be determined by referring to the manufacturer's manual or by measuring according to the usual method, in judging whether it can absorb the exposed light used. Generally, to enhance the chemical type of photoresist, generally use light of a wavelength that can be used, such as a KrF excimer laser, an ArF quasi-dispersive laser, or a photochemical type photoresist that is sensitive to a short-wavelength source, usually For light beams with wavelengths above 3 65 nm, they are not sensitive. Therefore, the component (C) is preferably a compound having a wavelength of 1 or more, more preferably a compound capable of absorbing 3 65 nm of light, and a dye capable of absorbing visible light, particularly at an absorption wavelength of 3 50 to 800 nm. The dye of light is preferably a dye of 3 to 50 to 550 nm, and the dye of 3 to 50 is preferred.

For example, the light which can absorb the wavelength near 40 〇 nm is a compound which is used as a yellow dye, specifically, for example, OY-105, OY-107, OY-108, OY-129, OY-3G.

The exposure is limited by the wavelength of the appropriate light source. The spectrophotometer has a resistance of 250 nm or less. This enhancement, for example, is visible and acceptable for wavelengths at 350 nm. It is good to absorb a photopolymer of 450 nm, mainly, trade name: OY-GG-S -40- 200832067 (above, manufactured by Global Chemical Co., Ltd.) Diaresin Yellow F ' Diaresin A (above, manufactured by Mitsubishi Chemical Corporation), Soldan Yellow GRN (above, manufactured by Sino-foreign Chemical Co., Ltd.), Sumiplast Yellow GG, Sumiplast Yellow F5G, Sumiplast Yellow FG (above, Sumitomo Chemical Co., Ltd.), CH-1002 (manufactured by Daito Chemical Co., Ltd.), and the like. (C) The component may be used singly or in combination of two or more kinds of cerium (C) components. The absorbance of the photoresist film formed using the positive photoresist composition is in the wavelength of the exposure light source. As long as each film thickness lOOnm has an amount of 0.08 or more, it can match the expected absorbance, the type of (C) component used, and whether the (A) component absorbs the wavelength of the exposure light source, and the like. , appropriate adjustments can be. The preferred addition amount of the component (C) is a ratio of 1 to 80% by mass, more preferably 3 to 75% by mass, particularly preferably 4 to 70% by mass, more preferably, relative to the component (A). It is 5 to 6 5 mass%, preferably 8 to 6 5 mass%. When it is 1% by mass or more, the absorbance can be improved. When it is 80% by mass or less, the coating property can be improved. &lt;arbitrary component&gt; The positive photoresist composition of the present invention has a post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer. It is preferable to add a nitrogen-containing organic compound (d) (hereinafter, also referred to as (D) component) of any component. -41 - 200832067 There are various proposals for the (D) component, which can be used by any of the known materials, among which amines, especially secondary lower aliphatic amines or tertiary lower aliphatic amines. It is better. Wherein, the lower aliphatic amine refers to an alkyl group having 1 or more and 5 or less carbon atoms or an amine of an alkanol, and examples of the secondary or tertiary amine are, for example, trimethylamine, diethylamine, triethylamine, Di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine, triethanolamine, triisopropanolamine, etc., especially tertiary alkanolamines such as triethanolamine and triisopropanolamine It is better. In addition, any one of them may be used alone or in combination of two or more. In the positive resist composition of the present invention, the component (D) is usually in the range of 0.01 to 5.0 parts by mass based on 100 parts by mass of the (Α) component. Further, in the positive resist composition of the present invention, in order to prevent the deterioration of the sensitivity caused by the addition of the component (D), or to improve the shape of the pattern, the storage stability of the deposit, and the like, an organic carboxyl group of any component may be further added. An acid or phosphorus oxyacid or a derivative thereof (hereinafter also referred to as a "ruthenium" component). Further, the component (D) may be used in combination with (Ε), or any of them may be used. The organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid or the like is preferred. Phosphorus oxyacid or a derivative thereof such as phosphoric acid, dibutyl phosphate, diphenyl phosphate or the like, or a derivative thereof, phosphonic acid, dimethyl phosphonate, phosphonic acid -η-butyl ester, phenyl-42- 200832067 phosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, etc., phosphinic acid, phenylphosphinic ester and other derivatives, among which It is preferred to use phosphonic acid. (E) Ingredients can be used alone or in combination. The 'E component' is in a ratio of 0. 0 1 to 5.0 parts by mass relative to the (A) component 1 enamel. φ The positive-type photoresist composition of the present invention can be further added with a blending additive, for example, an additive resin which can modify the properties of the coating film, an applicability improving agent, a dissolution inhibitor, a plasticizer, Stabilizer, and so on. Other preferred aspects of the positive-type photoresist composition of the present invention which are different from the above-mentioned (A) component, (B) component, and (C) component, for example, contain acid via the acid, and absorb heat. The exposure light base component (A') (hereinafter, also referred to as (A,) into B) used in the lithography etching is a positive resistive composition of an essential component. The positive photoresist composition of this aspect may be used without any content. That is, the (A,) component and the above (C) are light absorbing energy of light absorbing the wavelength of the exposure light source, so that even if the component (C) is not contained, it is possible. Since it is not necessary to contain the component (C), it is possible to heat the sublimate which is generated at a time, or a phosphinic acid such as a derivative acid such as an ester thereof, or a combination thereof, or a combination thereof, usually For the purpose that is expected, the interface coloring agent and anti-halogen agent used in the photoresist composition are good, that is, the light containing the type of the photoresist composition to increase the wavelength of the alkali dissolution source) In the same manner as the above (C), the composition of (c) has the effect that the effect of the present invention is lowered, for example, the yield of the film is deteriorated, and -43-200832067 is precipitated as a solution. (A ') component, for example, among the organic compounds exemplified in the above (A) component, a compound having a molecular structure of light capable of absorbing a wavelength of an exposure light source used for thermal lithography etching, etc. The positive photoresist composition of this aspect may further contain (A,) components and other components other than (B) components, such as the above (a) φ component, (B) component, (C) Ingredients, other optional ingredients, etc. In particular, when the component (C) is used, the (A,) component can also achieve the desired absorbance when a compound having a lower light absorption energy is used, and is preferably a positive photoresist composition of the present invention. The above components can be produced by dissolving the above organic solvent (S) (hereinafter also referred to as (S) component). (S) The component 'is soluble in the components to form a uniform solution. One or two or more kinds of known components which are conventionally used as a solvent for the photoresist composition can be appropriately selected. • Specific examples include lactones such as 'r·butyrolactone; acetone, methyl ethyl ketone, and cyclohexanone. a ketone such as methyl-η-pentanone, methyl isoamyl ketone or 2-heptanone; ethyl alcohol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, Propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether acetate (PMMEA), dipropylene glycol, or monopropylene ether of dipropylene glycol monoacetate, monoethyl ugly 'monopropyl ether' monobutyl ether Or a polyhydric alcohol such as monophenyl ether and a derivative thereof or a cyclic ether such as dioxane, or methyl lactate or lactic acid Ester (EL), methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl methoxypropionate, ethyl ethoxy propionate, etc. In 200832067, 2-heptanone, PGME A, EL, and propylene glycol monomethyl ether (PGM E) are preferred. These organic solvents may be used singly or in combination of two or more kinds. The solvent may be used singly or in the form of a mixture of two or more. The amount of the (S) component used is not particularly limited, and it may be blended with the concentration of the positive resist composition of the present invention applied to the support. The amount of liquid used, in addition to the positive-type photoresist composition of the present invention, the absorbance of the formed pupil film is compared to a commercially available enhanced chemical-type photoresist composition to a thickness of each film. The above (C) component is added in such a manner that the 〇〇nm has an amount of 0.08 or more (specific amount), and is produced by dissolving. In general, a commercially available reinforced chemical type positive resist composition, as described above, is a component obtained by blending the above-mentioned (A) component with a photoacid generator component which can be acid-based based on exposure, the photoacid generator component In order to use the same ingredients as the above (B). Therefore, the commercially available enhanced chemical type positive resist composition can produce the positive resist composition of the present invention by adding the above specific amount of the component (C). The photoresist film formed by using the enhanced chemical type positive resist composition for thermal micro-etching of the present invention, as described above, in the wavelength of the exposure light source used in the thermal micro-etching, each film thickness l 〇〇nm has an absorbance of 0.08 or more. Therefore, in the thermal lithography of the uranium engraving, when the light irradiated by the exposure light source is absorbed, heat of a temperature at which the acid generator component in the photoresist film is sufficiently acidic can be generated. Therefore, the photoresist film can form a photoresist pattern via thermal lithography etching of -45-200832067. <<Formation Method of Photoresist Pattern>> The method for forming the photoresist pattern of the present invention is included in a support, and the composition of the composition is formed by using the enhanced chemical type positive resist of thermal micro-image engraving of the present invention using HU. a step of a photoresist film (hereinafter also referred to as a photoresist film forming step), for which the photoresist film has a wavelength of 0.08 or more for each film thickness of the photoresist film of 1 〇〇 nm. The step of selectively exposing light (hereinafter referred to as 'exposure step)' and the step of developing the photoresist film to form a photoresist pattern (hereinafter also referred to as development step). The method for forming the photoresist pattern of the present invention can be carried out, for example, in the following manner. (Photoresist film forming step) In this step, first, the above-mentioned #thermolithography lithography positive resist composition of the present invention is applied onto a support using a spin coater or the like, and then 80 to 1. At 50 ° C, a pre-baked (post applied bake (PAB)) is applied for 40 to 120 seconds, preferably between 60 and 90 seconds, to form a photoresist film to produce light. Resistive laminate. The support is not particularly limited, and a conventionally known article such as a substrate for an electronic component or a material having a specific wiring pattern formed thereon can be used. More specifically, for example, a substrate made of a metal such as a germanium wafer, copper, chromium, iron or aluminum, or a substrate made of glass (such as quartz glass). As the material of the wiring pattern, for example, copper, aluminum, nickel, gold, or the like can be used. Further, an inorganic-based and/or organic-based anti-reflection film may be provided on the substrate -46 - 200832067. The thickness of the photoresist film is preferably from 30 to 100 nm, more preferably from 50 to 600 nm, most preferably from 50 to 450 nm. When it is within this range, a photoresist pattern can be formed with high resolution, and an effect of sufficient resistance to etching or the like can be obtained (exposure step). Next, for the obtained photoresist layer, a film for the photoresist film is used. Light having a thickness of 10 Onm having an absorbance of 0.08 or more is selectively exposed as an exposure light source. For the exposure light source, light having a wavelength of 3 5 Onm or more is preferable, and visible light laser is more preferable, and light having a wavelength of 3 50 to 4 50 nm is particularly preferable. In general, the components contained in the chemical-type positive-type photoresist composition (for example, the above-mentioned (A) component, (B) component, etc.) are generally used in a manner that hardly absorbs or does not absorb wavelengths below 25 Onm. Light, such as a KrF excimer laser, an ArF excimer laser, or the like, or a shorter wavelength light. Therefore, when light of a wavelength of 350 mm or more is used, the influence of light on the photoresist film can be reduced, and good thermal lithography etching can be performed. For selective exposure, a commercially available exposure device can be appropriately selected in accordance with the light source used. For example, when a visible light laser is used, a nano processing apparatus NEO-5 00 (semiconductor laser having a wavelength of 40 5 nm) manufactured by Pars Corporation can be used. The device is a device that can image a semiconductor laser light that has been collected by a lens by irradiating a target (photoresist laminate). In this step, when the surface of the photoresist layer (the photoresist film side) is irradiated with light -47 to 200832067, the light is absorbed by the photoresist film. Therefore, the photoresist (light absorbing portion) generates heat, and the acid present in the component B) is generated by the heat, and is increased by the action of the acid. Therefore, the acid is generated in the subsequent developing step. Part of the photoresist film is removed, and other photoresist patterns are left unremoved. When the light is irradiated, the intensity distribution of the absorbed light is the same as that of the absorbed light. In the case, the closer to the center, the stronger the intensity of the light is at the same height as the central portion. The thermal lithography is engraved on the temperature of the heated photoresist film to a specific temperature (sensing is generated, so that it can be spotted in light) The central portion reaches the high temperature portion (hot spot) and undergoes a thermal micro-etching reaction. Since the spot diameter of the light is small, the diameter of the irradiated thin can be drawn, and as a result, a fine pattern can be formed. The sensible temperature varies depending on the type of (A) used, and is usually 140 to 300 ° C. After selective exposure, the photoresist layer is PEB at a temperature of 80 to 150 ° C. Next, carry out 40~ processing for 60~90 seconds. )) ^ Next, use an alkali developer, for example, 〇. 0 5 is preferably 0.05 to 3% by mass of tetramethylammonium hydroxide (the absorption of (A) component in the light absorbing portion of the film absorption light In the case of alkali development, a part of the photoresist film may have a heat distribution of heat, such as light, and the heat generated may also be due to a base heat temperature or higher and a diameter of the hot spot above the sensible temperature. The spot diameter of the light is in the range of micro: part or (B) component (heating after exposure), preferably 1 to 10% by mass, compared with TMAH) aqueous solution -48-200832067 for development treatment. Thus, The exposed portion of the photoresist film can be selectively dissolved and removed to form a photoresist pattern. For the photoresist pattern formed by the photoresist pattern in the above manner, the formed photoresist pattern can be used as a mask pattern. An etching treatment for etching the support. For example, when the support is used for a substrate on which an organic film (lower film) is provided on a substrate, when the organic film is etched, the organic film can be transferred to a photoresist The photoresist pattern of the film is formed on the substrate The aspect ratio of the organic film may be performed by a conventionally known etching method, in particular, dry etching is preferred, and uranium engraving is preferably performed by oxygen plasma. [Embodiment] [Example] [Example 1] (Production of Positive Photoresist Composition 1) First, the following components were mixed and dissolved to prepare a positive resist composition 1. (A) Component: Resin 1 (1 1 · 9 7 Parts by mass) and Resin 2 (5 · 13 parts by mass) • (B) Ingredients: Acid generator 1 (〇. 5 6 parts by mass) • (D) Ingredients: Triethanolamine (0 · 〇〇 9 parts by mass) • (E) Ingredients: Salicylic acid (0.019 parts by mass) • Additive: dimethylacetamide (0-463 parts by mass). • Organic solvent: PGMEA (81.8 parts by mass). • Organic solvent: 2-heptanone (63 parts by mass). -49- 200832067 • Yellow dye ΟΥ-108 (manufactured by Nippon Chemical Co., Ltd.) In the above composition, the resin 1 is πμ and m in the mass average molecular weight 8000 formed by the following formula (1 structural unit, respectively, indicating each knot in the resin榍 position: Moer %), m!/n 1=61/39. The resin 2 is a resin having a mass average molecular weight of 8,000 represented by the following formula (2), and the formula (the ratio of each structural unit in the resin, m2/n2 = 6 1 / 3 9 〇, The acid generator 1 is represented by the following formula (3): [Chemical 2 0] (1·0 parts by mass). The two kinds of resins represented by the formula (1) I unit ratio (single structural unit M2 and η2 in the form 2) (unit: mol%) My compound.

1) -50- ...(3) ...(3)200832067

(Measurement of Absorbance) The positive resist composition 1 prepared above was applied onto a 2 inch quartz substrate using a spin coater (manufactured by MIKASA), and baked at 25 ° C for 15 minutes. As a result, a sample for measurement which forms a photoresist film having a film thickness of 1 〇〇 nm was obtained. For the sample, the Shimadzu self-recording spectrophotometer UV-3 100PC manufactured by Shimadzu Corporation was used, and the absorbance of the resist film was measured under the following measurement conditions. [Measurement Conditions] The range of the measurement wavelength is 600 nm to 200 nm. The measurement range of absorbance is 0~2.5 A b s. Scanning speed: high speed. Gap width: 2.0 n m. Sampling spacing: AUTO. Basic line. Air [background correction with data on the device side], quartz substrate of new product [background correction with data on the device side]. The absorbance of the photoresist film at a wavelength of 405 nm obtained by the above measurement and the absorbance at a film thickness of 405 nm of 10 nm from the film thickness of the photoresist film were calculated. As a result, it was found that the photoresist film formed by using the above-mentioned positive-type photoresist composition -51 - 200832067 1 had an absorbance at a wavelength of 405 nm of 0.08 / a film thickness of 100 nm (confirmation of pattern formation) using a spin coating The cloth (manufactured by MIKAS A Co., Ltd.) was coated on the glass substrate treated with hexamethyldioxane (HMDS) (70 ° C, 7 minutes), and the positive resist composition 1 prepared above was applied. Further, it was heated on a hot plate at ll ° C for 90 seconds to form a photoresist film (film thickness of 100 nm). Next, in the nano-processing apparatus ΝΕΟ-500 (manufactured by Pals Industries, Inc.), the resist film was irradiated with blue laser light (semiconductor laser wavelength of 405 mm) at an output of 1 OmW. The substrate was heated at 110 ° C for 90 seconds, immersed in a 0.24% by mass aqueous solution of tetramethylammonium tetrahydrochloride for 60 seconds, washed with pure water, and then dried on a hot plate. C, 60 seconds of heating. Thereafter, the surface of the substrate was observed using a scanning electron microscope (SEM), and it was confirmed that the via holes having an inner diameter of 900 nm were arranged at equal intervals (a pitch of 1200 nm), and the via holes having an inner diameter of 3 30 nm were equally spaced ( The resulting photoresist pattern is arranged at a pitch of 600 ηπι. [Example 2] In Example 1, except that 11.0 parts by mass of yellow dye CH-1002 (manufactured by Daito Chemical Co., Ltd.) was used instead of yellow dye 〇Υ-108 (manufactured by Universal Chemical Co., Ltd.) 1 · 〇 by mass, The positive resist composition 2 was produced in the same manner as in Example 1. Using the positive resist composition 2, as in the same manner as in Example 1, the absorbance was measured in the range of -52 to 200832067, and the photoresist film formed using the positive resist composition 2 was obtained at a wavelength of 405 nm. The absorbance was 0.32 / film thickness l 〇〇 nm 〇 Further, using the positive resist composition 2 in the same manner as in Example 1, when confirming the pattern formation, it was confirmed that the via holes having an inner diameter of 900 nm were formed at equal intervals (pitch). The photoresist pattern of the 1200 nm) configuration and the via holes of the inner diameter of 330 nm are arranged at equal intervals (a pitch of 600 nm). [Comparative Example 1] In the first embodiment, 0.55 parts by mass of the yellow dye OY-GG-S (manufactured by Universal Chemical Co., Ltd.) was used instead of the yellow dye OY-108 (manufactured by Universal Chemical Co., Ltd.). In the same manner as in Example 1, a positive resist composition 3 was obtained. Using the positive resist composition 3, the measurement results of the absorbance were carried out in the same manner as in Example 1, and it was found that the photoresist film formed by using the positive resist composition 3 had an absorbance at a wavelength of 0·〇7 / film. Thick lOOnm. % Further, using the positive resist composition 3, the result of pattern formation was confirmed in the same manner as in Example 1, and it was found that the photoresist pattern was not resolved. [Comparative Example 2] In Example 1, except that 0.90 parts by mass of a yellow dye OY-105C manufactured by Universal Chemical Co., Ltd. was used instead of yellow dye 0Y-1 08 (manufactured by Universal Chemical Co., Ltd.) 1 · 〇 by mass, everything else was implemented. In the same manner as in Example 1, a positive resist composition 4 was obtained. -53- 200832067 Using the positive-type photoresist composition 4, the measurement results of the absorbance were carried out in the same manner as in Example 1, and it was found that the photoresist film formed using the positive-type photoresist composition 4 had an absorbance at a wavelength of 405 nm of 0.07. / film thickness l 〇〇 nm. Further, using the positive resist composition 4, the result of pattern formation was confirmed in the same manner as in Example 1, and it was found that the photoresist pattern was not resolved. [Comparative Example 3] In Example 1, except that 1.25 parts by mass of yellow dye 0Y-129 (manufactured by Universal Chemical Co., Ltd.) was used instead of yellow dye OY-1〇8 (manufactured by Universal Chemical Co., Ltd.), 1 part by mass, In the same manner as in Example 1, a positive resist composition 5 was obtained. Using the positive resist composition 5, the measurement results of the absorbance were carried out in the same manner as in Example 1. The photoresist film formed using the positive resist composition 5 was found to have an absorbance of 0.06 / film thickness at a wavelength of 40,511,111. 〇〇11111. Further, using the positive resist composition 5, the result of pattern formation was confirmed in the same manner as in Example 1, and it was found that the photoresist pattern was not resolved. [Comparative Example 4] In Example 1, a positive resist composition 6 was obtained in the same manner as in Example 1 except that the yellow dye OY-108 (manufactured by Universal Chemicals Co., Ltd.) was added. Using the positive resist composition 6, the results of the measurement of the absorbance were carried out in the same manner as in Example 1, and it was found that the photoresist film formed using the positive resist composition 6 had an absorbance at a wavelength of 40,011,111 of 0.〇6/ The film thickness is 1〇〇11111. • 54-200832067 Further, using the positive-type resist composition 6, the result of pattern formation was confirmed in the same manner as in Example 1, and it was found that the photoresist pattern was not resolved. From the above results, it was found that the photoresist film formed in the wavelength (405 nm) of the exposure light source had an absorbance of 0·08 / film thickness of 100 nm or more, and a photoresist pattern was formed. Further, in Comparative Examples 1 to 3 in which the formed photoresist film had an absorbance at a wavelength (405 nm) of the exposure light source of 0.07 / a film thickness of 100 nm or less, a photoresist pattern could not be formed. From the results, it was found that the formation of the photoresist pattern of Examples 1 to 2 was obtained by directly applying blue laser light to the photoresist film, that is, the result obtained by photolithography was not confirmed. The pattern formed by the thermal microlithography process. According to the present invention, it is possible to provide a thermochemical lithographic resistive composition for thermal lithography which can form a photoresist pattern via thermal lithography, and an enhanced chemical positive type using the thermal lithography etching. The method for forming the photoresist pattern of the photoresist composition is extremely industrially usable. -55-

Claims (1)

200832067 X. Application for Patent Park 1. A reinforced chemical type positive photoresist composition for thermal microlithography etching, which is an enhanced chemical type positive type for thermal lithography etching for thermal lithography lithography to form a photoresist film. a photoresist composition characterized by using the photoresist film formed by the chemico-chemical positive resist composition for thermal micro-etching, and for each of the wavelengths of the exposure light source used in the thermal micro-etching A film thickness of lOOnm has an absorbance of 0.08 or more. Φ 2. The reinforced chemical type positive resist composition for thermal lithography etching according to the first aspect of the patent application, which comprises a substrate component (A) which increases alkali solubility via an action of an acid, and is based on heat The acid generator component (B) which acts as an acid, and the dye (C) which absorbs the light of the wavelength of the exposure light source. 3. 3. The enhanced chemical type positive light for thermal lithography etching according to the first item of the patent application. a resist composition which is a substrate component (A') φ containing light which increases alkali solubility via an action of an acid and which can absorb light of a wavelength of the above-mentioned exposure light source, and an acid generator which generates an acid based on the action of heat Ingredient (B). A method for forming a photoresist pattern, comprising the steps of forming a photoresist film on a support using the enhanced chemical type positive photoresist composition for thermal micro-etching of claim 1 or 2; For the photoresist film, a step of selectively exposing light having a wavelength of 100 nm or more for each film thickness of the photoresist film of 0.08 or more, and developing the photoresist pattern to form a photoresist pattern Type of steps. 5 . A thermochemical lithography composition for lithography, which is used for thermal lithography to form a photoresist film to enhance the thermal lithography of uranium engraving - 56-200832067 A photoresist composition characterized by comprising a substrate component (A) which increases alkali solubility via an action of an acid, an acid generator component (B) which generates an acid based on a heat action, and absorbs the aforementioned heat micro The dye (C) having a wavelength of 350 nm or more of the exposure light source used for the image etching is added in an amount of 8 to 65% by mass based on the component (a). a method for forming a photoresist pattern, comprising the steps of forming a photoresist film by using a reinforced chemical type positive photoresist composition for thermal microlithography etching according to item 5 of the patent application scope, The step of selectively exposing the photoresist film using light having a wavelength of 350 nm or more, and developing the photoresist film to form a photoresist pattern. -57- 200832067 VII. Designated representative map: (1) The representative representative of the case is: None (2), the representative symbol of the representative figure is simple: No 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -3-