TW200836004A - Resist polymer, resist composition, and method of producing substrate formed with fine pattern - Google Patents

Abstract

A resist polymer which is a polymer (P) having a lactone structure (B) or a hydrophilic group (C) satisfying the following formula (1) or (2); P[B]/PH[B] ≤ 0.99…(1) P[C]/PH[C] ≤ 0.99…(2), in which P[B] is the content ratio of the lactone structure in the polymer (P), PH[B] is the content ratio of the lactone structure in the polymer (PH), P[C] is the content ratio of the hydrophilic group in the polymer (P), PH[C] is the content ratio of the hydrophilic group in the polymer (PH), The polymer (PH) indicates a polymer the molecular mass of which is large than the average molecular mass (Mw(P)) of the polymer (P) and which is separated by the Gel Permeation Chromatography, and the content ratio of the lactone structure or the hydrophilic group in the polymer indicates a ratio of the peak integration value of the lactone structure or the hydrophilic group to the total of all peak integration value of the polymer measured by NMR, is disclosed.

Description

200836004 IX. Invention Description: This application claims Japan’s special request No. 2006-350766 filed on December 27, 2006 with the Japan Intellectual Property Office and Japan’s Intellectual Property Office on February 23, 2007. Priority is claimed on 2007-04398, the entire disclosure of which is hereby incorporated by reference. [Technical field to which the invention pertains]

The present invention relates to a photoresist polymer, a photoresist composition, and a method of producing a substrate having a fine pattern. [Prior Art] In recent years, due to advances in lithography technology, a photoresist pattern formed by a manufacturing process of a semiconductor element, a liquid crystal element, or the like has rapidly progressed toward miniaturization. As a method of miniaturization, there is a method of shortening the wavelength of irradiation light. Specifically, the irradiation light is changed from the ultraviolet rays represented by the conventional g-line (wavelength··43 8 n m) and the i-line (wavelength: 365 nm) to the shorter-wavelength DUV (Deep Ultraviolet). Recently, KrF Excimer Laser (wavelength: 248 nm) lithography technology was introduced to achieve shorter wavelengths of ArF excimer laser (wavelength.193 nm) lithography and EUV excimer Laser (wavelength·· Π nm) lithography technology is under study. Further research into these immersion U 汾 technologies is also being conducted for the lithography technology of the above-mentioned technology. A ruthenium-density photoresist composition that inhibits the use of the above-mentioned neon wavelength irradiation light or electron beam, and promotes a chemically amplified photoresist composition containing photoacid generator 6 200836004f, and is currently advancing the chemistry Improvement and development of large photoresist compositions. For example, as a chemically amplified photoresist used in ArF excimer laser lithography, an acrylic polymer which is transparent to light having a wavelength of 193 nm has been attracting attention. As the acrylic polymer, for example, a (meth) acrylate having an adamantane skeleton in a vinegar portion and a polymer having a lactone skeleton white thiophene acrylate in an ester portion have been proposed (Japanese Patent Laid-Open No. Japanese Patent Laid-Open Publication No. Hei 10-274852, and the like. However, the multicomponent compound obtained by polymerizing two or more kinds of monomers has different copolymerization reactivity ratios due to the respective monomers, so that the polymerization is contained in the polymer formed at the beginning of the polymerization and the ? The group derived from the composition of each monomer is different in composition (mole fraction), and the obtained polymer has a composition distribution. The composition of the constituent unit is higher than that of the uncontrolled polymer, so that the photoresist performance (solubility, sensitivity, resolution, and depth of focus in the developer is lowered), and thus the composition distribution is being studied. & For example, it is proposed as a copolymer. As a whole, the constituent elements of the unit are evenly distributed, and the distribution of the copolymerization composition is narrowed (Japanese Patent Laid-Open No. 2〇〇5_97516, No. 8). However, the light formed by the light of the polymer is formed: the film is analyzed. Degree of Depth, Depth of Focus (D0F), and Defective Aspects of Invention The present invention aims to provide a photoresist composition capable of forming a high-resolution photoresist having excellent focus (DOF) and defects. a polymer suitable for the photoresist composition; a method for producing a substrate having a fine pattern and having a high yield and having a fine pattern; 200836004 Photoresist polymer, the polymer skeleton (B) Or a hydrophilic group The first gist of the present invention relates to an article having an acid-releasing group (A) and a lactone (C) and satisfying the following formula (I) or (2). ]/PH[B]^ 0.99-(1) P[C]/Ph[C]^〇.99-( 2) The content of the lactone skeleton in the water repellent (P);

Ph[B] · content of lactone skeleton in polymer (pH); f P [C] · content ratio of hydrophilic group in polymer (P)';

Ph[C] · The hydrazine-containing conjugate (PH) of the hydrophilic group in the polymer (Ph) is a polymer which is infiltrated by the gel, and which has a molecular weight greater than the polymerization; ·Separated from ==; and, ten Sentence knife set (MwR) The internal vinegar skeleton in the polymer, the lactone skeleton determined by the hydrophilicity R: ': The rate of use. The integral value of all the peaks of the polymer is calculated relative to the square = The invention is directed to the polymerization of a monomer having a hydrophilic group, and the monomer or group of the monomer having a hydrophilic group, and Polymerization: Solvent; Self-polymer: Light == The third purpose is to use the photoresist of the present invention containing the above-mentioned photoresist, and the depth of focus is lacking. A photoresist composition of a strange photoresist film. The production method of the present-day photo resist polymer can produce a production efficiency. 200836004 26866pif A photoresist polymer having the above characteristics is favorably produced. Moreover, the photoresist polymer and the photoresist composition of the present invention can be applied to DUV excimer laser lithography, the above-mentioned immersion lithography and electron ray lithography, especially ArF excimer laser lithography, and the immersion liquid micro Shadow. Further, according to the pattern manufacturing method of the present invention, it is possible to form a fine-precision fine resist pattern, whereby a substrate on which a fine pattern with high precision can be formed can be manufactured.

The above and other objects, features, and advantages of the present invention will become more apparent from the <RTIgt; [Embodiment] The photoresist of the present invention must have an acid-releasing group (octaester skeleton (B) or a hydrophilic group (C). &gt; Acid-off radicals (4) have a secret acid The key to the fairy (four), the dream is cracked by ^ part or all of the acid leaving group from the main molecule of the polymer: the drop has a thief leaving the base - the polymer is used as a photoresist to form the pattern two: : It can be dissolved in the test due to the action of acid, and the photo-resist polymer which can form a photoresist or a pro-base group must also have __ and the development characteristics are improved. (4) Wettability' ' By the internal structure of the skeleton, the fine composition and the substrate 9 200836004 ^uouupn TMtt: shape, photoresist complex, ~ In the present invention, Neissy A force ^ 逑 (1) or formula (2).曰月七(8) or hydrophilic group (C) must be shocked~ P[b]/Ph[B]s〇.99...(1) P[C]/PH[C]钱99 ··· (2) Polymerization The content of the hydrophilic group in the material; the collected polymer; the separation method is separated from the polymer (7) (10); and the mass average molecular weight of the polymer (p) is greater than (4), the hydrophilic group content rate To: use all the peaks of the polymer The integral value relative to the polymerization case x means that when the comparative molecular weight is less than or equal to the sum (P) of the compound (P), the polymer (Pl) and the polymer having a molecular weight greater than the poly (including more == amount) In the case of H), in the case of polymerized polymerization tt(i), it means 'compare molecular weight less than or equal to compound=! quantity average molecular weight (tetra) compound (6) and polymer trace with molecular weight greater than polygraph more = water == amount Polymerization_Package 10 200836004 In the present invention, development is carried out by including a large amount of a highly polar lactone skeleton (8) or a hydrophilic group (Q) in a polymer (pH) having a molecular weight larger than the mass average molecular weight of the polymer (p). When the polymer of the present invention is used for a photoresist composition, it is possible to form a photoresist film having high resolution and excellent depth of focus (DOF), which is excellent in resolution and reduction in defects. In terms of a photoresist composition excellent in effect, it is preferred to satisfy both formulas (1) and (2). In addition, in terms of P[B]/PH[B], P[C]/PH[C] From the viewpoint of obtaining a photoresist composition having excellent resolution and excellent defect reduction effect, it is preferable that于〇·98; from the solubility in the solvent for photoresist, it is preferable that it is 0.2 or more. 2. The content of the lactone skeleton in the polymer (P) should be explained. From the viewpoint of the sensitivity and resolution of the photoresist composition, it is preferably equal to 60 mol% (mol%); and from the dense side of the substrate, it is preferably 20 mol% or more. It should be noted that the lactone skeleton is not particularly limited in the present invention, and 1 = an internal vinegar skeleton of about 2 to 2 G or a vinegar skeleton of only 2 to 2 G, and may be non-aromatic or aromatic. Carbocyclic ester ring condensation. In addition, the hydrophilic group refers to a type of -C(CF3)2_OH, a hydroxyl group, a cyano group, a soil, a group, and an amine group. The gas (1) and the formula (2) were measured by the methods described below. 200836004 Ζόδοορίϊ (1) Determine the mass average molecular weight (Mw(p)) of the polymer (Ρ). (9) Using a standard polystyrene, a calibration curve (the relationship between dissolution time and molecular weight) is obtained. (iii) The elution time dicence of the molecular weight of the step (i) w(p) is determined in the amount of the test and the line. The solution of the polymer (P) is taken into a column, and the component which is dissolved before the step: 卞) =: 峨T is separated and collected as a polymer =), and the polymer compound which is dissolved after the dissolution time τ is obtained. The content of the lactone skeleton in (p) and the hydrophilicity of the pot (4) and the pro-step (i): / the mass average molecular weight (MW (P)) of the 4 (P) The following GPC conditions, the polystyrene obtained by GPC, the lower - ο [GPC condition I] clothing set Ding Hao S〇h company, Tosoh high-speed GPC device HL 〇 822 〇 GPC (trade name); Shodex GPC K_805L (trade name)', three series are connected in series, and the temperature is measured: 4 〇ΐ; eluate · tetrahydrofuran (hereinafter referred to as THF) 5 pattern · about 20 mg A solution obtained by dissolving a polymer (Ρ) in 5 mL of THF and filtering it with a 犋·5 μηι 犋 ; filter; 12 200836004 26866pif Flow: 1 mL/min (ml/min)

Injection amount: ol mL detector · Differential refractometer calibration line I: Dissolve about 20 mg of standard polystyrene in 5 mL of THF, filter with a membrane filter of 〇·5 μηι, and use the resulting solution. The injection into the separation column under the above conditions was carried out to determine the relationship between the elution time and the molecular weight. As the standard polystyrene, the following standard polystyrene (trade name) manufactured by Tosoh Corporation was used. F-80 (Mw = 706,000), F-20 (Mw= 190,000), F-4 (Mw = 37,900), Fl (Mw = 10,200), A-2500 (Mw = 2,630), A-500 (Mw = 682) , a mixture of 578, 474, 370, 260). Step (ii): The GPC condition is changed to the GPC condition π, and the calibration curve II (the relationship between the elution time and the molecular weight) is obtained using standard polystyrene. [GPC Condition II]

Device: Tosoh Co., Ltd., Tosoh high-speed GPC device HLC_8220GPC (trade name); Separation column: Shodex GPC K-2005 (trade name), two series in series; measuring temperature: 40 ° C;

Eluate: THF 13 200836004 ΖΟδΟΟρίΙ Sample · A solution obtained by dissolving about 120 mg of the compound (Ρ) in 5 mL of butyl hf and filtering with a membrane filter of 〇·5 μηι; :4 mL/min Injection volume: 1 mL Detector: Differential refractometer calibration line II ·· Dissolve about 120 mg of standard polystyrene in 5 mL of THF and filter with a 〇·5 μιη membrane filter Using the obtained solution, it was injected into the separated crucible under the above conditions, and the relationship between the elution time and the molecular weight was determined. As the standard polystyrene, the following standard polystyrene (trade name) manufactured by Tosoh Corporation was used. F-80 (Mw-706,000) F-20 (Mw= 190,000) F-4 (Mw-37?900) M (Mw= 10,200) A-2500 (Mw = 25630) A-500 (Mw=682, 578, a mixture of 474, 370, 260). Step (iii): In the calibration curve II, the elution time T at which the molecular weight is Mw (P) obtained in the step (i) is determined. Step (iv): a solution of the polymer (P) is injected into the separation column, and the component eluted before the dissolution time T obtained in the step (iii) is collected as a polymer (PH) according to the GPC condition, and separated and collected. The component which eluted after the dissolution time T was used as the polymer (Pi). 14 200836004 ^όδόόριί Step (V): NMR^Ht The content of the skeleton and hydrophilic group is: the integral value of the peak of the hydrophilic base of all the bones of the polymer is compared with the death of the yaws The ratio of the sum of the integral values. When the content ratio is determined by 朿 曰Μ 曰Μ NMR NMR measurement, the measurement is performed by 13 Cwmr by the measurement of H_NMR, the overlap of the Bezifeng, and the like, which cannot be determined by measurement. Find out. Γ Measurement] In the H NMR measurement, a solution of about 5 wt% (plus %) of the polymer (7) or the compound|Ph) was used using GSX-400 plastic FTNMR (trade name) manufactured by JEOL Ltd. (Listening to chloroform solution money) The dimethyl hydrazine solution was introduced into a test tube having a diameter of 5 mmcp, and accumulatively performed 64 times in the single pulse mode at an observation frequency of 4 〇〇 MHz. Incidentally, in terms of the measurement temperature, when deuterated chloroform was used as a solvent, the measurement was carried out at 40 ° C; and when deuterated monomethyl aspartate was used as a solvent, the measurement was carried out under 6 Torr. [13C-NMR measurement] In the measurement of 13 C-NMR, about 20 wt% of the polymer (P) or polymer (PH) was used in the UNITY_INOVA type FT-NMR (trade name) manufactured by vaHan Techn〇l〇gies Co., Ltd. The deuterated dimercaptosulfoxide solution was placed in a test tube with a diameter of 5 〇1!11 (?, at a measuring temperature of 60. (::, observation frequency 125]\/[1^, using the removal of internuclear austen The effect (NOE) proton decoupling method is performed 50,000 times. (Production method of polymer (P)) Next, a method for producing the photoresist polymer of the present invention will be described. 15 200836004 26866pif Photoresist polymerization of the present invention The material is obtained by having a monomer and a monomer having a lactone skeleton or a functional group. (IV) A method for polymerizing a hetero group-monomer copolymer, for example, before the start of the reaction = early body or A monomer having a hydrophilic group-monomer polymerization === group and a polymerization initiator are subjected to solution autolysis. In the base polymerization, a high molecular weight polymer is formed in the initial stage of polymerization, and then Ik is polymerized. Producing a low molecular weight polymer. In the present invention, due to the start of the reaction; There is a hydrophilic group ϋ, and the internal enthalpy system contains a large number of monomers with a _= body group _ fresh elements. The cation has a hydrophilic group t, when the reaction is opened with an acid leaving group Monomer A to A, a monomer other than a monomer having a deactivating group, can be supplied as a side with an acid-free monomer or a hydrophilic group. The monomer of the 4 = θ 丄 hydrophilic group before the start of the reaction includes a monomer having a skeleton of the internal § or a monomer having or having a hydrophilic supply of a monomer having an internal skeleton having an internal vinegar skeleton or: ♦ In time, preferably, in wt%), there are 3 wt% or 3, the total amount of monomers having a hydrophilic group (100 &lt; Wt% or more of the polymerization before the start of the reaction 16 200836004 26866pif solution The monomer having a skeleton having an internal singularity is not particularly limited as long as it can be used for a photo-blocking person. From the viewpoint of excellent adhesion, σ is preferably selected from substituted or unsubstituted. The δ_pentane ring of &amp; ^ ' dilute vinegar, monomer with substituted or unsubstituted γ_τ_ ring: At least one of the groups is particularly suitable for the use of a monomer having an unsubstituted γ-butene. Specific examples thereof include: β-mercapto acrylate-di-bromo^, lactone, 4,4·dimethyl-2 - methylene butyrolactone, &quot; propylene: oxybutyrolactone, β-methyl propyloxy alkoxymethylbutyrolactone, propylene oxy-γ-butane, 2 The methacrylic acid oxy) ethyl-diester: pantothenic acid methacrylic acid vinegar, etc. Further, as a similar soap body, a methacrylic acid valent anhydride or the like can also be mentioned. On ^ ^ can be used alone as needed, or _ or more than two groups =

In terms of the adhesion between the composition and the substrate, in the case where the polymer (Ρ) is formed in the early 兀 (10) lion 1%), the inner (four) H is greater than or equal to 3 Gm 〇 1%, and more preferably 岐 转 = 5 ^] Preferably, the degree of degree and resolution is equal to 60% of the brain of the _skeleton, and more preferably less than or equal to 50 mol%. *, 55_/. 'Into the monomer as a monomer having a hydrophilic group, no special dimethyl acrylate vinegar, and the derivatives of these monomers have a substituent such as a burnt group, a silk, a county, etc. Or 17 200836004 hexyl vinegar, bismuth (mercapto) yttrium isophthalate, adamantyl (meth) acrylate, tricyclodecyl methacrylate, dicyclopentanyl (meth) acrylate, 2 曱A monomer having a hydrophilic group such as a hydroxyl group or a carboxyl group as a substituent on a cyclic hydrocarbon group such as a polymer such as a methyl (meth) acrylate or a 2-ethyl 2 - adamantyl (meth) acrylate. Specific examples of the monomer having a hydrophilic group include (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 3_light propylene, and (meth) propylene. The acid is n-propyl propyl ester, (mercapto)acrylic acid butyl vinegar, 3-hydroxyadamantyl methacrylate, and the like. As a monomer having a hydrophilic group, it is considered from the viewpoint of the adhesion of the polymer to the substrate when used for the photoresist composition material, and among them, it is preferred that the μ-mercaptopropene-oxy-3 is cooled by the fund. Wait. The above monomers may be used singly or in combination of two or more kinds as needed. 30 mol%, more preferably 10 to 25 m〇1%.

In the case of the (meth)acrylic acid vinegar, in the case of having a carbon atom number of 6 to 2 〇 "the rectangular shape of the photoresist pattern, in the total constituent unit (100 mol 〇 / 0) of the polymer (7), The monomer having a hydrophilic group is preferably a 5- to alicyclic hydrocarbon group, and has a third position at a site where the oxygen atom is bonded, and a third stage which constitutes an ester bond of the (meth) acridine vinegar. Carbonic acid (meth) acrylate vinegar. 18 200836004 zoouuyu The above-mentioned alicyclic hydrocarbon group may be bonded directly to an oxygen atom constituting a vinegar bond of (mercapto)acrylic acid vinegar, or may be carried out via a linking group such as an alkylene group. Further, the "(meth) acrylate" includes a alicyclic hydrocarbon group having a carbon number of -20, and the -COOR group 氓 represents a third-stage hydrocarbon group, a tetrahydrofuranyl group, a tetrahydropyran which may have a substituent. The oxepanyl group or the oxepanyl acrylate is bonded to the above-mentioned alicyclic diketone (meth) acrylate either directly or via a linking group. u Soil The specific examples of the monomer having an acid-releasing group include 2-mercapto-2-adamantyl decyl acrylate and 2-ethyladamantyl methacrylate. The above monomers may be used singly or in combination of two or more kinds as needed. π From the viewpoint of sensitivity and riding degree, in the early (100 mol%) of the total composition of the polymer (p), the monomer having an acid leaving group is preferably 20 m〇l% or more. More preferably, it is greater than or equal to 25%. From the viewpoint of the adhesion to the substrate surface, etc., the specific group-monomer is preferably 60 mol% or less, more preferably 55 m〇p/〇 or less, preferably further. It is less than or equal to 50 m〇1%. The polymerization solvent is not particularly limited, and examples thereof include a chain (four) such as a bis (diethyl bond, a propylene-alcohol monomethyl amide (hereinafter also referred to as "PGME"), and a four-gas smear. ), W, Wei, etc., etc.), I (E. 夂-曰, ethyl acetate, butyl acetate, ethyl lactate, lactic acid butyl vinegar, C: two mornings) B (hereinafter also referred to as "PGMEA" h•丁议, etc., - the same (five), butanone (hereinafter also referred to as "MEK".), methyl isobutyl ketone (also referred to as "MIBK" under 19 200836004), and amine ( N,N-dimethyl ketone, dimethyl sulfoxide, etc.), sulfoxide (dimethyl hydrazine, etc.), smoke (benzene, methyl, benzene, aromatic hydrocarbons, etc.) An alicyclic formula such as smoke or cyclohexane: #), a mixed solvent of the above solvents, and the like. The polymerization is not particularly limited as the polymerization initiator, and a polymerization initiator which efficiently generates radicals by action is preferred. The above polymerization can be exemplified by: 2,2,-azobisisobutyronitrile, dimethyl-2,2, azobis; vinegar, 2,2,-azobis[2_(2-flavored wow)琳_2_基) propyl azo compound, ^ (mercapto:, 5; 3 tertiary butyl peroxy) hexane, peroxydicarbonate di('罘 butyl butyl hexyl) ester and other organic Peroxide and the like.姨 For the supply of the feed body 'polymerization initiator, you can connect: ί, should be added to the supply. After the dropwise addition is carried out, the polymerization vessel is heated to a predetermined polymerization temperature, and the initiator and the initiator mixture are added dropwise to the polymerization = dropwise addition monomer, which may be Body: In:, also referred to as "drip addition solvent" two into the "preparation solvent". ) inside the package. In the case where there is no pre-filling of the filler lysine polymerization vessel monomer or polymerization into a polymerization vessel, the container is placed. D%fl is added dropwise to the polymerization in the absence of a filler solvent. The polymerization initiator can be directly dissolved in the monomer or dissolved in a single 20: solution.

u 200836004 It can be dissolved only in the dropping solvent. Adding to the polymerization vessel; after the two initial swords are mixed in the same storage tank, the dropping polymerization container can also be mixed with the independent storage tank before being added to the container, and the soldiers are supplied to the polymerization from the independent storage tank. Monomers and polymerizations are in _==, ==. In the case of the drop acceleration, the same time can be used to drop the force. It can also be added to the end of the drop according to the speed of the monomer or the two small deniers. The acceleration of the starter is changed in multiple stages. :: Continuous addition, intermittent addition can also be carried out. ♦ mouth, the degree of dish is preferably 50~15 (TC. % of the composition of the resistance is the two days of the polymer (p) dissolved in the solvent The photoresist composition of the present invention is used as a chemically amplified photoresist, and a composition, in which a photoacid generator is further dissolved. (Photoacid generator) &quot; Photoacid generator can be used as a chemical The photoacid generator may be used singly or in combination of two or more kinds. (Nitrogen-containing compound) Chemically amplified photoresist composition. The material may include a nitrogen-containing compound, and the shape of the photoresist pattern, stability over time, and the like are further improved by including a nitrogen-containing compound, that is, the cross-sectional shape of the photoresist pattern is made closer to a rectangular shape, and in addition, although the semiconductor element is The production line is the photoresist After the light irradiation, the name 21 200836004 ζοδοοριι, the baking is performed, and then left for a few hours until the subsequent development processing, but the cross-sectional shape of the photoresist pattern is further suppressed from deteriorating upon the above placement (time). ^ (Organic: Acidic acid, phosphorus oxyacid or its derivative) ^ Chemically amplified photoresist composition may include organic carboxylic acid, phosphorus oxyacid or its derivatives (hereinafter they are collectively referred to as oxygen compounds) By including an oxygen compound, it is possible to suppress the deterioration of sensitivity due to the addition of the nitrogen-containing compound, and to increase the shape of the photoresist pattern by the stability of the time-setting step. (Additive) Adding the photoresist of the present invention The composition may include various additives such as interfacial activity other quenching substances, sensitizers, antihalation agents, storage stabilizers, defoaming, etc. as needed. The above additives may be used as long as they are well-known in the art - The amount of the above additives is not particularly high, and can be appropriately determined.

A method of manufacturing a substrate on which the thin film of the present invention is formed will be described. J Shi Xi曰曰 =, = The composition of the present invention is applied to the surface of the substrate to be processed of the mussel 4 to be formed into a desired fine pattern by a spin coater or the like. The shovel, the ruthenium coated with the photoresist composition, and the like are dried, thereby forming a photoresist on the substrate = red baking treatment (previously, the photoresist is irradiated to the photoresist film by 250 or less via the reticle) Surface ^. As the illumination light 'better than KrF quasi-i-thro laser, fine excimer laser, F2 excimer laser, 22 200836004 20δ00ρΐΓ" is particularly good for ArF excimer two shots, sound, and It can be cherished and ejected by electrons. ^ 液 液 液 , , , 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液The fine (4), (), and the developer (developing) which dissolves the exposed portion in the developer to remove the developer, may be a known developer. Operation, ^ by force = water # to the substrate for the appropriate # rinse treatment. Thus, wood's formed a photoresist pattern on the substrate to be processed. Heat treatment (post-hong) with the 』:=== substrate, pattern 2,. __Removing the photoresist, from the subsidiary to the formation is slightly limited: to illustrate the present invention, but the present invention does not "part" table * "heavy = part, § 兄 brother, then in the examples, comparative examples The compound and ^=_, the evaluation of the freshness_copolymerization, the poly-average molecular weight Mw was determined. Using the silica gel permeation chromatography to obtain the polystyrene conversion <GPC condition I> T〇S〇h System, T〇soh high speed GPC device

Shodex GPC K-805L (trade name),

200836004 ΖΟδΟΟρίΙ HLC-8220GPC (trade name); Separation column: 3 sets in series by Showa Denko; Measurement temperature: 40 ° C; Eluate · · THF; Sample: Dissolve about 20 mg of polymer (P) in 5 a solution obtained by filtering with a 0.5 μm membrane filter in ml of THF; flow rate: 1 ml/min injection amount·· 0.1 ml detector: differential refractometer calibration line I: about 20 mg of standard polyphenylene Ethylene was dissolved in 5 mi of THF, and filtered through a membrane filter of 55 μm, and the obtained solution was injected into a separation column under the above conditions to determine the relationship between the elution time and the molecular weight. Standard polystyrene uses the following standard polystyrenes (to be trade names) manufactured by Tos〇h. F-80 (Mw= 706,000) F-20(Mw= 190,000) F_4 (Mw = 37,900) Fl (Mw= 10,200) A-2500 (Mw = 2,630) A-500 (Mw two 682, 578, 474, 370, a mixture of 260). 2. Separation of the polymer The polymer (PH) having a molecular weight greater than the mass average molecular weight (Mw(P)) of the polymer (Ρ) and the mass average molecular weight of the polymer (P) is less than or equal to the mass average molecular weight of the polymer (P) 24 200836004 ΔΌουυμη (Mw(P) The polymer (pL) of the)) is isolated and collected from the polymer (P) by the following method (steps (1) to (4)). (1) The mass average molecular weight (Mw(P)) of the polymer (P) was determined according to the above GPC condition I. (2) The GPC condition was changed to the following GPC condition II, and the calibration curve 11 (the relationship between the elution time and the molecular weight) was determined using standard polystyrene. (3) In the calibration curve II, the elution time T at which the molecular weight is Mw (P) obtained in the above (1) is obtained. (4) The solution of the polymer (p) is injected into the fractionation column under the following GPC condition II, and the component eluted before the dissolution time T obtained in the above (3) is separated and collected as the pH, and the solution is separated and collected. The component eluted after time T was taken as PL. &lt;GPC Condition II> Device: Tosoh Co., Ltd., Tosoh High-speed GPC Device HLC-8220GPC (trade name) Separation column: manufactured by Showa Denko, sh〇dexGpCK_2〇〇5 (trade name), two connected temperatures are measured in series :40. (: bath effluent and butyl sample) A solution of about 12 〇mg of polymer (p) dissolved in 5 ml of thf and filtered with a membrane filter of 0·5 μm was used: 4 ml/min. :1 ml Tested as: Differential Refractometer 25 200836004 Check Line II: Dissolve about 120 mg of standard polystyrene in 5 ml of THF, filter with a 0.5 μm μm membrane filter, and use the resulting solution. The above conditions were injected into the fractionation column to determine the relationship between the elution time and the molecular weight. The standard polystyrene used the following standard polystyrene (trade name) manufactured by Tosoh. F-80 (Mw=706,000) F- 20 (Mw= 190,000) F-4 (Mw= 37,900) Fl (Mw= 10,200) A-2500 (Mw = 2,630) A-500 (Mw = 682, 578 '474, 370, 260 mixture). The composition of the material (the content ratio of each constituent unit) is analyzed by the content ratio of each constituent unit. When it can be determined by H-NMR measurement, it is determined by measurement; it cannot be borrowed due to overlapping of proton peaks and the like. In the case of the measurement by H_NMR measurement, it was determined by nc-NMR measurement. In the H-NMR measurement, gSX_4 manufactured by JEOL Ltd. was used. FT-NMR (trade name), about 5 wt% of a polymer solution (deuterated chloroform solution or deuterated dimethyl hydrazine solution) was injected into a test tube having a diameter of 5 mm (p, 400 MHz, In the single pulse mode, the correction is performed. It should be noted that when the temperature is measured, when deuterated chloroform is used as the solvent, the measurement is performed at 4 (TC); when deuterated dimethyl sulfoxide is used as the solvent, at 6 The measurement was carried out at 〇 ° C. In the measurement of 13 C-NMR, about 2 〇 wt% of the polymerized deuterated dimercapto was used using a VA_NMR (manufactured name) manufactured by Vadan Techn〇1〇gies Co., Ltd. 26200836004 UNITY-mOVA type FT_NMR (trade name) The ruthenium solution was placed in a test tube at a diameter of 5 mm (p, 5 (8) (8) times at a measurement temperature of 6 (TC, observation frequency of 125 MHz, using a proton-completed stochastic method with the inter-nuclear austenite effect (NOE) removed. The substance (P) and the poly(A) separated from the polymer (P); the internal s of the substance A) is composed of a water-based base_containing a rate, and the internal S is determined by nmr to be a skeleton or a hydrophilic group. The integral value of the peak is obtained from the ratio of the sum of the integral values of all the peaks of the polymer. The resultant polymer solution, 400 parts of the polymer solution, 2 parts of a photoacid generator triphenylsulfonium Yue trifluoromethyl sulfonate (triphenyl sulf〇nium

Mate) is mixed with the solvent PGMEA to make the polymer concentration ΐ2·5, = into a homogeneous solution, and then the film is coated with a photoresist filter having a pore size of 〇·! The composition obtained above was spin-coated on a wafer, and pre-baked at 120 ° C for 60 seconds using a hot plate to produce a photoresist film having a film thickness of 〇·3 μm: ArF excimer at a wavelength of 193 nm via a mask. After exposing the above-mentioned photoresist moon fruit to the laser, it was exposed to a hot plate at 12 (rc for 6 sec seconds, followed by f baking. Next, using 2.38 wt% of tetramethylammonium hydroxide dissolved in water at room temperature. The development was carried out, and the resist pattern was produced by washing with pure water and drying. The photoresist pattern was evaluated according to the following criteria: The defect detection device was used, and the defect of Comparative Example 1 was evaluated as 1 (10)%. Equal to 10〇/〇△• Defect is less than or equal to 70% 27 200836004 ^Kjouuyu χ : 100% ® Case Freshness @度: Based on the line and space pattern of Comparative Example i, the SEM image of the resist pattern is used to visually determine 0.16 μηι线······························································· , mixer, condenser, dropping funnel and temperature The flask was charged with 393 parts of hydrazine methacrylic acid oxybutyrolactone (monomer having a lactone skeleton, hereinafter referred to as GBLMA), and 7740 parts of ethyl lactate. The flask was placed in a hot water bath. The temperature of the water bath was raised to 8 Torr while stirring the inside of the flask. Then, the following mixture was added dropwise to the flask over 4 hours using a dropping funnel, and further kept at 8 (TC temperature for 3 hours. 2570 parts of GBLMA, 3931) Parts of 2-mercapto-2-adamantyl methacrylate (monomer having an acid-releasing group. Hereinafter referred to as MAdMA.), 1982 part of 3-hydroxyadamantyl methacrylate (having A monomer of a hydrophilic group, hereinafter referred to as HAdMA.), 12730 parts of ethyl lactate, and 1020 parts of dimercapto-2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., V601) (trade name)) The obtained reaction solution was added dropwise to a mixed solvent of methanol and water (methanol/water = 80/20 capacity ratio (volume ratio)) with stirring to obtain a white precipitate ( Precipitation of the polymer P1). After the filtration is immersed, it is again put into about 10 times relative to the above reaction solution. In a mixed solvent of methanol and water 28 200836004 ^UOUU]Jii (methanol/water = 90/10 capacity ratio), the precipitate is washed while stirring. Then, the washed precipitate is filtered to obtain a polymer wet powder. The wet powder was dried under reduced pressure at 40 ° C for about 40 hours. The obtained polymer P1 was evaluated. The results are shown in Table 1. P [B] / PH [B] satisfies the formula (1).

t The remaining polymer wet powder was put into 88,000 parts of PGMEA, and completely dissolved and passed through a nylon filter having a pore size of 0·04 μm (P'NYLON N66FILTER0.04M (trade name), manufactured by PALL Corporation, Japan) ), filtering the polymer solution. The t compound &gt; trough solution was heated under reduced pressure, and the methanol and water were removed from the crane, and PGMEA was distilled off to obtain a polymer pi having a polymer concentration of 25 wt%. At this time, the highest reached vacuum was 0/7 kPa, the highest solution temperature was 65 〇c, and the de-de-time was 8 hours. [Example 2] In a nitrogen atmosphere, a flask equipped with a nitrogen inlet, a stirrer, a condensed crying, a dropping funnel, and a thermometer was placed in 198 parts of HAdMA and 7610 parts of lactic acid ethyl acetate. The flask was placed in a hot water bath, and the temperature of the water bath was raised to the same level while stirring the inside of the sonic. ^. After the mixture, the following mixture was added dropwise to the flask over 4 hours using a dropping funnel, and the temperature was maintained at 80 ° C for 3 hours. 2856 copies of GBLMA, 3931 parts of MAdMA, 1784 parts of HAdMA, 12,860 parts of ethyl lactate, and 1062 parts of "indolyl-2,2,-azodi-g-butyrate (Wako Pure Chemical Industries, Ltd. 29 200836004 26866pif, V601 ( Product name)). The obtained reaction solution was applied to the polymer P2 in the same manner as in Example i. The evaluation result of the polymer P2 satisfies the formula (2) as shown in Table i仃 P[C]/PH[C]. . Further, using Polymer P2, a polymer P2 solution was obtained by the same operation as in Example i. [Example 3] 286.Q parts of GBl (monomer (8)) and 198.0 parts of HAdMA were placed in a flask equipped with a nitrogen inlet, a stirrer, a condenser, a dropping funnel, and a thermometer under a nitrogen atmosphere. (Monomer (c)), 7973 parts of ethyl lactate. The flask was placed in a hot water bath towel, and the flask was heated to 80 ° C while the flask was heated. Thereafter, the following mixture was added dropwise to the flask over 4 hours using a dropping funnel, and the temperature was further maintained at 80 ° C for 3 hours. 2,570 parts of GBLMA, 3931 parts of MAdMA, 1784 parts of HAdMA, 12,428 parts of lactic acid, and 1,062 parts of dimethyl-2,2 oxadiisobutyrate (Wako Pure Chemical Industries, V601 (trade name)). The obtained reaction solution was operated in the same manner as in Example 1 to give a polymer P3. The evaluation results of the polymer P3 are shown in Table 1. P[B]/PH[B] satisfies the formula (1). Further, p[C]/pH[c] satisfies the formula (7). Using the polymer P3, the solution of the polymer Ρ3 was carried out in the same manner as in Example 1. [Example 4] Except that the dimercapto group, 2 2, μ ^ from the dropwise addition solution was prepared from % ^ I / 'z &quot; azobisisobutyrate (and light ', ' / 彡, . In the same manner as in Example 1, except that the amount of use of the V60K product name) was changed to 250 parts, the polymer P4 was obtained. The physical property values of the obtained polymer P4 are shown in Table 1. P[B]/Ph[B] is full (1). Further, p[c]/pH[c] satisfies the formula (2).

Using Polymer P4, the same procedure as in the case of Convention 1 was carried out to obtain a polymer P4 solution. &lt;Comparative Example 1&gt; In a nitrogen atmosphere, 7310 parts of ethyl lactate was placed in a flask equipped with a nitrogen gas introduction port, a stirrer, a condenser, a dropping funnel, and a thermometer. The flask was placed in a hot water bath, and the temperature of the water bath was raised to 80 ° C while stirring the inside of the furnace. Thereafter, the following mixture was added dropwise to the flask using a dropping funnel using a dropping funnel, and the temperature was further maintained at 80 ° C for 3 hours. 2856 copies of GBLMA, 3931 parts of MAdMA, 1982 parts of HAdMA, 13150 parts of lactic acid, and 1,062 parts of dimercapto-2,2,-azo; isobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., V601 (trade name) ). The obtained reaction solution was operated in the same manner as in Example 1 to give the polymer P,1. The evaluation results of the polymer P'1 are shown in Table i.

200836004 Z05D0P1I shows. Ρ[Β]/ΡΗ[Β] does not satisfy the formula (1). Also, P[C]/PH[C] does not satisfy the formula (2). Using the polymer p'1, the same procedure as in Example 1 was carried out to obtain a polymer P'l solution. &lt;Comparative Example 2&gt; A full amount of 393 g of MAdMA and 7900 parts of ethyl lactate were placed in a flask equipped with a nitrogen inlet, a stirrer, a condenser, a dropping funnel, and a thermometer under a nitrogen atmosphere, and stirred. While raising the temperature of the water bath to 80 °C. Thereafter, the following mixture was added dropwise to the flask over a period of 4 hours using a dropping funnel to carry out polymerization, and further polymerization was carried out at this temperature for 3 hours. 2856 copies of GBLMA, 3538 parts of MAdMA, 1982 parts of HAdMA, 12560 parts of ethyl lactate, 250 parts of dimercapto 2,2M bismuth diisobutyric acid vinegar (Wako Pure Chemical Industries, Ltd., V-601 (trade name) )). The obtained reaction solution was operated in the same manner as in Example 1 to give the polymer P'2. The evaluation results of the polymer P'2 are shown in Table 1. P[B]/PH[B] does not satisfy the formula (1). Also, P[C]/Ph[C] does not satisfy the formula (2). Using the polymers P, 2, the same procedure as in Example 1 was carried out to obtain a polymer P'2 solution. &lt;Comparative Example 3&gt; In addition to the amount of dimercapto-2,2, azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., V601 (trade name)), the amount of use was changed to 261 parts. The polymer was obtained by operating in the same manner as in the case of 32 200836004 268 ό 6ριί m. The evaluation results of the polymer Ρ, 3, are shown in the table. Quasi]/Ρη[β] does not satisfy the formula (1). Also, P[C]/PH[C] does not satisfy the formula (2). Using the polymers P, 3, the same procedure as in Example 4 was carried out to obtain a polymer P, 3 solution. &lt;Evaluation Results&gt; When the polymer of the example was used, the photoresist film had excellent resolution, depth of focus (DOF), and defects, and a line and space pattern of 〇 μ μm was obtained with sharpness and precision. However, when the polymer of the comparative example was used, the resolution and depth of focus (DOF) of the resist film were inferior, and the sharpness of the pattern was insufficient. 200836004

[1竺 evaluation result ί pattern fresh i 〇〇〇〇X &lt;] X 〇〇〇〇X &lt;] X hydrophilic group content rate! P[C]/ I Ph[C] 1.00 0.94 I 0.97 ! 0.99 1.00 5 1.00 Ph[C] 17.8 18.5 1 17.8 L——18.3 I 1 18.3 1 P[C] ;17.8 \ 18.0 | 17.9 17.5 17.8 | 18.5 1 18.3 1 1 lactone skeleton content P[B]/ Ph[ B] 1 0-95 1.00 1 | 0.97 0.96 | 1.00 s 1 i.oo 1 Ph[B] 40.0 L 41: 〇-1 LiMj 1 40.0 1 L"g·5 丨41.0 1 P[B] 40.0 | 39.9 1 1 39.8 i | 40.9 | 39.8 40.3 ! 40.8 I Acid leaving group content P[A]/ Ph[A] 〇〇r—^ 1—1 or—^ 0.98 ! ο r—η Ph[A] 40.3 40.9 ! 40.5 | 39.9 1 L—i2—:.g... 42.2 1 40.7 1 P[A] 42.2 42.3 l-il6—, LiMJ “1:2—. 1 40.9 1 Mw/Mn r—' VD r—&lt; Cn VO (N ττ-&lt; ί Mw 5,500 5,300 1 5,400 1 9,600 5,200 9,900 1 9,700 1 |Example ί | |Example 2 1 |Example 3 1 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 200836004 Using the photoresist polymer of the present invention, it is possible to obtain a high resolution, a depth of focus (DOF) and excellent defects. Further, in the method for producing a photoresist polymer of the present invention, a photoresist polymer having the above characteristics can be produced efficiently. Γ And, the photoresist polymer of the present invention and the photoresist composition For the object, it is possible to apply =^DUV excimer laser lithography, these immersion lithography and electron ray lithography, special ArF excimer thunder ray and this immersion lithography. In addition, by using the pattern manufacturing method of the present invention, The shape of the fine photoresist can be formed in the form of a substrate that has not been in July. Money can be manufactured to form a fine pattern with high precision. The present invention has been exposed by a preferred embodiment as above. Hjt Nonfield [Illustration between drawings] 疋f is准 [Main component symbol description]

Claims (1)

200836004 ζοουυριι X, 曱 专利 patent scope: ι·- kinds of photoresist polymer 'The polymer (ρ) has an acid and an internal S skeleton (Β) or a hydrophilic group (c), and a group (Α) ( 2): 疋 述 ( (1) or Ρ Β [Β] / ΡΗ [Β] $0 · 99 ... (1) P [C] / Ph [C] ^ 0.99 - (2) (where P [B] · · Ph[B] of the internal vinegar skeleton in the polymer (P): content of the lactone skeleton in the polymer (PH), /', P[C] · hydrophilic group in the polymer (P) The content rate ΡηΜ: the content of the hydrophilic group in the polymer (PH), the polymer (PH) is a polymer collected by gel permeation chromatography, and its molecular weight is large (I) (Mw(P)); and the stomach of the shell! The internal lactic acid skeleton or the hydrophilic group in the average molecular polymer, the internal vinegar skeleton or the hydrophilic base of the hydrophilic group, the ratio of the sum of the integral values of all the peaks of the polymer. For the preparation method of the two kinds of photoresist polymers, please refer to the patent range 1st, +, and 丨, and the conjugate is a photoresist polymer such as 申 反 , ,, the method is: π π I The supply of the polymerization solvent has acid leaving; early body tt initiator to carry out solution free radical polymerization two t! (D) single 贱 has a hemp range! The silk composition comprises a manufacturing method for forming a substrate in a fine pattern as in the patent application 4. The method comprises: 36 200836004 ζοδοοριι coating the substrate as described in claim 3 a process for forming a photoresist film by blocking a composition; a process of forming a latent image by irradiating light of a wavelength of 250 nm or less to the photoresist film; and a process of developing a photoresist film having a latent image by a developing solution 0 37 200836004 ΖΟδΟΟρυ VII. Designated representative diagram · (1) The representative representative figure of this case is: None (2) The symbol of the symbol of this representative figure is simple: No. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: none