TW567405B - Positive resist composition - Google Patents

Abstract

Provided is a resist material in rectangular shape. Such resist material exhibits sufficient resolution and heat resistance when a pattern is formed during the production of a semiconductor device. The dimension of the pattern may be reduced by flow-baking it at a suitable temperature, and the flow can be easily controlled by an adequate flow rate. A positive resist composition comprises (1) an acid-decomposable resin whose solubility in an alkaline developing solution is increased when decomposed by the action of an acid and (2) a photoacid generating agent, said resin (1) consists of a resin A and an resin B which have grass transition points, before and after being decomposed by acid, satisfy the following relations. Before acid decomposition: grass transition point of A > grass transition point of B. After acid decomposition: grass transition point of A < grass transition point of B.

Description

567405 V. Description of the Invention (1) Technical Field The present invention relates to a chemically amplified positive photoresist composition for semiconductor manufacturing, and more particularly to a chemically amplified positive photoresist for heat flow, and light for contact hole formation. Resist and its pattern forming method. Prior art has hitherto used a reduced projection exposure method using light (g-line, 1-line, K rF excimer laser light). In general, the resolution R of a lens is expressed by the following formula by Rayleigh's theoretical formula. R = k [λ /(N.Α.)] Where λ is the exposure wavelength and N. A. Is the number of lens openings (Numerical Aparture). For the wafer, the incident opening angle is Θ, N. A · = si η 0. The k-series means 値 which differs depending on the photoresist, and is mostly used as a characteristic parameter having photoresist performance. With the experience of photoresist for i-line, even if the photoresist is improved, it can only be as small as 0.5. It can be seen from the above expression that the resolution must be increased to make R smaller, N. A larger, λ smaller, and k smaller. Therefore, when the current N.A. is as large as 0 · 7, k is the critical threshold reaching 0 · 5. In terms of shortening the wavelength, review 248nm of KrF excimer laser light to I93nm of ArF excimer laser light? 2 157nm of excimer laser light, but because it can actually slow the development of photoresist materials or devices used in semiconductor manufacturing, so we are looking for photoresist materials or pattern formation methods that can form finer patterns in exposure devices. The technique corresponding to the above method is disclosed in Japanese Patent Application Laid-Open No. 6-37〇71, 'Illuminating ultraviolet rays (UV) in a vacuum and heating a wafer to shape a photoresist 567405 5. Invention description (2) Shape change Flow), a modulation method of the contact aperture of a semiconductor device that can reduce the size of a photoresist pattern, but the photoresist material suitable for this is insufficiently developed. In addition, since UV irradiation in a vacuum and the wafer flow baking process are extremely complicated ', a photoresist material that achieves the same effect by only baking in the air flow is sought. However, when using a flow baking process suitable for the photoresist materials known until now, there are problems such as fast flow speed, difficult to control the pore size, or practical flow temperature (below 1 50 ° c). Problems such as full flow. In addition, Japanese Patent Application Laid-Open No. 2000-1 37329 discloses that a polymer having a malonate group in a polymer structure and a polymer that thermally decomposes below the glass transition point of the polymer to increase intermolecular interactions. It is a mixture, but the shape after flowing is not rectangular, and heat resistance may be a problem. Problems to be solved by the invention

The present invention aims to provide a photoresist composition having sufficient resolution and high heat resistance in a general pattern forming method, and an appropriate photoresist material and a pattern forming method thereof that can reduce a pattern size only by flow baking. The present invention provides a rectangular profile with sufficient resolution and heat resistance in a general pattern forming method, which can reduce the size of a pattern only at an appropriate flow baking temperature, can easily control an appropriate flow rate at an appropriate flow rate, and has a rectangular profile. Photoresist material. The inventors who solved the problem have repeatedly studied the constituent materials of the positive-type chemically amplified photoresist composition. As a result, by using the materials with the following constitutions, the invention can be described in (3). The purpose of the invention is to complete the invention. In other words, the above object is achieved by the following constitution. (1) A positive photoresist composition, which is characterized by containing (丨) an acid-decomposable resin that increases the solubility in an alkali imaging solution by the action of an acid, and (2) a photoacid generator 'and (1) ) Resin is composed of resin A and resin B whose glass transition points before and after acid decomposition can satisfy the following characteristics. Before acid decomposition: glass transition point of resin A &gt; after acid decomposition of glass transition point of resin B ... Glass transition point &lt; Resin B glass transition point. (2) A positive photoresist composition for heat flow constituted by the above (1). (3) A pattern forming method, characterized in that a photoresist film is formed on a semiconductor substrate by using the positive photoresist composition described in (1) or (2) above, and then radiation with a wavelength below 300 nm is sequentially performed The pattern exposure, heat treatment, and development treatment are performed to form a pattern larger than a desired size, the semiconductor substrate is heated to 120 to 160 ° C, and the photoresist is thermally deformed to form a pattern of a desired size. Embodiments of the invention [1] Acid-decomposable resin A resin that increases the solubility in an alkali developing solution by the action of an acid, and an alkali-soluble group having a resin can be prepared by protecting the acid-decomposable group. The alkali-soluble group is preferably a phenolic hydroxyl group or a carboxylic acid group. The protecting group of the alkali-soluble group includes an acetal group, a ketal group, an acetal ester group, a 3 -butyl ester, a 3 -butoxycarbonyl group, and the like. More preferred is an alicyclic tertiary ester group. Among these, the acetal group and the 3-butyl ester group are better. In terms of sensitivity, exposure 567,405 V. Description of the invention (4) Sensitivity change and dimensional change stability (PED) after light exposure An acetal group is preferred. Further, when the exposure light source is A rF ', when the absorption of the phenol structure is high, a 3-butyl ester group or a carboxyl acetal ester or the like is preferred. Especially for the introduction of dry polymers suitable for acid-decomposable groups suitable for K rF excimer laser and electron beam exposure, hydroxystyrenes are preferred, and the hydroxystyrenes are compatible with 3-butyl acrylate or 3-butyl methyl ester. Copolymers of acid-decomposable (meth) acrylates such as acrylates. In addition, for the purpose of adjusting the alkali solubility of the dry polymer, a non-acid-decomposable group may be introduced. The method of introduction is preferably a copolymerization method with styrenes, (meth) acrylates, ammonium (meth) acrylates, or a method of protecting the hydroxyl groups of hydroxystyrenes with non-acid-decomposable groups. Non-acid-decomposable substituents are preferably ethylamido, mesylsulfonyl, tolylsulfonyl and isopropoxy, but are not limited by these. In addition, when acid-decomposable acid-decomposable groups such as 3-butoxy, 3-butoxyoxy, tetrahydropyranyloxy, and tetrahydrofuranoxy coexist in the same main chain, the profile can be adjusted. It is better. The general formula (E) of the acid-decomposable resin suitable for K rF excimer laser exposure and electron beam irradiation is shown below. He ring-like 0-C 丨 H OH \ r5 〇 r4 (E) 567405 V. Description of the invention (5) R3 'each independently represents a hydrogen atom, a methyl group, several r3, which may be the same or different, R4 Represents a linear, branched, or cyclic carbon group with 12 substituents, an aromatic group with 6 to 18 carbons that can be substituted, or an aromatic group with 7 to 18 carbons that can have substituents. Alkyl, linear, branched or cyclic carbons of 1 to 12 are methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, 3-butyl, pentyl Group, hexyl, heptyl, 2-ethylhexyl, octyl, cyclopropyl, cyclopentyl, 1-adamantylethyl and the like. The alkyl group of R4 may have a substituent. The substituent includes a halogen atom having a hydroxyl group, fluorine, chlorine, bromine, iodine, an amine group, a nitro group, a cyano group, a carbonyl group, an ester group, an alkoxy group, a cycloalkyl group containing a heterocyclic atom, an aryloxy group, Substituent for sulfofluorenyl. Here, the carbonyl group is preferably substituted with an alkyl group (carbonyl group bonded to an alkyl group), an aromatic substituted carbonyl group (carbonyl group bonded to an aromatic group), and an ester group is substituted with an alkyl group (bonded to an alkyl group) An ester group) and an aromatic substituted ester group (an ester group bonded to an aromatic group) are preferred. The alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group, or a 3-butoxy group. Cycloalkyl includes cyclohexyl, adamantyl, cyclopentyl, cyclopropyl and the like, and those containing heteroatoms are, for example, oxazolyl. An aryloxy group, such as a phenoxy group, may have a substituent. Examples of the substituent having a sulfonyl group include an alkylsulfonyl group such as a methylsulfonyl group and an ethylsulfonyl group, and an arylsulfonyl group such as a phenylsulfonyl group. The aromatic group of R4 is, for example, a group derived from a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring. These aromatic groups may have an alkyl group as 1 ^ or a substituent described as a substituent on the ring. The aralkyl group of R4 is, for example, benzyl, phenethyl, benzopyridyl, naphthylmethyl 567405, etc. 5. Description of the invention (6). These aralkyl groups may have an alkyl group as R4 or may have a substituent described as a substituent. R5 represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, butyl, 2-butyl, 3-butyl, etc.), straight chain, Alkoxy groups with 1 to 4 carbon atoms (such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, 3-butoxy, etc.) , Acetamyloxy, methanesulfonyloxy, p-benzylsulfonyloxy, 3-butoxycarbonyloxy, 3-butoxycarbonylmethoxy, tetrahydrofuranoxy or tetrahydropyranyloxy As the group, a 3-butyl group, an ethyl fluorenyl group, an isopropoxy group, and a tetrahydrofluororanyloxy group are more preferable. R6 represents a hydrogen atom, or a linear, branched, or cyclic carbon group having 1 to 8 carbons, 6 to 12 carbons having an aromatic group which may have a substituent, or 7 to 18 carbons having a substituent. Aralkyl, to 3-butyl, 1-methylcyclohexyl, and the like. R7 and 1 ^ each represent an independent hydrogen atom, a straight chain, a branched chain or a cyclic carbon number of 1 to 8 alkyl groups, a carbon number of 6 to 12 aromatic groups, or a carbon number of 7 to 18 optionally substituted Aralkyl. These may also have substituents. Specific examples of the alkyl group, aromatic group, and aralkyl group of R6 to R8 are those in the above-mentioned carbon number range in the specific examples of R4. In the present invention, two or more acid-decomposable resins must be mixed, and the glass transition temperature (Tg) of these two resins must satisfy a specific relationship. Each acid-decomposable resin has a different glass transition temperature depending on the molecular weight, molecular weight distribution, the type or introduction amount of the acid-degradable protective group and the non-acid-degradable group, and the copolymerization component. 567405 V. Description of the invention (7) In addition, the acid-decomposable resin is decomposed and removed by its acid to remove its protective group, which produces phenolic hydroxyl or carboxyl groups, and raises the glass transition temperature. In the present invention, the glass transition point of the resin A before the acid decomposition in the two types of acid-decomposable resins a and b is Tg (A 1), the glass transition point of the resin A after the acid decomposition is Tg (A2), and the resin B before the acid decomposition When the glass transition point of the glass transition point is Tg (B1) and the glass transition point of the resin B after acid decomposition is Tg (B2), it must be satisfied as shown in Figure 1.

Tg (Al) &gt; Tg (Bl), and g (A2) &lt; Tg (B2). When the glass transition temperature Tg (A2) of resin A after acid decomposition is lower than that of resin b after the lipolytic glass transition point T g (B 2) after acid decomposition, the molecular weight of the precursor resin before the introduction of the acid-decomposable group is used. Compared with resin B, it is extremely effective in the introduction of non-acid-decomposable groups or the copolymerization of monomers having a low glass transition point. When the same non-acid-decomposable group is introduced, a glass transition point lower than that of the tree B can be obtained by increasing the introduction amount. When the introduction amount is the same, it is extremely effective to use a group having a high Tg reduction effect such as a long-chain alkyl group. When the glass transition point Tg (B 1) of the resin B before the acid decomposition is lower than that of the resin A before the acid decomposition, the introduction amount of the acid-decomposable group is increased, or a long-chain alkyl group is used. Or an acid-decomposable group having a large number of substituents is extremely effective as the introduced acid-decomposable group. The synthesis of the resin allows the monomer to be polymerized by general free radical polymerization, cationic polymerization, anionic polymerization, etc. in the presence of a solvent or in the form of a block, and if necessary, an acid-decomposable group is introduced by a polymer reaction. . In addition, 567405 V. Description of the invention (8) The monomer having an acid-decomposable group can be prepared by copolymerizing alone or with other polymerizable monomers. In addition, Tg (Al) is 5 ~ higher than Tg (Bl). 60 ° C is better, and the better is 10 ~ 50 ° C. Tg (A2) is preferably 10 ~ 70 ° C higher than Tg (Al), and more preferably 15 ~ 50 ° C. Tg (B2) is 5 ~ 7 higher than Tg (A2) (TC is better, more preferably 10 ~ 50 ° C. Tg can be measured using differential scanning calorimeter (DSC). Tg after acid decomposition is used to make acid The degradable polymer is dissolved in a suitable solvent, and acids such as hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid are added, and heated in the presence of water to remove the protective group, and the solvent is removed by water precipitation, etc., to solidify and powder It can be obtained by drying. The Tg of the polymer before the reaction can be measured when a polymer reaction is used to introduce an acid-decomposable group. The mixing ratio of the resin A and the resin B is generally a weight ratio of 10: 90 to 90: 10. It is preferably 20: 80 ~ 80: 20, and more preferably 30: 70 ~ 70: 30 °. The acid-decomposable resin used in the present invention may also contain other acid-decomposable resins other than the resin A and the tree moon purpose B. The total amount of resin a and resin B in the acid-decomposable resin is generally 10 to 100% by weight, preferably 30 to 100% by weight, and more preferably 50 to 100% by weight. Specific examples of the resin, resin structure, composition, molecular weight, and glass transition point before and after acid decomposition are shown below. -10- 567405

567405 V. Description of the invention (10)

OH

-12- 567405 V. Description of the invention (11)

-13- 567405 V. Description of the Invention (12)

-14- 567405

V. Description of the invention (ι〇

P-21

-15- 567405

V. Explanation of the invention (14) Table 1 Composition ratio of acid-decomposable polymer and glass transition point polymer 1 Before decomposition 1 After decomposition ab C Mw Tg a. B, c? Mw but g P-1 40 70 11200 9Ί 100 ref. 10300 183 P-2 20 15 65 16900 111 15 85 • 15800 148 P-3 35 15 50 8600 93 15 85 8600 132 P-4 40 5 55 21500 102 5 95 20800 171 P-5 15 20 65 3820 100 20 80 3650 117 P-6 20 10 70 17400 108 10 90 • 16800 149 P-7 30 70 — 12200 94 100 11100 184 P-8 35 65 6840 92 100 6660 172 P-9 30 70 _ 8970 121 100 • Repair 8550 175 P-10 50 50 • 1 17500 94 50 50 __ 16300 141 P-11 20 10 70 14100 142 20 10 70 13700 158 P-12 35 65 _Edit 31500 139 35 65 29700 188 P-13 40 60 3650 87 100 3410 161 P-14 25 10 65 12800 109 10 90 11600 158 P-15 25 10 65 24200 118 10 90 23500 160 P-16 25 10 65 22600 127 10 90 • 21300 157 P-17 20 60 20 13900 87 80 20 12700 136 P-18 15 65 20 8020 108 80 20 __ 7500 141 P-19 25 65 10 5850 112 90 10 __ 5730 148 P-20 25 75 12400 114 100 __ __ 11800 152 P -21 20 60 20 14400 108 80 20 13600 141 -16- 567405 i. Description of the invention (15) The combination of the resin of the present invention is, for example, the combination of P -5, P-4, P- 18, P-21, P-6, P-14, P-2, P-19, P-20, P-15, P-9, P16, P-11, etc., for P-4 Combination of P-18, P-21, P-6, P-14, P-2, P-19, P-20, P-15, P-16, P-11, etc., for P-7, P -5, P-1, P-4, P-18, P-21, P-6, P-14, P-2, P-19, P-20, P-15, P-9, P-16 , P-12, P-11, etc. For P-8, combine P-3, P-10, P-5, P-18, P-21, P-6, P-14, P-2, P -19, P-20, P-15, P-16, P-11, etc. For P-13, combine P-3, P-10, P-5, P-18, P-21, P-6 , P-14, P-2, P-19, P-20, P-11, etc. For P-17, P-3, P-5, etc., For P-9, P-16, P -11 and so on. For P-14, the combination of P-2, P-19, P-20, etc. is a better combination. The respective weight average molecular weights of the resins A and B are polystyrene conversion molecular weights (Mw) by gel permeation chromatography (GPC), preferably 2,000 to 200,000, and more preferably 4,000 to 50 7,000, the best is 7,000 ~ 30,000. If the molecular weight is more than 200,000, the solubility is poor and the resolution is lowered, while if the molecular weight is less than 2,000, the film edge tends to be uneven. In addition, a resin having a narrow molecular weight distribution (weight average molecular weight / number average molecular weight) (1.03 to 1.40) is preferable in terms of resolution. [2] Photoacid generators The compounds used in the present invention to generate acids by irradiation with active light or radiation (photoacid generators: also include compounds that generate acids with electron rays) can be appropriately selected as photoinitiator for photocationic polymerization 、 Light initiation of photoradical polymerization-17- 567405 V. Description of the invention (16) Conventional light (400 ~ 200nm UV, Far ultraviolet rays, preferably g-line, h-line, 'i-line, KrF excimer laser light), ArF excimer laser light, F 2 excimer laser light, electron beam, X-ray, molecular beam or ion beam generate acid Compounds and mixtures thereof. In addition, other photoacid generators used in the present invention include, for example, diazo iron salts, ammonium salts, iron salts, iodonium salts, phosphonium salts, selenium phosphonium salts, arsenic phosphonium salts, organic halogen compounds, organic metals / Organic halides, photoacid generators with ortho-nitrobenzyl-type protective groups, imidosulfonates and other typical photodecomposition compounds to generate acids, dimaple, diazolone maple, diazobis Grind compounds and so on. In addition, a compound in which a group that generates an acid by such light or a compound is introduced into a main chain or a side chain of a polymer is used. Alternatively, 'VNRPillai, Synthesis, (1), 1 (1 980), A. Abad et a 1, Tetrahedron Lett, (47) 4555 (1971), DHR Barton et al, J. Chem. Soc (C), 32 9 (1 970), US Pat. No. 3,799,7 78, and European Patent No. 1 26,7 1 2 are compounds which generate acid by light. Among the photoacid generators, those which are particularly effective are described below. (1) An oxazole derivative substituted with a trihalomethyl group and represented by the following formula (PAG 丨) or an S-triazole derivative represented by the general formula (PAG2). • 18- 567405

V. Description of the invention (17

N-NR ^ CVC, C (Y) 3 (PAG1) p2D2 into (Y) 3CAN human C (Y) 3 (PAG2) (wherein, it represents substituted or unsubstituted aryl, alkenyl; R2 () 2 series Represents a substituted or unsubstituted aryl group, an alkenyl group, an alkyl group, and -c (Y) 3. Y represents a chlorine atom or a bromine atom. Specifically, for example, there are the following compounds, but not limited thereto. 〇: ’C- COa CH, —CH-CH» C. J C ~ C〇3 (FACl-1) (fAQl-2)

(P / C2-5) (ΓΑ02-Ο (PAK-7) 567405 V. Description of the invention (18 α • 9

CH-CH CH = CH N 乂 N 〇aC Human N 乂 CC (PAC2-B)

CH-CH N / V Human CC (PAC2-S) N ^ N (PACZ-10) (2) An iron iodide salt represented by the following general formula (PAG3) or a phosphonium salt of the general formula (PAG4).

Ar! »Θ

Ar2 (PAG3) R ^ 3 R2 ^ -S® 2 R205 (PAM) (wherein the formulas A r 1, A 1 · 2 each independently represent a substituted or unsubstituted aryl group. R2 03, R2 (H and R205 are each independently a substituted or unsubstituted aryl group

Z · is a counter anion, for example, perfluoroalkenylsulfonic acid anions such as BF4 ·, AsF6 ·, PF6 ·, SblV, SiFr, C1CV, CFsSOr, etc., pentagas benzenesulfonate anion, naphthalene-1 -sulfonic acid anion Polycondensation polynuclear aromatic sulfonic acid anions, naphthalenesulfonic acid anions, sulfonic acid group-containing dyes, etc. are not limited by these. In addition, two of 'R2CH, R2 (H' ... ", and ^ and ^ may each be a single bond or bonded through a substituent). Specific examples include the compounds shown below, but are not limited to these. -20- 567405 V. Description of the invention (μ ^ 12 ^ 5 (PAG3-1) c4h,-

SOj (PA63-2) ΟτΆ CfaS0p 1o- (PAC3-3) (PAG3-4)

_ NH ^ Fine-s) (n) 〇7H15

Or-(η) 〇7Ηι5 h3co

{PAC3-10) OCHa _ 〇 _ OCH3 (PAG3-13) sof -21-567405 V. Description of the invention (20) f3c 丨 @ —CFaSQj0 (PAC3-12) (PAC3-13)

(PAC3-15) _ 〇- ^ θ〇Ρ ^ &gt; -Θ (PAG3-1E)

α = 3 ^ 03θ (PAG3-17) α

(PACM8)

Θ

(PAG3-19)

CF. 3δ〇3θ (PAC3-20) plant

0 C4FgS〇3 (PAG3 -21) -22- 567405

V. Description of Invention (21)

(PAG3-23)

(PAG3-24)

(PAG3-25) -23- 567405

V. Description of Invention (22)

3

(PA04-1) S0

(PAG4-5)

CH3 · K »c-^^ sdf 2) CHa

S0 F

F F

F F (PAG4-7) (PAG4-9) (PAG4-2) ν \ / ΓΓ ^ AsFe € &gt; (PAG4-3) -S® CF3S〇3e

Cf ^ SoP (PAM-8) H ^ C HOκ ^ ς

〇 CF ^ SO ^ © fCHa StF ^ CH3 (PAG4-11) e -S-CH3 CHa (PAW-10) c4h »Θ

HO (PAG4-12) 〇aH ^ 5〇?

K »cq HO HjCO c〇 Θ -24- 567405 V. Description of the invention (23 (nJC ^ Hg HO (π ^ Κ, bf4 e CH, (PAG4-15) H &lt;

KiC

0 ^ ¾ ° (PAW-16) op ό c, F17so3 Θ a o C-CI ^ —S—CHj SbFee (PAG4-17) 〇 ^ j ^ c-ch2-s0] PFe〇 (PAC4-1S)

(PAC4-23)

(PAW-25) O ^ 50? -25- 567405 V. Description of the invention (24)

-26- 567405 V. Description of the invention (25

Me〇-S-Ph; e〇3s-cf3 (PAG4-38) Ph2% S-C4Fs (PAG4-39) — one. h2 eo3s-cf3 (PAG4-40) — ^^-s-Ph2% s- &lt; Qh 03S—C4Fs (PAG4-41) CH3 (PAG4-42) ^ 〇 _ ^ _ I_Ph2 VO-CH3 {PAG4-43)- 〇 — ^^ &gt; -S-Ph2 e03S-CF3 (PAG4-44)-Ph2 e〇3S-C4F9 (PAG4-45) -27- 567405 # V. Description of the invention (26 ^ Qr CH3 (PAG4-46) S -Ph2 9〇3S * ~ 〇- Js-Ph2 03S-CF3 (PA64-47) ^ -S-Ph2 o3s-c4f3 (PA64-48) 0o3s ~ cf3 (PAG4-49) 6035-0 ^ 8, .J (PA64-50)% S-CP3 (PAG4-51) &lt; ^-s-Ph2 i-e〇3S ~ C, Fe (PAG4-52) In the above, Ph represents a phenyl group. General formula (PAG3), ( , PAG4) is known. For example, it can be described in U.S. Patent Nos. 2,8 0 7,6 4 8 and 4,24 7,473, JP 53-101,331 and the like. (3) A difluorene derivative represented by the following general formula (PAG5) or an iminosulfonic acid derivative represented by the general formula (pA (36). 〇S02-S02-Ar4 (PAG5) Human -SOfO—NAY ο (PAG6) (wherein Al · 3 and Al · 4 each independently represent a substituted or unsubstituted aryl group. R2Q6 represents a substituted or unsubstituted alkyl group or an aryl group. A series represents an Substituted or unsubstituted alkylene, alkenyl, arylene)- 28- — 567405 V. Description of the invention (27) Specific examples are shown below, but are not limited by these

CHi (PAGS-1) (PACS-2)

(PAG5-13) SOj— (PAE5 &gt; 15) -29- 567405 V. Description of the invention (28

CcJ—-ο CHn 〇 (PAG6-1) 〇 (PAG6-2) — 0 ° (PAGfi-3) 〇 (PAS € -4) N—〇-S〇2-O {PAG € -〇O hf-O -SOj- ° y ° (PAC6-6) &lt; PAfiS-5) VJO 〇N- O— S〇2-

O (PAC6-7) o (PAW-9)

O

o O (PAW-8 &gt; N-0 "S〇2- (CH ^-CH3 ° (PAM-11)

-30- 567405

567405

V. Description of the invention (30) 04 · 0. 0-CH3 (PAG6—21) 〇 〇 0 (PAG6-22) I N—0—S—CF, W 丨 丨 0 Ο

CPAG6-23) (PAG6-24) N — Ο—S —CH3 (PAG6-25)

(PAG6-26) (PAG6-27) -32- 567405 V. Description of the invention (31

(PAG6-28)

N-〇-S-C3H7 (PAG6-29)

S-C4H9 (PAG6-30) 〇

(PAG6-32) (PAG6-33) (PAG6-34) N—◦ — 1-0-- (PAG6-3I) -33- 567405

V. Description of the invention (32) (4) The diazodimaple derivative represented by the following general formula (7): 0 X, 0 H V2 II R—S—LS—R II II 0 (PAG7) (wherein, R each represents a linear, branched or cyclic alkyl group, or an aryl group which may have a substituent) Specific examples include the compounds shown below, but are not limited thereto. 〇- 〇

(PAG7-1) (PAG7-2) (PAG7-3) (PAC7-4) ο Μ〇II p 11 • s—u—s- II Π ο ο (PAG7-5) Also, you can use TK 2000- 24 1 457, JP 2000-240060, JP 2000- 2347 33, JP 2000- 1 502 17, JP 2000-1 88077, JP 2000-623 78 Agent. The addition amount of these photoacid generators is usually 0.1 to 30% by weight, preferably 0.3 to 20% by weight, and more preferably -34- 567405 based on the solid content of the composition. Description of the invention (33) is 0.5 to 10% by weight. If the added amount of the photoacid generator is less than 0.1% by weight, the sensitivity tends to decrease, and if the added amount is more than 30% by weight, the light absorption of the photoresist is too high, the profile is deteriorated, or the engineering (especially baking) range圔 Narrow, so it is not required [3] When alkali soluble resin is used in the present invention for K rF excimer laser light and electron beam exposure, the above acid-decomposable resin can be used, and it can also be used in a positive photoresist composition An alkali-soluble resin containing no acid-decomposable group, thereby improving sensitivity. The above-mentioned alkali-soluble resin containing no acid-decomposable group (hereinafter referred to as alkali-soluble resin) is preferably a resin that is soluble in alkali, such as polyhydroxystyrene, phenolic resin, and derivatives thereof. Further, a copolymer resin containing p-hydroxystyrene units may be used as long as it is alkali-soluble. Among them, poly (p-hydroxystyrene), poly (p- / m-hydroxystyrene) copolymer, poly (p-/-o-hydroxystyrene) copolymer, and poly (p-hydroxystyrene / benzene) are used. Ethylene) copolymers are preferred. In addition, such as poly (4-hydroxy-3 -methylstyrene), poly (4-hydroxy-3, 5-dimethylstyrene) poly (alkyl-substituted hydroxystyrene) resins, and the above resins A resin in which a part of the phenolic hydroxyl group is alkylated or acetylated can be used as long as it has alkali solubility. In addition, 'when hydrogenation of some phenolic cores (less than 30 mol% of all phenolic cores in the above-mentioned resins) is performed in terms of transparency, sensitivity, resolving power, and rectangular shape of the contour are preferred. The weight-average molecular weight of the soluble resin is determined by gel permeation

-35- 567405 V. Description of the invention (34) Polystyrene conversion molecular weight (M w) of analytical method (GPC), preferably 2,000 to 200,000, more preferably 4,000 to 50,000, the best Those are 7,000 ~ 30,000. In the present invention, the amount of the alkali-soluble resin containing no acid-decomposable group added to the composition is preferably 2 to 60% by weight, and more preferably the total amount of solid components in the composition. 5 to 30% by weight. [4] Acid-decomposable dissolution preventing agent In addition, in the present invention, it is possible to use an acid-decomposed group having a certain molecular weight for an alkali imaging solution decomposed by an acid action, and an acid-decomposed group introduced into a compound having a single structure, and an acid It is a low-molecular compound that acts to increase the solubility in an alkali imaging solution. It is preferred that a low-molecular compound which is increased in solubility in an alkali developer by decomposition by an acid action is introduced into a compound having a certain molecular weight with a molecular weight of 3000 or less and having a single structure, and an acid-decomposed group is introduced. Decomposes into alkali-soluble compounds. Preferred is a compound having at least two acid-decomposable groups in its structure and having at least 8 bonded atoms in addition to the acid-decomposable group at a position farthest between the decomposable groups. 10 is more preferred, 12 are the most preferred, or there are at least 3 acid-decomposable groups, and at least 9 bonds are passed through the acid-decomposable group at the furthest distance between the decomposable groups. Atom-binding compounds are more preferably 10, and most preferably 11. The preferred upper limit of the above-mentioned bonding atoms is 50, more preferably 30. In the present invention, the acid-decomposable dissolution preventing compound has three or more compounds, which are more than 36-567405. 5. Description of the invention (35) When the number of the acid-decomposable groups is four or more, or the acid has two acid-decomposable groups When the degradable groups have a certain distance or more from each other, the alkali-soluble resin can significantly improve the dissolution preventing property. In addition, the acid-decomposable dissolution preventing compound may have a structure having several acid-decomposable groups on one benzene ring, preferably a structure having one acid-decomposable group on one benzene ring. In addition, the molecular weight of the dissolution preventing compound is preferably 3,000 or less, more preferably 500 to 3,000, and most preferably 10,000 to 2500 °. The group decomposed by the acid is a silyl ether group, a cumyl group, an acetal group, Tetrahydropyranyl ether group, ethanol ether group, ethanol ester group, tertiary alkyl ether group, tertiary alkyl ester group, tertiary alkyl carbonate and the like are preferred. More preferred are tertiary alkyl ester groups, tertiary alkyl carbonates, cumyl esters, tetrahydropyranyl ether groups, and the like. [5] Organic basic compound An organic basic compound may be added to the composition of the present invention. The preferred organic basic compounds that can be used in the present invention are those which have a stronger test than phenol. Among them, nitrogen-containing test compounds. By adding an organic basic compound, the sensitivity change over time can be improved. The organic basic compound is, for example, a compound having a structure shown below. R251 Η220—N—R252 (A) (wherein R25 », RU and R252 may be the same or different carbon atoms, alkyl groups having 1 to 6 carbon atoms, amino alkyl groups having 1 to 6 carbon atoms, and carbon number Hydroxyl group of 1 to 6 or substituted or unsubstituted aryl group of 6 to 20 carbon atoms, and R251 and -37-567405 V. Description of the invention (36) R 2 5 2 can be bonded to each other to form a ring)-N- C = N *. (B) = C—Nc = C — (C) = C—N— [R255 -NC-R256 (E) where R253, R254, R255, and R256 can be the same or different carbon numbers} ~ 6) The more preferred compounds are nitrogen-containing basic compounds with two or more nitrogen atoms in different chemical environments in one molecule, especially containing substituted or unsubstituted amine groups and rings containing nitrogen atoms. Compounds which constitute both or compounds having a fluorenylamino group are preferred. Preferred examples are, for example, substituted or unsubstituted guanidine, substituted or unsubstituted amino group, substituted or unsubstituted amino alkyl pyridine, substituted or unsubstituted amino pyrrolidine, Substituted substituted miwa, substituted or unsubstituted _, substituted or unsubstituted picone, substituted or unsubstituted pyrimidine, substituted or unsubstituted: purine, substituted or unsubstituted Substituted imidazolines; Substituted oxazolines, substituted or unsubstituted pulses, substituted; = substituted aminomorpholine, taken # ^ &amp; — substituted or unsubstituted amidane Is it _ wait? The substituents of t β are amine group and amine group. Preferable amine group, "base group", "base group", "base group", "base group", "base group", "base group", "base group", "base group", "base group", "base group", "base group" (37) radical, meridian, cyano. Preferred specific examples of the nitrogen-containing basic compound include dicyclohexylmethylamine, guanidine, 1, K dimethylguanidine, 1 / 1,3,3-tetramethylguanidine, 2-aminopyridine, and 3-amino group. Pyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino- 3-methylpyridine, 2-amino-4 -methylpyridine, 2-amino-5 -methylpyridine, 2-amino-6 -methylpyridine, 3-aminoethylpyridine, 4-amine Ethylpyridine, 3-aminopyrrolidine, piperidine, N · (2-aminoethyl) piperidine, N- (2-aminoethyl) piperidine, renamino-2, 2, 6,6-tetramethylpiperidine, 4-piperidinylpiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5 · methyl Pyridazole, 5-Amino-3 -methyl-1 -p-tripyrazole, Pyrazine, 2 (Aminomethyl) -5 -methylpyridine 'Pyrimidine' 2,4 · Diamino Pyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morphine, 1,5-diazodi Ring [4,3,0] non-5-one, 1,8-diazobicyclo [5,4, 0] Undecane-7-one, 1,4-diazobicyclo [2,2,2] octane, 2,4,5-triphenylimidazole, N-methylmorpholine, N-ethyl? Tertiary morpholine derivatives such as N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethyl sulfide urea (CHMETU), Japanese Patent Laid-Open No. 11-5 25 7 5 The hindered amines described (for example, those described in the publication [00005]) are not limited to these. More specific examples are 1,5-diazobicyclo [4,3,0] non-5-one, 1,8-diazobicyclo [5,4,0] undecane-7-one , 1, 4-diazobicyclo [2, 2, 2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimide-39- 567405 5. Description of the invention (38) 3rd order morpholine, bis (1,2,2,6, 6) such as oxazoline, dicyclohexylmethylamine, pyrrole, pyrazole, imidazole, pyrimidine, pyrimidine, CHMETU, etc. -Hindered amines such as pentamethyl-4.pyridyl) decanoate. Among them, 1,5-diazobicyclo [4,3,0] non-5 · one, 1,8-diazobicyclo [5,4,0; M--alk-7-one, 1,4-diazobicyclo [2,2,2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4 · dimethylimidazoline, 〇 ^ 仙 1!] , Bis (1,2,2,6,6-pentamethyl-4-pyridyl) decanoate and dicyclohexylmethylamine are preferred. These organic basic compounds can be used alone or in combination of two or more. The amount of the organic basic compound to be used is based on the solid content of the composition, and is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight. If it is less than 0.001 wt%, the effect of adding the above-mentioned organic basic compound cannot be obtained. If it is more than 10% by weight, the sensitivity tends to decrease or the developability of the non-exposed portion tends to deteriorate. [6] Surfactant The positive photoresist composition of the present invention may contain other fluorine-based and / or silicon-based surfactants in addition to the fluorine-based polymer of the present invention. The positive-type photoresist composition of the present invention may contain a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom, or may contain two or more kinds thereof. These surfactants include, for example, JP-A-Sho 62-3666 3, JP-A-Sho 61-226 7 46, JP-A-Sho 6 1-226745, JP-A-Sho 62- 1 709 50, and JP-A-Sho 6 3 -No. 34540, JP 7-230 1 65, JP 8- ^ 40- 567405 V. Description of the invention (39) 6 2834, JP 54432, JP 9-59 88, A commercially available surfactant was used directly. Commercially available surfactants include, for example, Gefton's EF301, EF3 03 (made by Shin Akita Kasei Co., Ltd.), Floraton FC430, 431 (made by Sumitomo Siriem Co., Ltd.), and Meka Method. Gram F171, F173, F176, F189, (Da Nippon Ink Co., Ltd.), Safron S-382, SCI 01, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Toronto Rolu S-3 66 (made by Dun Long Chemical Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant. The compounding amount of these surfactants is based on the solid content in the composition of the present invention. Usually, it is preferably 0.001% to 2% by weight, and more preferably 0.001% to 1% by weight. These surfactants may be added singly or in combination. Examples of other usable surfactants include polyethylene oxide, such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide cetyl ether, polyethylene oxide oleyl ether, and the like. Alkane ethers, polyethylene oxide octyl phenol ether, polyethylene oxide nonyl phenol ether and other polyethylene oxide alkyl aryl ethers, polyethylene oxide and polypropylene oxide ether blocks Copolymers, sorbitol monolaurate, sorbitol monoester vinegar, sorbitol monostearate, sorbitol monooleate, sorbitol dioleate, sorbitol mono Sorbitol such as stearic acid esters, fatty acid vinegars, polyoxoethyl sorbitol monolaurate, poly-41-567405 V. Description of the invention (4〇) Ethylene oxide sorbitol mono Polyepoxy groups of palmitate, polyethylene oxide sorbitol monostearate, polyethylene oxide sorbitol trioleate, polyethylene oxide sorbitol tristearate, etc. Nonionic surfactants such as sorbitol fatty acid esters. The compounding amount of these other surfactants is usually 2 parts by weight or less, preferably [parts by weight] of 100 parts by weight of the solid content in the composition of the present invention. [7] A compound that promotes solubility in a developing solution may include a compound having two or more phenolic OH groups that promotes solubility in a developing solution. The compound is, for example, a polyhydroxy compound. Preferred polyhydroxy compounds include phenols, resorcinol, fluorinated saccharin, 2, 3, 4-trihydroxybenzophenone, 2, 3, 4, 4, and tetrahydroxyl. Benzophenone, α, α ,, α 'ginseng (4-hydroxyphenyl) -1,3,5-tricumene, ginseng (4-hydroxyphenyl) methane, ginseng (4-hydroxyphenyl) Ethane, 1,1'.bis (4-hydroxyphenyl) cyclohexane. The chemically amplified photoresist composition of the present invention is one in which the above components are dissolved in a solvent and coated on a carrier. The solvent that can be used is diethyl chloride, cyclohexanone, cyclopentanone, 2- Heptone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol mono Methyl 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, dimethyl maple, N-methylpyrrolidone, tetrahydrofuran, etc. are preferred, and these can be used alone or in combination. -42- 567405 V. Description of the invention (41) In addition, N-methylformamide, Ν, Ν-dimethylformamide, N-methylacetamide, Ν, Ν-dimethylacetate can be mixed. High boiling point solvents such as fluorenamine, N-methylpyrrolidone, dimethyl arylene and benzyl ether are used. The above-mentioned chemically amplified composition is applied to a substrate (for example, silicon / silicon dioxide coating) used in manufacturing precision integrated circuit elements by a suitable coating method such as a spin coater or a coater. After coating, it is exposed through a predetermined mask, and baked and developed to obtain a good photoresist pattern. The developing solution of the chemically amplified positive photoresist composition of the present invention may use, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, ammonium water, and ethylamine. Primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and tetramethylammonium hydroxide Compounds, quaternary ammonium salts such as tetraethylammonium hydroxide, alkali aqueous solutions such as cyclic amines such as pyrrole and piperidine, and the like. The positive photoresist composition of the present invention is coated on a substrate to form a thin film. The film thickness of the coating film is preferably 0. 2 to 1. 2 μΐΏ. In the present invention, a commercially available inorganic or organic antireflection film may be used as necessary. As the anti-reflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon dioxide, or an organic film type made of a light absorbing agent and a polymer material can be used. The former must use equipment such as a vacuum evaporation apparatus, a CVD apparatus, and a sputtering apparatus for film formation. The organic antireflection film is, for example, a product formed from a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin, an alkali-soluble resin, and a light absorbing agent described in Japanese Patent No. 7-69 6 1 1 or U.S. Patent No. 43-567405. V. Description of the invention (42) 52946 80 The reactant between the maleic anhydride copolymer and the diamine-type light absorbing agent 'KOKAI 6-1 1 8 6 3 No. 1 contains a resin binder and methylolmelamine For thermal crosslinking agents, JP-A-Hei '6-1 1 8 6 5 6 describes an acrylic resin type antireflection film having a carboxylic acid group, an epoxy group and a light-absorbing group in the same molecule, JP-A Hei 8- A product made from methylolmelamine and a benzophenone-based light absorbing agent described in Japanese Patent Publication No. 87115, and a low molecular weight light absorbing agent added to a polyethylene glycol resin described in Japanese Patent Application Laid-Open No. 8-1 79509. In addition, the organic anti-reflection film can also use DUV30 series or DUV-40 series manufactured by Newark Sainz Co., AC-2, AC-3 manufactured by Western Lightning Corporation, and the like. The above photoresist liquid is applied to a substrate (such as a silicon / silicon dioxide coating) used in manufacturing a precision integrated circuit element (on a substrate provided with the above-mentioned antireflection film as needed) by a spinner, a roller, etc. After coating by an appropriate coating method, exposure is performed through a predetermined hood, baking is performed, and a good photoresist pattern is produced by development. Here, the exposure light source is preferably light having a wavelength of 150 nm to 250 nm. Specifically, there are KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, electron beams, and the like. After a photoresist film is formed on the semiconductor substrate by using the chemically amplified positive photoresist composition of the present invention, pattern exposure, heat treatment, and development treatment are sequentially performed by radiation with a wavelength below 300 nm, and development is performed. It is necessary to form a contact hole with a diameter of about 10nm ~ 150nm in the rear view, and make the substrate at 120 ~ 150; [6 (Heating at TC for 30 ~ 120 seconds, the photoresist can be heated by heat flow. Make the required size -44- 567405

V. Contact hole of invention description (43). For example, 80 nm in diameter can be obtained from 150 nm in diameter by heat flow. Examples The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. [Examples 1 to 8 and Comparative Examples 1 to 6] Each raw material shown in Table 2 was dissolved in 700 parts by weight of PGMEA (propylene glycol monoethyl ether acetate), and filtered through a 0.1 μm filter to prepare a photoresist solution. Each of the photoresist solutions obtained above was coated on a substrate on which a 60 nm DUV-44 (manufactured by Brewer Science) was formed on a silicon wafer using a spin coater, and baked at 90 ° C for 90 seconds to obtain A photoresist film with a film thickness of 0.76 μm. -45- 567405

V. Description of the invention (44) Table 2 Examples and polymers * Photoacid generators Other additives Comparative examples Types by weight Types by weight Types by weight Types Example 1 P-1 50 PAG-A1 3.0 Add-Al 0.2 P-2 50 Example 2 P-1 70 PAG-A2 1.5 Add-A2 0.1 P-20 30 PAG-B1 1.5 Example 3 P-7 30 PAG-A1 1.5 Add-A3 0.1 P-16 70 PAG-B1 1.5 PAG-A4 0.1 Example 4 P-13 50 PAG-A7 3.0 Add-Al 0.1 P-6 50 PAG-A4 0.2 Example 5 P-9 60 PAG-A1 1.5 Add-A2 0.2 P-16 40 PAG-B1 1.5 PAG-A4 0.1 Example 6 P-4 40 PAG-A2 2.0 Add-A3 0.1 P-11 60 PAG-A3 1.0 Example 7 P-8 50 PAG-A1 3.0 Add-Al 0.1 P-16 50 PAG-A6 0.5 Add-A2 0.1 Example 8 P-3 50 PAG-A1 3.0 Add-Al 0.1 P-5 50 PAG-A6 0.5 Add-A2 0.1 Comparative Example 1 P-8 50 PAG-A2 1.5 Add-A2 0.1 P-13 50 PAG-B1 1.5 Comparative Example 2 P-16 50 PAG-A1 1.5 Add-A2 0.2 P-11 50 PAG-B1 1.5 PAG-A4 0.1 Comparative Example 3 P-2 50 PAG-A1 3.0 Add-Al 0.2 P-9 50 Comparative Example 4 P-1 50 PAG-A1 3.0 Add-Al 0.1 P-8 50 PAG-A6 0.5 Add-A2 0.1 Comparative example 5 P-6 50 PAG-A 7 3.0 Add-Al 0.1 P-16 50 PAG-A4 0.2 Comparative Example 6 P-13 50 PAG-A1 1.5 Add-A2 0.1 P-9 50 PAG-B1 1.5 PAG-A4 0.1 * Polymer is shown in Table 1 in the specification Acid-decomposable group. -46- 567405

5. Description of the invention (45) In addition, the photoacid generator and nitrogen-containing basic compound used are shown below. The resin is an acid-decomposable resin shown in Table 1.

ch3coo PAG-A6

PAG-A7

• 〇3S

CFa -47- 567405 V. Description of the invention (46) PAG-B1 0 ^. 2-strict 0 λ ~ / Ν2

Add-A1 Add-A2

A pattern exposure was performed on the photoresist film through a 6% half-tone mask with a 248 nm KrF excimer laser phenol exposurer (NA = 0.55). After the exposure, heating was performed at HO ° C for 90 seconds, immersion in a 0.26N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsing with water for 30 seconds, and drying. The wafer thus obtained was processed on a hot plate for 90 seconds (pre-baking process). The temperature of the hot plate during the pre-baking process is referred to as a pre-baking temperature in the following. The pattern on the wafer without pre-baking treatment was observed with a scanning electron microscope, and the mask size portion of 240 nm (mask size) was an optimal exposure amount at an exposure amount of 180 nm (the first target size). The first target size in the optimal exposure amount is calculated by different pre-baking temperatures, and the optimal flow temperature (flow temperature forming a pore diameter of 1 3 Onm) and flow speed are evaluated from the first figure. In addition, the cross-sectional shape of the first target size when flowing at 130 nm was observed with a scanning electron microscope, and the lengths of △ U and Δ LR shown in Fig. 2 were measured, and (△ Ll + △ LR) / 2 was added as the amount. , Evaluation -48- 567405

V. Description of the invention (47) The shape of the hole after flow. The smaller the amount added, the better. The evaluation results are shown in Table 3. Table 3 Examples and Comparative Examples Shape before flow Optimum flow temperature Flow speed Shape after flow Example 1 ◎ 138. . ◎ Example 2 ◎ 137〇C ◎ ◎ Example 3 ◎ 140 ° C ○ ◎ Example 4 ◎ 139〇C ◎ 〇 Example 5 ◎ 140 ° C ○ ◎ Example 6 ◎ 136〇C ◎ ◎ Example 7 ◎ 138 ° C ◎ ◎ Example 8 ◎ 138 ° C ◎ 〇Comparative Example 1 X 135 ° CXX Comparative Example 2 X 150 ° C 〇X Comparative Example 3 X 141 ° CXX Comparative Example 4 X 133 ° CX 〇Comparative Example 5 134〇CXX Comparative Example 6 X 140 ° CXX The angle of the side wall of the shape before flowing to the substrate ◎ 8 8 degrees or more 86 to 88 degrees X 86 degrees or less -49- 567405 V. Description of the invention (48) Flow rate '◎ Less than 1 〇nm / ° C 〇1 0 nm / ° C ~ 1 5 nm / ° CX 1 5 η in / ° C Above flow shape (addition amount) ◎ Less than 20nm 〇20 ~ 30nm X 3 0 nm Effect The present invention can provide a rectangular profile with sufficient resolution when forming a general pattern. 'The pattern size can be reduced only at a proper flow baking temperature, and a good shape can be formed after the flow at a suitable flow baking speed. Photoresist material for controlling flow. Brief Description of Drawings Fig. 1 is a graph showing the relationship between glass transition points of resins A and B used in the present invention before and after acid decomposition. Figure 2 shows the relationship between the contact hole size (nm) and the flow baking temperature (° C) in order to calculate the flow rate and the optimal flow temperature. Fig. 3 is a typical diagram for measuring the number of photoresists ΔLl and ΔLR when calculating the amount of pore shape after the flow is evaluated. -50-

Claims (1)

567405 ____ Bulletin, &gt;) f .1.. 1 — _ _ .... VI. Patent Application No. 901 306 1 8 "Positive Photoresist Composition" Patent Case (April 24, 1992 Amendment) Six patent applications: 1. A positive photoresist composition, which includes (1) an acid-decomposable resin that increases the solubility in an alkali developing solution by the action of an acid, and (2) a photoacid generator The (1) resin is composed of resin A and resin B whose glass transition points before and after acid decomposition can satisfy the following characteristics. Before acid decomposition: glass transition point of resin A &gt; glass transition point of resin B after acid decomposition : Glass transition point of resin A &lt; glass transition point of resin B. 2. A positive photoresist composition for heat flow, comprising (1) an acid-decomposable resin that increases solubility in an alkali developing solution by an acid action, and (2) a photoacid generator, (1) The resin is composed of resin A and resin B whose glass transition points before and after acid decomposition can satisfy the following characteristics. Before acid decomposition: glass transition point of resin A &gt; glass transition point of resin B after acid decomposition: glass of resin A Transfer point &lt; Glass transition point of resin B. 3. A pattern forming method, which is characterized in that a photoresist film is formed on a semiconductor substrate by using a positive photoresist composition as described in item 1 or 2 of the patent application, and then sequentially emits radiation with a wavelength of 150 to 300 nm. Pattern exposure, heat treatment, and development treatment are performed to form a pattern larger than the required size, the semiconductor substrate is heated to 120 ~ 160 ° C, and the photoresist is thermally deformed to form a pattern of the required size. One 1 -