TW591336B - Positive photoresist composition - Google Patents

Abstract

Provided is a positive photoresist composition having lower variation of sensitivity with time, improved denseness dependency when used in the manufacture of semiconductor devices. The positive photoresist composition has sufficient sensitivity and resolution as well as little formation of the particle of the resist solution when used in the formation of the pattern of contact hole. Furthermore, the positive photoresist composition may improve the edge roughness of the resist pattern and has excellent storage stability. A positive photoresist composition comprises a specific resin, a specific additive and surfactant, a specific onium acid generating agent, and a specific solvent.

Description

9 Printed by A7 __B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (1) [Technical Field] The present invention relates to a semiconductor integrated circuit element, a photomask for integrated circuit manufacturing, a printed wiring board, and the manufacture of a liquid crystal panel Etc. The positive photoresist composition used. [Prior art] A patterning method for manufacturing electronic components such as semiconductor elements, magnetic memory cells, and integrated circuits. Since ancient times, a photoresist method using ultraviolet rays and visible light has been widely used. The photoresist is a negative type and a relatively soluble positive type in which the irradiated part is insoluble in the developing solution by light irradiation. When the negative type is more positive than the positive type, the negative type has better sensitivity. Excellent adhesion to necessary substrates and chemical resistance, so it has been the mainstream of photoresists until recent years. However, with the increase in the density and integration of semiconductor devices, in order to make the line width or spacing of the patterns extremely small and dry feed engraving when the substrate is engraved, the resistors are required to have high resolution and high dry etching resistance. Some are positive photoresist. In particular, the positive photoresist is excellent in sensitivity, resolution, and dry etching resistance, for example, by Jay Weston Rietta, Kodak, Microelectronics, Workshop, Conference Record, page 116 (1976) (JCStrieter, Kodak Micro electronics Seminar Proceedings, 116 (1976)) and other alkali-developing positive photoresist systems based on alkali-soluble phenolic lacquer resin are the current projects. In addition, in recent years, along with the multifunctionalization and advancement of electronic devices, there has been a strong demand for miniaturization of patterns for high density and high integration. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

9 / t Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (2) In other words, because the k-inch in the vertical direction of the integrated circuit is almost not reduced compared to the reduction in the horizontal size of the integrated circuit, the resist pattern In terms of width, the height ratio cannot be increased. Therefore, the dimensional change of the photoresist pattern extruded on a wafer with a complex step structure cannot be performed by miniaturizing the pattern. In addition, there are various problems associated with the reduction in the minimum size in various exposure methods. For example, when exposed by light, the interference effect of reflected light based on the substrate step has a great influence on the dimensional accuracy. In addition, in the electron beam exposure, the close-up effect produced by the back-scattering of electrons cannot make fine light. The height-to-width ratio of the resist pattern is increased. Many of these problems can be solved with multilayer photoresist systems. Multilayer photoresist systems such as solid state technology, 74 (1 98 1) [So lid State Technology, 74 (1 98 1)], and many other studies on the system have been published in other publications. Others have published a lot of research on this system. Generally speaking, the multilayer resistive method is a 3-layer resistive method and a 2-layer resistive method. The 3-layer resistive method is to coat an organic planarizing film on a stepped substrate, and superimpose an inorganic intermediate layer and a resist on it. After patterning the resist, use it as a photomask to dry-etch the inorganic intermediate layer and use the intermediate A method in which a layer is used as a photomask to pattern an organic planarization film by 02 RIE (reactive ion etching). This method basically uses the known technology, but it has been reviewed a long time ago that the related projects are extremely complicated. The intermediate layer or the organic film, the inorganic film, and the three layers of the organic film have different physical properties, and it is easy to produce in the intermediate layer. Problems with cracks or pinholes. This paper size applies to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page)

591336 A7 B7 V. Description of the invention (3) For the 3-layer resistive method, the 2-layer resistive method is a resistive body having both the properties of the 3-layer resistive method and the inorganic intermediate layer, in other words because The use of plasma-resistant resistors can control the occurrence of cracks or pinholes, and it can be simplified from 3 to 2 layers. However, for the three-layer resistive method, for the conventional resistive layer to be used as the upper resistive layer, the two-layer resistive method must develop a new resistive plasma resistance. In view of the above background, it is required to develop a positive photoresistor with oxygen plasma resistance, high sensitivity, and high resolution as an upper layer resistive body such as a two-layer resistive body method. Especially, it is required to develop an alkaline resist that does not change the current project Photoresist like the way. In addition, in the manufacture of LS I, which must be processed with ultra-fine patterns with line widths of less than half a micron, the wavelength used by the exposure device used for photolithography is shortened, and the current KrF excimer laser light, ArF excimer laser light. In this short-wavelength lithography, a resistive system is generally called a chemically amplified type. Among them, when using ArF excimer laser light, it is not appropriate to introduce a phenol structure into the binder resin of the main component of the barrier in terms of the optical transparency of the film. Generally, a tertiary ester containing a 3 -butyl ester or the like is used. -Resin polymers such as alkyladamantyl esters, THP protectors of carboxylic acids, etc., which use the structure of acid decomposition to generate carboxylic acids as image formation sites, are used as adhesives. S 1 -containing polymers containing transparent image-forming sites in A rF excimer laser light, for example, JP-A No. 8-1 60623, JP-A No. 1 0-324748, JP-A No. 1 1-60 733, JP-A No. 1 Revealed 1-60 734. Furthermore, it is disclosed in SPIE, Vol. 3678, and 241 that it is used in acid-decomposable esters. 5- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back first) Fill out this page again), 11 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 591336 A7 B7 V. Description of the invention (4) (Please read the precautions on the back before filling this page) The end contains ginseng (trimethylsilyl group) ) Chemically amplified resist for silylethyl ethylene polymers, disclosed in SPIE, Vol. 3678, Item 241 and Item 562 using acid-decomposable esters containing trimethylbis (trimethylsilyl) disin Chemically Amplified Resistors for Alkyl Methyl Propyl Ethylene Polymers. These resistors have various points to be improved as described below. For example, those who have excellent resolution in the processing of ultra-fine patterns, but their stability over time still needs improvement. In addition, in the preparation of the body fluid, the compatibility with the photoacid generator is poor, turbidity occurs, or insoluble matter is precipitated over time, resulting in the problem of stability over time. In addition, there is also a problem with the correlation between density and density in the above technology. Recent devices tend to have various performances because of various patterns. One is sparse correlation. There are dense lines in the device, patterns with gaps wider than the lines, and isolated lines. Therefore, it is extremely important to have a system capable of resolving various lines with high reproducibility. However, it is extremely difficult to reproduce various lines by an optical factor, and a solution by a resistor is currently unclear. Especially, the performance difference between the isolated pattern and the dense pattern in the resistance system containing the above resin is extremely significant, and it is required to improve the printing by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, for the purpose of forming a fine line width in the manufacture of semiconductor devices, additional requirements are required. The miniaturization of the metal used for the electrodes of semiconductor devices to the surface of the semiconductor surface through holes, that is, the contact holes, requires a suitable positive photoresist composition. Until now, it was completely unknown what kind of resistive material would be used to make tiny contact holes. It can be seen that a resistor having a fine line width is not suitable for use in a contact hole. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7_ V. Description of the invention (5) In addition, it is necessary to maintain the stability of body fluids Improvements. For example, if the chemically amplified photoresist is stored in a liquid state, the resin has poor compatibility with the photoacid generator, and particles may be generated in the liquid, and the performance of the resist may be problematic. In addition, even when the resolution is excellent in ultra-fine pattern processing, rough edges (concavities and convexities) are generated on the edges of the resist pattern. Among them, the roughness of the edges is because the edges of the top and bottom of the line pattern of the resistive body are characteristic of the resistive body, and irregular changes occur in the line direction and vertical direction. Therefore, the edge has unevenness when viewed from above the pattern. [Disclosure of the invention] An object of the present invention is to provide an excellent positive-type photoresist composition required for manufacturing a semiconductor device using a specific resin. A first aspect of the present invention is to provide a positive-type photoresist composition having a small change in sensitivity over time and an excellent density correlation. A second aspect of the present invention is to provide a positive photoresist composition which has sufficient sensitivity and resolution when forming a contact hole pattern, and has less occurrence of particles in a body fluid. A third aspect of the present invention provides a positive-type photoresist composition having improved edge roughness of a resist pattern in manufacturing a semiconductor device and excellent storage stability. The object of the present invention can be achieved by combining a specific resin (component (A)) with specific various components. In other words, the present invention provides a composition having the following constitution. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

591336 A7 B7 V. Description of the invention (6) (1) A positive photoresist composition characterized by using a compound containing (A) an acid generated by active light or radiation, (B) having the following general formula (I) A resin having a partial structure as shown in the figure, which can increase the solubility to an alkali developer by acid action, (C) an organic test compound, and (D) a fluorine-based surfactant and / or a silicon-based interface. Agent and at least one of formula (I) among nonionic surfactants

c-〇-C

(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where m is an integer from 1 to 6 in general formula (I); R1 and R2 are each Represents an alkyl group or a cyclic alkyl group, or R1 and R2 are bonded to each other to form a cyclic alkyl group; R3 and R4 each represent a hydrogen atom, an alkyl group or a cyclic courtyard group, or R3 and R4 are bonded to each other to form a cyclic alkane R5 to R7 each represent an alkyl group, a cyclic alkyl group, an aryl group, a trialkylsilyl group, or a trialkylsilyloxy group; (2) the positive-type photoresist composition according to the above (1), Among them, the resin (A) that increases the solubility in an alkali developer by the action of an acid contains a repeating unit represented by the following general formula (II). General formula (II) -ch2-c ίΓ 〇 ο—c

Si—R6 This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 OX297 mm) 591336 A7 B7 V. Description of the invention (7) (where R1 ~ R7 and m are as defined by formula (I); Y1 Represents a hydrogen atom, a methyl group, a cyano group, or a chlorine atom; L1 represents a single bond or a divalent linking group) (3) The positive-type photoresist composition according to the above (1), wherein the The resin (A) having a large solubility in an alkali developer contains a repeating unit represented by the following general formula (III).

(Wherein R1 to R7 and m are as defined in formula (I); M represents an atomic group having 2 carbon atoms bonded and forming an alicyclic structure which may have a substituent; η represents 1 or 2; L2 Refers to a single bond or a η + 1 bonding group bonded to a carbon atom forming a ring). (4) A positive photoresist composition, which is characterized by containing a salt compound (A) represented by the general formula (PAG4) which generates an acid through active light or radiation, and (B) has the general formula ( I) A resin having a partial structure shown in FIG. 1 and increasing the solubility in an alkali developing solution by an acid action, and a resin (A) having an increasing solubility in an alkali developing solution by an acid action contains the following general formula (II) ) Repeating unit shown, (PAG4)

Rs2

Rs1 ~ S —Rs3 1 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

Printed by 1T Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs 591336

A7 —-_______ B7 _ V. Description of the invention (8) (where Rs 1 ~ Rs3 each represents an independent alkyl group which may have a substituent, and an aryl group which may have a substituent; and 2 of Rs1 ~ Rs3 may each Bonded via a single bond or a substituent; Z-represents a counter ion). (5) The positive photoresist composition according to (4), wherein the salt of (A) is a compound represented by the following general formula [s I] which generates an acid by active light or radiation irradiation . [si] (Please read the notes on the back before filling in this page) .— Refer to ·, · ιτ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where Rs4 ~ Rs6 are each independently substituted alkane Group, cycloalkyl group which may have substituent, alkoxy group which may have substituent, alkoxycarbonyl group which may have substituent, fluorenyl group which may have substituent, fluorenyl group which may have substituent, nitro, Halogen atom, hydroxyl group, and carboxyl group; 1: 1 to 5 m · 0 to 5 η: 0 to 5 1 + m + η-1, Rs4 represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, Substitutable alkoxy group, substitutable alkoxycarbonyl group, substitutable fluorenyl group, substitutable fluorenyl group; X: r-so3; -10- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 591336 A7 _ B7 V. Description of the invention (9) R: Represents an aliphatic hydrocarbon group that may have a substituent, and a substituent that may have a substituent Zhifang: gastric hydrocarbon group). (6) A positive photoresist composition, characterized in that it contains (A) a compound that generates an acid by irradiation with active light or radiation, (B) has a partial structure shown in the general formula (I) above, and can be borrowed Reacted by acid ^ Resin with large solubility in alkali developer, (E) mixed solvent, containing at least one solvent of the following group A and at least one solvent of the following group B, or at least one of the following group A Solvents and solvents of the following group e, group A: propylene glycol monoalkyl ether carboxylate B group: propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate group C: τ-butyrolactone, ethylene carbonate Ester and propylene carbonate (7)-a positive photoresist composition, characterized by containing (A) a compound that generates an acid by active light or radiation, and (B) having the general formula (I) Partially structured resin that can increase the solubility in an alkali developer by the action of an acid, (E) a mixed solvent containing at least one solvent of the following group A, at least one solvent of the following group B, and at least one of the following Solvents for group C, group A: propylene glycol monoalkyl ether carboxylate B group: propylene glycol monoalkyl ether, lactic acid Esters and alkoxyalkylpropionates c group: r-butyrolactone, ethylene carbonate and propylene carbonate (8)-a type of positive photoresist composition, characterized by (A) by active light or Compounds that generate acid from radiation, -11- 'This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page}

591336 A7 B7 V. Description of the invention (10) (B) A resin having a partial structure shown in the general formula (I) above, which can increase the solubility in an alkali developing solution by the action of an acid, (E) a mixed solvent containing A mixed solvent of at least one alkyl lactate and at least one ester solvent and an alkoxyalkyl propionate. (9) A positive photoresist composition, characterized in that it contains (A) a compound that generates an acid by irradiation with active light or radiation '(B) has a partial structure represented by the general formula (I), and can be obtained by (E) A resin containing heptanol, which is a resin which increases the solubility of an alkali developer in acid action. (10) The positive photoresist composition according to (9), wherein the solvent of (E) further contains at least one kind of propylene glycol monoalkyl ether, alkyl lactate, and alkoxyalkyl propionate. (1 1) The positive photoresist according to any one of (8) to (1 0), wherein the solvent of (E) further contains at least one kind of r-butyrolactone, ethyl carbonate and propylene carbonate ester. [Embodiments of the Invention] The compounds used in the present invention will be described in detail below. [1] Compound that generates acid by active light or radiation (component (A)) The compound used in the present invention (photoacid generator) that is decomposed to generate acid by active light or radiation (photoacid generator) can be photocationically polymerized. Photo-initiator, photo-radical polymerization photo-initiator, photochromic agent for pigments, photochromic agent, or micro-resistor, etc. (400 ~ 200nm UV, especially g-line, h-line) , I-line, KrF excimer laser light), ArF excimer

-1 2-X This paper size applies Chinese National Standard (CNS) Α4 specification (210X297 mm) (Please read the precautions on the back before filling this page) — · ， 1T Printed Economy Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperatives 591336 A7 B7 V. Description of the Invention (11) Lasers, electrons, X-rays, molecular rays or ion beams generate acid compounds and select these mixtures appropriately. In addition, other compounds used in the present invention to generate acid by irradiation with active light or radiation include, for example, SIschlesinger, Photogr. Sci. Eng., 18,387 (1974), TSBal et al, Polymer, 21,423 (1 980), etc., ammonium salts described in U.S. Patent Nos. 4,069,05 5, same as 4,069,056, same as 27,992, Japanese Unexamined Patent Publication No. 3-1 40 1 40, etc., DCNecker et al, Macromolecules, 17, 2468 (1984), CSWen rt al, The, Proc. Conf. Rad Curing ASIA, p. 478 Tokyo, Oct (1988), U.S. Patent No. 4.069,05 5, and Phosphorus described in No. 4,069,056 Onium salt, JV Crivello et al, Macromoreccules, 10 (6), 1307 (1977), Chem. &Amp; Eng. News, Nov. 28, p. 31 (1988), European Patent No. 1 04, 1 43, the same 3 39,049, same as 410,201, Japanese Patent Application Laid-open No. 2-1 508 48, Japanese Patent Application Laid-open No. 2-2965 1 4 etc., JV Crivello et al, Polymer J. 17, 73 (1985), JV Crivello et al, J. Org. Chem., 43, 3055 (1978) 'WR Watt et al, J. Polymer. Sci., Polymer Chem. Ed., 22, 1789 (1984), JV. Crivello et al, Polymer

Bull ·, 14, 279 (1 985), J.V. Crivello et a 1,

Macromorecules, 14 (5), 1141 (1981) ^ JV Crivello et a 1, J. Polymer. Sci., Polymer Chem. Ed., 1 7,2877 (1 979), European Patent No. 3 70,69 3, Same as No. 161, 811-13- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1; ^^ ------ Order ------ (Please read the notes on the back first Fill out this page again) 591336 A7 B7 V. Description of the invention (12) (Please read the notes on the back before filling out this page), same as 410,201, same as 3 39,049, same as 23 3,567, same as 297,443, and same as 297,442 US Patent No. 3,092,114, US Patent No. 4,933,377, US Patent No. 4,760,013, US Patent No. 4,734,444, US Patent No. 2,83 3,827, US Patent No. 2,904,626, US Patent No. 3,604,580, US Patent No. 2,604,58, Japanese Patent Application No. 7-2823 No. 7, same as No. 8-27 1 No. 02, etc., J.V.Crive 1 1 〇eta 1, Macromorecules, 10 (6), 1307 (1977), JV Crive11o et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1 047 (1 979), etc., C. S. Wen et a 1., The, Proc. Co nf. Rad. Curing ASIA, p. 47 8 T Salts such as arsenic salts as described in okyo, oct (1 988), etc., US Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-3628, Japanese Patent Publication No. 55-32070 JP-A Sho 60-23 973 6, JP-A Sho 6 1-1 6983 5, JP-A Sho 6 1-1 69837, JP-A Sho 62-5824 1, JP-A Sho 62- 2 1 240 1 No., JP-A-Sho 63-70243, JP-A-Sho 63-2983 39, etc., K. M e 1 ereta 1, J. R ad. Curing, 13 (4), 26 (1986) TP Gill et al, Inorg.

Chem ·, 19, 3007 (1980), D. Astruc, Acc. Chem. Res ·, Printed by Employee Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 19 (12), 3 77 (1 896), JP 2-1 6 1 Organometals / organohalides described in No. 445, S. Hayase et al, J. Polymer Sci., 25, 753 (1987) 'E. Reichmanis et al, J. Polymer Chem. Ed., 23, 1 (1 98 5), QQ Zhu et al, J. Photochem., 36, 85, 39, 3.17 (1 987), B. Amit et al, -14- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 (Mm) 591336 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (13)

Tetrahedron Lett., (24) 2205 (1973) N DHR Barton et al, J. Chem. Soc., 3571 (1965), P.M. Collins et a 1, J. Chem. Soc., Perkin I, 1695 ( 1975) 'M. Rudinstein et a 1, Tet rahedon Lett, (17), 1 445 (1 975), JW Walker et a 1, J. Am. Chem. Soc., 110, 7170 (1988) ^ SC Busman et al, J. Imaging

Technol., 11 (4), 191 (1985), H.M. Houlihan et al,

Macromolecules, 21, 2001 (1988), PM Collins et al, J. Chem. Soc., Chem. Commun., 53 2 (1 972), S. Hayase et a 1, Macromolecules, 18, 1 7 9 9 (1 985), E.

Reichmanis et a 1, J. Elect rochem. Soc., Solid State Sci. Technol., 130 (6), FM Houlihan et al, Macromolecules, 21, 2001 (1988), European Patent No. 0290,750, and No. 046,083 , Same as 156,535, same as 271,851, same as 0,388,343, US patent No. 3,901,710, same as 4,181,531, Japanese Patent Application Laid-Open No. 60-1 985 38, Japanese Patent Application Laid-Open No. 5 3-1 3 3 022, etc. Photo-generating agent for o-nitrobenzyl protective group, M. TUNOOKA et a 1, Polymer Preprints Japan, 35 (8), G. Berner et a 1, J. Rad. Curing, 13 (4), W J, Mijs et a 1, Coating Technol, 55 (697), 45 (1983), Akzo. H.

Adachi et al, Polymer Preprints, Japan, 37 (3), European Patent No. 0 1 99,672, Same as 84,515, Same as 044,1 15, Same as 618,564, Same as 0101,122, U.S. Patent No. 4,371 No. 605, -15- This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

591336 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (14) Same as No. 4,431,774, JP 64- 1 8 1 43, JP 2-245756, JP 3-1 40 Typical sulfonic acid compounds such as aminosulfonic acid esters described in No. 1 09 and the like are disclosed in JP-A-Sho 3-1 03854, same as 3-1 03 85 6, and 4- 2 1 0960, etc. Diazolone mill, diazodi maple compound. In addition, these compounds that generate an acidic group by light or introduce the compound into the main or side chain of a polymer can be, for example, M. E. W ο 〇dh 〇use et al, J. Am. Chem. Soc ·, 104, 5586 (1982), SP Pappas et al, J. Imaging Sci ·, 30 (5), 218 (1986), S. Kondo et a 1, Mak rom 1. Chem., Rapid Commun., 9 , 625 (1988), Y. Yamada et al, Makromol. Chem., 152, 153, 163 (1972), JV. Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 3845 (1979) US Patent No. 3,849,137, German Patent No. 39 1 4407, JP-A-Sho 63-26653, JP-A-Sho 55-1 64824, JP-A-Sho 62-69263, JP-A-Sho 63-1 46038 The compounds described in Japanese Patent Application Laid-Open No. 63-1163452, Japanese Patent Laid-Open No. 62-1 5 3 85 3, Japanese Patent Laid-Open No. 63-1 46029, and the like. In addition, VNRPilUi, Synthesis, (1), 1 (1 980) ^ A. Abad et al, Tetrahedron Lett., (47) 4555 (1971), DHR Barton et al, J. Chem. Soc ·, (C), 329 (1970), US Pat. No. 3,799,778, and European Patent No. 1 26,7 1 2 are compounds which generate acid by light. The following describes the above-mentioned generation by active light or radiation -16- (Please read the precautions on the back before filling this page)

, 1T

This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 V. Description of the invention (15 acid compounds are particularly effective-Shuangruo, these can be used. (1) Trihalomethyl An oxazole derivative represented by the following α ~ general formula (PAG1) or an S-ergonomic derivative represented by the general formula (PAG2) >

Is —i---I ·

-I- n IN—N l ^ 'C, 〇 / C, C (Y) 3 (pag'd OO3C 乂 N and C (Y) 3 (PAG2) (wherein R2 ϋ 1 means that after taking Mangyi, which is substituted or unselected, represents a substituted or unsubstituted aryl group, and square & represents a chlorine atom or a bromine atom. Examples of the alkyl group include the following compounds and the alkenyl group restricted by this temple, R2Q2 -C (Y) 3 γ ----- (Please read the precautions on the back before filling out this page) 1-I--II ·, 1 '

Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -17- This paper size applies to the Chinese National Standard (CNS) A4 specifications (210X297 public envy 591336 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

CI — ^) -ch = ch-c ", ': c-ca3 (PAG1-1) Ό H3C CH = CH-C ", 〇: C-CC13 (PAG1-2) H3C〇- / VcH = CH-C ^ Jc-CBr3 (PAG Bu3) 0 N—N it \ v ⑻ C4H90 CH = CH-C, 〇,-cc] 3 (PAG1-4) .〇〇

CH = CH (PAG Bu 5) (PAG1-6) (Please read the precautions on the back before filling this page) i ·· N — N w C — CQ-q 、 v '口 • c / NN // 、、 c, / C —CC13 〇NN, cy

Qt > -CH = CH-C:; c-ca (PAG1-7)

CH = CH N-N CH = CH-C / C — CCU 〇 (PAG Bu 8) 18 This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 591336 A7 B7 V. Description of the invention (17) 0CH3

CC】 3 Cl Λ 1 N + N χ Ν + Ν (PAG2-1) C13C ^ N ^ I (PAG2-2) CCU

(Please read the notes on the back before filling this page) N Λ Λa3c ν cci3 (PAG2-3) N ^ N C13C ^ N ^ CC13 (PAG2-4)

(PAG2-5)

COCH3 OCH3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Cl3C ^ N ^ CCl3 (PAG2-7) -19-

CH = CH N People N Λ Λ C13C N CCU (PAG2-8) 'This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 18 α

Ρ CH = CH CH = CH N people Ncv: people n people ca3 (PAG2-9)

CI3C

N CCI3 (PAG2-10) (2) An iodine salt represented by the following general formula (PAG3), or a phosphonium salt represented by the following general formula (PAG4A).

Ar \ ΓΘZOΘ (PAG3)

Κ203 ^ S ^ sQzQ R205 (PAG4A) (wherein Ai ^ 'Ar2 represents each independently substituted or unsubstituted aryl group, and the preferred substituents are, for example, academic groups, halogenated academic groups, cycloalkyl groups, Aryl, alkoxy, nitro, carboxyl, alkoxycarbonyl, hydroxyl, thiol and halogen atoms; broad and wide represent independent substituted or unsubstituted nosyl or aryl groups; represent an anionic group Perfluoro chain alkyl sulfonic acids such as βρ4 ·, SiF6_, C104_, CF3S03_, etc. -20-Chong 6 ·, SbF6 ·, anion, pentafluorobenzene Paper standards are applicable to Chinese National Standard (CNS) A4 specifications (210 X297 mm) 2f Read the notes on the back first, then fill out this ¥ 0

591336 A7 B7 V. Description of the invention (19) Condensed polynuclear aromatic acid expanding anions such as sulfonic acid anion, naphthalene-1 -sulfonic acid anion, anthraquinone sulfonic acid anion, sulfonic acid group-containing dyes, etc., but the present invention is not limited thereto And other restrictions. Furthermore, two of R2G3, R2Q4, and R2 ° 5 and Ar1 and Ar2 may each be a single bond or bonded through a substituent.) Specific examples include the compounds shown below, but the present invention is not limited by these

Or'Or Or. 'Or. Θ

Θ

Θ

^ 12 ^ 25 (PAG3-1) c4h9 Ό) —SC ^ (PAG3-2)) Θ AsF6U (PAG3-3) SbF60 (PAG3-4) (Please read the precautions on the back before filling out this page) Wisdom of the Ministry of Economy Printed by the Employees' Cooperative of the Property Bureau-21 This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 9 5 / C 3 3 A7 B7 V. Description of the invention (20)

0 ~ ιθ_Ηί (PAG3-5) 〇-ιΘ- < (PAG3-6) GH (PAG3-7) ρΡβθ (PAG3-8) ν〇2 1Θ ~ ^) τ Ν〇2 CF3S03 θ (PAG3-9) AsF6Q ) CF3S〇3G ^ h-OCH3 PF® ^ -〇CH3 SbF60

SbF6G Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (η) 〇7Η15-^^-1Θ ~ ⑻ ° 7Ηΐ5 PP6Θ (PAG3-12) / -.rv /-ν ^ 12 ^ 25 (PAG3-13) — -22 -(Please read the notes on the back before filling this page)

This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 5 9 5 3 3 A7 B7 V. Description of the invention (21) ® (PAG3-14) pf € g

F3C ~ A — (\ ^ j ^ CF3 CF3S03G

Cl— <, / > -I. I &';-^-Cl PF, (PAG3-16) Θ (Please read the precautions on the back before filling this page)

C12H25

SbF6®

sof (PAG3-18)

PF Θ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

CF3SO3 Θ 23- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 591336 A7 B7 V. Description of the invention (22

CF3SO3 Θ 〇-

0CH3 (Please read the notes on the back before filling in this page) .1 ·· Θ

e〇3S- \ yoc ^ Us 、 1Τ (PAG3-23)

Or ©

θ 〇3s (PAG3-24) ΝΗ

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -24- This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) 591336 Α7 Β7 V. Description of the invention (23 (n) HnCs

Cl

(PAG3-26) SO

〇CH3 (Please read the notes on the back before filling out this page) ---- ---- Order --------- Line Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

V (PAC3-27) (PAG3-28) Όγ ^ Οτ (PAG3-29) 25- Θ CF3 (CF2) 3S〇3 Θ cf3 (cf2) 7so3 This paper standard applies to China National Standard (CNS) A4 specification (210 X 297 mm) 591336 A7 B7 V. Description of the invention (24 (3) The second derivative represented by the following general formula (PAG5), or the iminosulfonate derivative represented by the general formula (PAG6). 0

At3—S02-S02—Ar4 (PAG5) Λ v (PAG6) ^

A (wherein A r3 and A r4 represent independent substituted or unsubstituted aryl groups. R2 () 6 each represent independent substituted or unsubstituted alkyl or aryl groups. A represents Substituted or unsubstituted Nosinyl, Nosinyl, and Hynyl) Specific examples are the compounds shown below, but the present invention is not limited by these (please read the precautions on the back before filling this page) } Printed by the Intellectual Property Bureau ’s Consumer Cooperatives of the Ministry of Economic Affairs 26 This paper size applies the Chinese National Standard (CNS) M specification (21〇 > < 297mm) 9 5 / V 3 3

Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (25) as〇2 ~ s〇2 ~ ^ ~ ^ ci (PAG5-1) h3c so2— so2- ^ y ~ ch3 (PAG5-2) h3co so2— so2-〇ch3 (PAG5-3) h3c 乂)-so2- so2-^^ K a (PAG5-4) f3c so2— so2-^^ · * cf3 (PAG5-5) as〇2-s〇 : A (PAG5-6)

(PAG5-8) -27- This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

5 3 3 1X 9 A7 B7 V. Description of the invention (26 S〇2 一 S〇2 -ο- CH,

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Please read the notes on the back before filling this page)

(PAG5-9) so2—so2— (PAG5-10) —S02—S〇2 (PAG5-11) ^ C ^ 0 ~ S〇2 ~ S〇2_0

och3 a h3c (PAG5-12)

OCH 3

F (PAG5-13)

H. One S02 one S〇2 (PAG5-14) S02— S02— (PAG5-15)

-28- The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 591336 A7 B7 V. Description of Invention (27 0

CH〇

OCH3

cf3

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

och3 -29 (Please read the notes on the back before filling this page)

This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 591336 A7 B7 V. Description of the invention (28 〇N-0-S02-C2H5 〇 (PAG6-7) 〇N-0-S02 -〇〇 ( PAG6-8) 0

(Please read the notes on the back before filling out this page), 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

30- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 591336 A7 B7 V. Description of invention (29)

〇 F V

(Please read the notes on the back before filling this page)

、 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -31-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 9 3 A7 B7 V. Description of the invention (30 〇

ch3 (PAG6-17) 〇 H3c h3c

N — Ο-S〇2 — CF3 〇 (Please read the notes on the back before filling this page) (PAG6-18) 〇

F Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. (4) Diazodimaple derivative compounds The diazodimaple derivative compounds are represented by the following general formula (PAG7), for example. R2it-s〇2-C-S02 ~ R: -32 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (PAG7) Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 591336 A7 B7 V. Invention Explanation (31) (where R2l and R22 each represent an independent alkyl group which may have a substituent, a cycloalkyl group, and an aryl group which may have a substituent) The alkyl group is linear or branched with 1 to 20 carbon atoms. The chain alkyl group is preferably, more preferably, a linear or branched alkyl group having 1 to 12 carbon atoms. Cycloalkyl is preferably cyclopentyl or cyclohexyl. The aryl group is preferably an aryl group having 6 to 10 carbon atoms which may have a substituent. Examples of the substituent include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl, n-pentyl, n-hexyl, and n-octyl. , 2-ethylhexyl, nonyl, decyl, dodecyl, etc. alkyl, methoxy, ethoxy, propoxy, butoxy, etc. alkoxy, halogen atom, nitro, ethyl醯 基. Specific examples of the diazobis derivative compound include the following compounds. Bis (methylsulfo) diazomethane, bis (ethylsulfo) diazomethane, bis (propyl-expansive) -azomethane, bis (butyl-expanded) diazo-methane, Bis (1-methylpropylsulfo) diazomethane, bis (butylsulfo) diazomethane, bis (1-methylbutylsulfo) diazomethane, bis (heptylsulfo) ) Diazomethane, bis (octylsulfo) diazomethane, bis (nonylsulfo) diazomethane, bis (decylsulfo) diazomethane, bis (dodecylsulfo) Diazomethane, Bis (trifluoromethylsulfo) diazomethane, Bis (2-chlorobenzylsulfo) ~ Azomethyl, Bis (4-Gasthylmethylsulfo) Dicouple Azoin, bis (phenylsulfo) diazomethane, bis (4-methoxyphenylsulfo) diazomethane, bis (xylylsulfo) diazomethane, bis (3_ Methylphenylsulfo) diazomethane, bis (4-methylphenylsulfo) diazomethane, bis (2,4_dimethyl) • 33- This paper is suitable for financial standards (CNS ) A4 size (21GX297mm)-(Please read the precautions on the back first (Fill in this page)

591336 (PAG8) A7 B7 V. Description of the invention (32) phenylphenylsulfo) diazomethane, bis (2,5-dimethylphenylsulfo) diazomethane, bis (3,4 -di Methylphenylsulfonyl) diazomethane, bis (2,4,6-trimethylphenylsulfonyl) diazomethane, bis (4-fluorophenylsulfonyl) —Azomethylamine, bis (2,4-monofluorophenyl extension) diazomethane, bis (2,4,6-trifluorophenylsulfo) diazomethane, bis (4-nitrophenylsulfo) Azomethane. (5) The diazolone derivative compound The diazolone derivative compound has, for example, r211-co-c-so2-R212 represented by the following general formula (PAG8) (where R21 and R22 are each R21 and R22 in (PAG7) are synonymous. Specific examples of the diazolone derivative compound include the following compounds. Methylsulfo-phenylfluorenyl-diazomethane, ethylsulfo-phenylfluorenyl-diazomethane, methylsulfo-4-bromophenylfluorenyl-diazomethane, ethylsulfo_ 4-bromobenzyl-diazomethane, phenylsulfo-phenylfluorenyl-diazomethane, phenylsulfo-2-methylphenyl-diazomethane, phenylsulfo-3- Methylphenyl-diazomethane, phenylsulfo-4-methylphenyl-diazomethane, phenylsulfo-trimethoxyphenyl-diazomethane, phenylsulfo-4 -Methoxyphenyl-diazomethane, phenylsulfo-3-chlorophenylamidino-diazomethane, phenylsulfo-4-chlorophenyl-diazomethane, tolylsulfo- 3-chlorobenzyl-diazomethane, tolylsulfo-4-chlorophenyl-diazomethane, phenylsulfo-4-fluorophenyl-diazomethane, fluorenylsulfonyl- 4-Fluorophenyl- -34- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 591336 A7 B7 V. Description of the invention (33) Diazomethane. The addition amount of these compounds that are decomposed by active light or radiation irradiation is based on the total weight of the photoresist composition (except the coating solvent), which is usually 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight. The addition amount of these compounds that are decomposed by active light or radiation irradiation is low when the amount is less than 0.001% by weight, and if the amount is more than 40% by weight, the light absorption of the resist is too high, the appearance is not good, and The scope of the project (especially baking) is so narrow that it is not desirable. In addition, it has been found that by using the resin (B) component and a specific acid generator, the contact hole resolution and storage properties can be improved. This specific photoacid generator is an acid salt compound which generates an acid by irradiation with active light or radiation as shown in the following general formula (PAG4). (PAG4)

Rs2

Rs1 —S —Rs3 Z a (where R s 1 to R s 3 represent each independently substituted or unsubstituted academic group, substituted or unsubstituted aryl group, and R s 1 to R Two of s 3 may each be a single bond or bonded through a substituent, and Z is an anion.) Here, the generated acids are, for example, sulfonic acid, carboxylic acid, disulfoimine, and N-sulfofluorene. Imine and so on. Among them, Rs1 to Rs3 in the general formula (PAG4) represent independent alkyl groups which may have a substituent, and aryl groups which may have a substituent. -35- This paper size is applicable to China National Standard (CNS) A4 (210X297). (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 591336 A7 B7 V. Description of Invention (34)

Rsl to Rs3 are preferably aryl groups having 6 to 14 carbon atoms, alkyl groups having 1 to 8 carbon atoms, and substituted derivatives thereof. Preferred is aryl. Examples of aryl include phenyl, naphthyl, anthryl, and phenanthryl. Examples of alkyl include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, and 3-butyl. , Pentyl, hexyl, heptyl, octyl. Examples of such preferred substituents are alkyl, halogenated alkyl, cycloalkyl, aryl, alkoxy, nitro, carboxy, alkoxycarbonyl, fluorenyl, fluorenyl, hydroxy, thiol And halogen atoms. Z · is a counter anion, such as BF4 ·, AsF6 ·, PF6 ·, SbF6_, SiP, C104_, CF3S (V and other perfluoroalkanesulfonic acid anions, pentafluorobenzenesulfonic anions, naphthalene-1-sulfonic acid Anions such as polynuclear aromatic sulfonic acid anions, anthraquinone sulfonic acid anions, sulfonic acid group-containing dyes, methanesulfonic acid, and other sulfonic acids, etc., but the present invention is not limited to these. Moreover, Rsl ~ Rs3 Each of them may be a single bond or a substituent. The specific examples of the photoacid generator represented by the general formula (PAG4) are as follows (PAG4-1) to (PAG4-37). (Please read the note on the back first (Please fill in this page for more details)

, 1T

Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -36- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 5 9 5 3 3 A7 B7 V. Description of the invention (35 ^ 12 ^ 25

Of (PAG4-1)

SO θ

H3C

Of (PAG4-2) S® CH3 ch3

AsF6G (PAG4--3)

Oh

SbFe Θ (PAG4-4)

Ofs ® cf3so3 丨 Θ (PAG4-5), @ 0.8 ^ I7SO3 Θ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (PAG4-6)

F F F

SO- Θ

(PAG4-7) F F 37- (Please read the notes on the back before filling this page)

This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 9 5 3 3 A7 B7 V. Description of the invention (36 h3c 5Θ

〇c2H5 CF3S〇3G (PAG4-8)

H3CO a cf3s〇30

HO (PAG4-9) Θ CHs PF60 ch3 (PAG4-10)

(PAG4-11)

HO O ~ s9 (PAG4-12)

sof Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

(PAG4-13) CF3SO3 -38- This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) Θ (Please read the precautions on the back before filling this page)

591336 A7 B7 V. Description of the invention (37 (11) 04¾ HO (11) 04¾ (PAG4 -14) pf6 Θ bf4ch3 (PAG4-15) Θ (Please read the precautions on the back before filling out this page) ·

HO PFe θ

H3C (PAG4-16)

AsR Θ

, 1T

(PAG4-17) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

CgF17S03 (PAG4-18) -39- This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) ㊀ 591336 A7 B7 V. Description of invention (38

Or 0 II © C ~ CH ^ ~ S- CH3 ch3 (PAG4-19) 〇

SbF Θ 6 ΙΨ6Θ (PAG4-20) — ° c-CH2- S® ^) AsF € 0 (PAG4-21)

AsF, Θ

Cl (PAG4-22) ^^ c-ch2-s® ^) pf60 (PAG4-23) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy ca 〇If C-CH, (PAG4-24) 40- This paper standard applies China National Standard (CNS) A4 specification (210X297 mm)

Cl 2 ^ 25 so Θ 3 (Please read the notes on the back before filling this page)

9 yt A7 B7 V. Description of the invention (39

〇 II C-CH ^-S-(11) 04¾ (i) QH9 (PAG4-25)

PF € G

CsH17S〇3 Θ (PAG4-26)

^ 12 ^ 25

S '; 〇f (PAG4-27)

S 2CF3SO3 S 2H3C ^ = rs〇3 ch3 (PAG4-29) Θ Θ

〇) rsS Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs h3c (PAG4-30) O ~ s§ ~ fO ~ (PAG4-31)

-41 (Please read the notes on the back before filling this page)

This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 A7 B7 V. Description of the invention (40) s—ch2ci ce3 (PAG4-32)

so, 0

(PAG4-34) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -42- (Please read the notes on the back before filling this page)

This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 A7 B7 V. Description of invention (41)

Θ CFaiCF ^ ySOa

Θ CF3 (CF2) 3S03 (Please read the precautions on the back before filling this page) c8h17

Θ CF3 (CF2) 3S03 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition, in the present invention, the photoacid generator shown by the above general formula [s I] is more preferable. This can reduce the number of particles after the resistor composition is prepared, and the number of particles increased after the liquid storage over time. In the general formula [si], the alkyl group of Rs4 to Rs6 is a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a 2-butyl group, a 3-butyl group, or a pentyl group. Carbonyl, hexyl, heptyl, octyl, 3-fluorenyl, decyl, dodecyl, hexadecyl have 1 to 25 carbon atoms. The cycloalkyl group includes, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, a cyclohexadecyl group, or the like, which may have a substituent, having 3 to 25 carbon atoms. The alkoxy group has, for example, -43- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (42) Methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, 3-butoxy, pentoxy, 3-pentyloxy 1 to 25 carbons such as n-hexyloxy, n-octyloxy, n-dodecyloxy, etc. Alkoxycarbonyl has, for example, methoxycarbonyl, ethoxycarbonyl, and Oxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, 2-butoxycarbonyl or 3-butoxycarbonyl, pentyloxy, 3-pentyloxy Carbonyl, n-hexyloxycarbonyl, etc. 2 to 25 carbon atoms. The fluorenyl group includes, for example, a methylamino group, an ethylfluorenyl group, a butylfluorenyl group, a pentanyl group, a hexamethylene group, an octyl group, a 3-butylcarbonyl group, a 3-fluorenylcarbonyl group, and the like having a substituent. By. Examples of the fluorenyloxy group include ethoxyl, butylfluorenyl, 3-butanyloxy, 3-pentamyloxy, n-hexanecarbonyloxy, n-octanecarbonyloxy, and n-octyloxy. Those with 2 to 25 carbons such as dodecylcarbonyloxy and n-hexadecylcarbonyloxy. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. For these groups, substituents include alkoxy having 1 to 4 carbon atoms, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), fluorenyl group, fluorenyloxy group, cyano group, hydroxyl group, carboxyl group, Alkoxycarbonyl, nitro, etc. In addition, when l + m + n = 1, Rs4 represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and A substituted fluorenyl group may have a substituted fluorenyl group. In addition, R4 is preferably 2 or more carbon atoms, and more preferably 4 or more carbon atoms. In the above, it is an alkyl group that can have R.S4 ~ Rs6, for example, methyl, ethyl -44- (Please read the precautions on the back before filling this page)

, 1T

This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (43), propyl, isopropyl, butyl, 3rd -Butyl, n-pentyl, 3-pentyl, n-hexyl, n-octyl, decyl, etc. are preferred. Cycloalkyl is substituted with cyclohexyl, cyclooctyl, and cyclododecyl. Preferably, the alkoxy group is methoxy, ethoxy, isopropoxy, n-butoxy, 2-butoxy, 3-butoxy, pentoxy, or 3 -Pentyloxy, n-hexyloxy, n-octyloxy, and n-dodecyloxy are preferred, and the alkoxycarbonyl group is methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, N-butoxycarbonyl, 2-butoxycarbonyl, 3-butoxycarbonyl, pentoxycarbonyl, 3-pentoxycarbonyl, n-hexyloxycarbonyl, n-octyloxycarbonyl, n-dodecane The oxycarbonyl group is preferred, and the fluorenyl group may be substituted with methylamyl, ethylamyl, butylamyl, pentamyl, hexamethylene, octyl, 3-butylcarbonyl, and 3-pentylcarbonyl. The alkoxy group is preferably an ethoxy group, an ethoxy group, a butoxy group, a 3-butoxy group, a 3-pentoxy group, a n-pentyloxy group, which may have a substituent. The residues of Zhengxinyuan are better. Among the above-mentioned substituents, specific examples of preferred Rs4 to Rs6 are methyl, ethyl, propyl, isopropyl, n-butyl, 3-butyl, n-pentyl, 3-pentyl, and n-hexyl. Base, n-octyl, cyclohexyl, methoxy, ethoxy, isopropoxy, n-butoxy, 3-butoxy, pentoxy, 3-pentyloxy, hexyloxy, n- Octyloxy, methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, 3-butoxycarbonyl, 3-pentoxycarbonyl, hexyloxycarbonyl, n-octyloxycarbonyl, formamyl , Ethylfluorenyl, butylfluorenyl, hexylfluorenyl, octylfluorenyl, 3-butylcarbonyl, 3-pentylcarbonyl, ethynyloxy, butylfluorenyl, 3-butylfluorenyloxy, 3-pentamidine Oxygen, n-hexyl carboxyl-45- This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

591336 A7 _____B7_ 5. Description of the invention (44), n-octyl carboxyl, hydroxyl, chlorine, bromine, and nitro. For these groups, the substituents are methoxy, ethoxy, 3-butoxy, chlorine, bromine, cyano, hydroxyl, methoxycarbonyl, ethoxycarbonyl, and 3- Butoxycarbonyl and 3-pentyloxycarbonyl are preferred. The salt compound represented by the general formula [s I] used in the present invention uses a sulfonic acid having the above-mentioned specific structure for the anions and X _. The aliphatic hydrocarbon group which may have an R substituent in the anion has, for example, a linear or branched alkyl group having a carbon number of 1 to 20, or a cyclic alkyl group. Further, R is, for example, an aromatic group which may have a substituent. Examples of the alkyl group of R include a methyl group, ethyl group, propyl group, n-butyl group, n-hexyl group, n-octyl 2-ethylhexyl group, decyl group, and dodecyl group. By. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, a diamond group, a protosyl group, a camphor group, a tricyclodecyl group, and a cover group. Examples of the aromatic group include a phenyl group and a naphthyl group which may have a substituent. Examples of the alkyl group which may have a substituent of R in the above are methyl, trifluoromethyl, ethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, n-propyl, n-butyl, and nona Fluorobutyl, n-pentyl, n-hexyl, n-octyl, heptadecafluorooctyl, 2-ethylhexyl, decyl, dodecyl, and cyclic alkyl are, for example, cyclopentyl, cyclohexyl, camphor . Examples of the aromatic group include phenyl, naphthyl, pentafluorophenyl, p-tolyl, p-fluorophenyl, p-chlorophenyl, p-hydroxyphenyl, and dodecylphenyl which may have a substituent. , Fluorenyl, triisopropylphenyl, 4-hydroxy-1-naphthyl, 6-hydroxy-2-naphthyl. -46- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page), tr

Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 591336 A7 B7 V. Description of the invention (45) Specific examples of preferred sulfonic acid substituents R are methyl, trifluoromethyl, ethyl, pentafluoroethyl, 2, 2 , 2-difluoroethyl, n-butyl, nona-butyl n-hexyl, n-octyl, pentafluorooctyl, 2-ethylhexyl, camphor, phenyl, naphthyl, pentafluorophenyl, p- -Tolyl, p-fluorophenyl, p-chlorophenyl, p-methoxyphenyl, dodecylphenyl, carbyl, diisopropyl basic, 4-hydroxy-1-naphthyl, 6 -Hydroxy-2-naphthyl. The total carbon number of the generated acid is preferably 1 to 30. The number is more preferably 1 to 28, and the number is more preferably 1 to 25. If the total carbon number is less than one, a pattern such as a t-top shape may cause obstacles, and if it is more than 30, development residue may be generated, which is not desirable. Specific examples of the compound represented by the general formula [s I] in the following are shown in the following [s I-1] to [s I-20], but the present invention is not limited thereto. These compounds can be used alone or in combination of two or more. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-47- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 591336 A7 B7 V. Description of the invention (46) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

-48- (Please read the notes on the back before filling this page)

, 1T

The size of this paper applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 591336 A7 B7 V. Description of invention (47 C8H17

CF3 (CF2) 3S〇3 一 [si-7]

CF3 (CF2) 3S〇3 一 [si-8]

CH3 (CH2) 3COO

CF3 (CF2) 3S〇3- [sI-9] cf3 (cf2) 7s〇3-1 [sI_1〇] coo

-o-f

CF3 (CF2) 7S〇3 一 [sl_ll] (Please read the precautions on the back before filling in this page), order • 〇c〇

CF3 (CF2) 7S〇3— [b, I-12]

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

c〇-〇-sH

CF3 (CF2) 7S〇3 一 [SH3] 49- This paper size applies to China National Standard (CNS) A4 (210 X297 mm) 591336 A7 B7 V. Description of Invention㈠ 8) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

-50- (Please read the notes on the back before filling this page)

The size of this paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 591336 A7 _____B7 ___ V. Description of the invention (49) The compound shown in the above general formula [s I] which generates acid by active light or radiation ( Photoacid generator) Other photoacid generators described above can be used. (Please read the precautions on the back before filling this page) The iron salts shown in (PAG4) or [s I] are the same as the phosphonium salts that are different from the general formulas (PAG3) and (PAG4A). For example, jWKanpczyk et al , Am. Chem. Soc., 91,145 (1969) ^ ALMaycok et al, J. Org. Chem., 35, 2532, (1970), E. Geothas et al, Bull.

Soc. Chem. Belg., 73, 546, (1964) ^ HM Leicester. J. Am. Chem. Soc., 51, 3587 (1929) Λ JV Crivello et al, J. polym · Chem · Ed., 18, 2677 (1 980), U.S. Patent No. 2,807,648 and the methods described in 4,247,473, Japanese Patent Application Laid-Open No. 53-101,331 and the like.

The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints these general formulas (PAG4), or the general formula [s I], and the amount of the compound that generates acid through decomposition by active light or radiation irradiation is the total amount of the photoresist composition. The weight (except for the coating solvent) is generally 0.01 to 20% by weight, preferably 0.1 to 15% by weight, and more preferably 0.5 to 10% by weight. The added amount of these compounds that are decomposed by active light or radiation irradiation is low when the weight is less than 0.01% by weight, and if the amount is more than 20% by weight, the light absorption of the resist is too high and the appearance is not good. , And the scope of engineering (especially baking) is narrow, so it is not desirable. The photoacid generator that can be used is 300% by weight or less, preferably 200% by weight, and more preferably 100% by weight based on the amount of the photoacid generator of the present invention. [2] Secondly, the resin (called acid-decomposable polymer or acid-decomposable tree-51) that is used as the component (B) to increase the solubility in the alkali developer solution is described in this paper. Standard (CNS) A4 specification (210X297 mm) 591336 A7 ____ B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (50) grease). The acid-decomposable resin (B) of the present invention is characterized by having a partial structure represented by the general formula (I). In the general formula (I), the alkyl group represented by R1 to R4 is a straight or branched alkyl group having 1 to 10 carbon atoms, and more preferably a straight or branched chain having 1 to 6 carbon atoms. Alkyl, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl, etc. These alkyl groups may also be substituted base. Examples of the cyclic alkyl group represented by R1 to R4 include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, an orthospinyl group, and a norbornyl group which may have a substituent. , Isobornyl, tricyclodecyl, dicyclopentyl, orthospinyl epoxy, calanyl, isocanyl, neocanyl, tetracyclododecyl and the like. The alkyl group and cyclic alkyl group of R1 to R7 are the same as those described in R1 to R4. The aryl group may have a substituent, for example, a phenyl group, a tolyl group, a naphthyl group, or the like. The tolylalkyl silyl alkyl group is preferably a straight or branched alkyl group having 1 to 6 carbon atoms, and more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl Methyl, 2-butyl and 3-butyl, with methyl being the most preferred. The alkyl group of the trialkylsilyloxy group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl Methyl, 2-butyl and 3-butyl, with methyl being the most preferred. Specific examples of the repeating unit represented by the general formula (I) are as follows. However, the present invention is not limited by these specific examples. -52- This paper size applies to Chinese National Standard (CNS) A4 specification (21〇'297mm) (Please read the precautions on the back before filling this page)

591336 A7 B7 V. Description of the invention (51 ch3 ch3 • C—〇—C _ CH2 — Si ——CH〇II II 〇ch3 ch3 (M) CH3 CHs CHa C- 0- c— CH2— Si— C— CH3II I II o (1-2) CH3 ch3 ch3 ch3 Si (CH3) 3 Si (CH3) 3 • COC—CHo—Si II II 〇CH3 Si (CHa) 3 ch3 C— O—C — CH2—Si — CH3 II II o ch3 ch3 (1-3) ch3 CH2CHc (1-4) CH2CH (CH3) 2CH3 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs—C-10—C " II I CH2—Si—CH3 (1-5) 〇 CH3 ch3 ch3 ch3 C- II • oc—ch2ch2-, Si—CH3 (1-6) II 〇ch3 CHa ch3 ch3 C— 0_ C—CH2CH2- Si- CH2 ~ CH = CH2 〇ch3 ch3 ch3 Si (CH3) 3 c ~ II oc—ch2ch2- -Si—Si (CH3) 3 9 1 〇ch3 Si (OH3) 3 (1-8) 53- (Please read the precautions on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 9 5 / V 3 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 Invention Description (52) CH3 1 〇Si (CH3) 3 —C -0-C-II I CH2CH2-Si-OSi (CH3) 3 (1-9) II 1 0 ch3 OSi (CH3) 3 ch3 CH2CH3 —C_ 0—C CH2CH2 — Si CH3 (MO) 0 ch3 CH2CH3 ch3 CH2CH3 — coc— 11 1 CH2CH2— Si — CH2CH3 (MD 11 1 0 ch3 CH2CH3 ch3 ch3 1 —c—o_c— Μ I CH2CH2CH2-fi—CH3 (M2) II 1 0 ch3 ch3 ch3 Si (CH3) 3 —C one 0 one c— η I CH2CH2CH2-Si — Si (CH3) 3 (1-13) II 1 0 ch3 Si (CH3) 3 ch3 Si (CH3) 3 C—〇—C — CH2CH2CH2CH2—Si — Si (CH3) 3 (1 —14) II II 0 CH3 Si (CH3) 3 54- (Please read the precautions on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 591336 A7 __B7 V. Description of the invention (53) The acid-decomposable tree structure of the present invention having a part of the structure shown in the general formula (I) (B) ), It is preferable to include a repeating unit represented by the general formula (II) or a repeating unit represented by the general formula (II). In the general formula (II), the divalent linking group of L1 is, for example, a single bond in the general formula (II), or alone or two or more selected from an alkylene group, a substituted alkylene group, and having a crosslinked structure. Cycloalkylene, ether, thioether, carbonyl, ester, amido, sulfoamido, carbamate, and urea. The alkylene group and substitutable alkylene group of L1 may be a group represented by the following formula. -[C (R a) (R / 5)] Γ — (wherein R α and R / 3 represent a hydrogen atom, an alkyl group, a replaceable alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, both of which may be The same or different. The lower system is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl, or butyl, and more preferably, it is selected from methyl, ethyl, propyl, and isopropyl. Examples of the substituents that replace a hydroxy group include a hydroxyl group, a halogen atom, and a oxy group. The oxy group includes, for example, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group having 1 to 4 carbon atoms, and the halogen atom includes, for example, chlorine Atom, bromine atom, fluorine atom, iodine atom, etc. r represents an integer of 1 to 10. Cycloalkylene groups which may have a crosslinked structure include, for example, 5 to 8 carbon atoms, and specific examples include cyclopentyl groups, Cyclohexyl, Cycloheptyl, Shenyuan Heji etc. Specific examples of the repeating unit represented by the above general formula (II) are described below, but the present invention is not limited by these. -55- · This paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page), 11 Printed by Fei Cooperative 591336 A7 B7 V. Description of the invention (54 CH3 • CH2—c— CH COC—CHII I 〇ch3 3 2 CH3 Si—I ch3 ch3 (ii-υ CH〇I 3 ch2 ~ c— ch3 COC—CHo -II I 0 CHq

Si {CH3) 3 Si—Si (CH3) 3 Sf (CH3} 3 (II-2) CH, ch2-c— ch2ch3 ch3 c- o- c—CH2— si— CH3II IIO CH〇CH〇 (II-3 ) CH〇I CH2-C— CH3 0Si (CH3) 3 C- 0- C— CH〇- Si— OSi (CH3) 3 (11-4) II II 0 CH3 OSi (CH3) 3

H Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ch2—c— ch3 ch3 C— 0_ C — CH2— Si ——CH3 II I I 〇 ch3 ch3 H I ch2—c— CH3

Si (CH3) c C " ~ 0—C—CH2—Si—Si (CH3) 3 (Π-6) 〇 CH3 Si (CH3) 3 -56 (Please read the precautions on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 591336 A7 B7 V. Description of the invention (55 ch3 ch2-c- ch3 ch3 Printed by COC—CH2CH2 ~ Si— CH3 (II-7) 〇ch3 ch3 ch3 —ch2-c— CHa Si (CH3) 3 c- o- c— CH2CH2- Si— Si (CH3) 3 (II, 0 ch3 Si (CH3) 3 fH3 —ch2 ~ c— B I ch3 1 ch2ch3 1 c—〇- II, c— | CH2CH2-Si—CH3 (II-9) II 〇ch3 ch2ch3 H | —CH2—c— ch3 ch3 1 1 coc— 11 1 1 CH2CH2-Si —CH3 (11-10) 〇ch3 ch3 HI —CHo—C— 1 ch3 Si (CH3) 3 c- o- c— CH2CH2 ~ Si— Si (CH3) 3 (IM1) 0 ch3 Si (CH3) 3 CH3 _CHp -C-1 CH2CH3 Si (CH3) 3 c-〇-II • C— CH2CH2- Si— Si (CH3) 3 (IM2) II 〇ch3 Si (CH3) 3 -57- (Please read the precautions on the back before (Fill in this page) This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 591336 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7 V. Description of the invention (56) In the general formula (III) above , M1 is shaped The alicyclic structure atom group is an atom group of a repeating structural unit of an alicyclic hydrocarbon which may have a substituent in the resin. Among them, a 5 to 8 nitrogen ring is a monocyclic or a bridged alicyclic hydrocarbon is formed. Repeated units of the bridged alicyclic structure are preferred. The preferred structure of the bridged alicyclic hydrocarbon is, for example, as shown in the following structure. -58- This paper size applies to the Chinese National Standard (CNS ) A4 size (210X 297mm) (Please read the notes on the back before filling this page)

591336 A7 B7 V. Description of the invention (57 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

(Please read the notes on the back before filling this page)

This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 A7 B7 V. Description of invention (58 (28) (29)

V]

A (32) (33) (34) (35)

Ο (38) (39)

(40) (41) (42) (43) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

(44) (45) (46)

-60-(Please read the notes on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 591336 A7 B7 V. Description of the invention (59) " The above-mentioned alicyclic hydrocarbon structure may also have substituents. The substituent is, for example, a halogen atom, cyano, -COOH, -COOR1Q (R1Q represents a radical, a cyclic hydrocarbon group, or a group decomposed by an acid), -CO-X-T-R, or a substituent Alkyl or cyclic hydrocarbon. Here, X represents an oxygen atom, a sulfur atom, _NH- or -NHS02-. T represents a single bond or a divalent linking group. Represents a hydrogen atom, a cyano group, a hydroxyl group, -COOH, -COOR11, -CO-NH-R12, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a cyclic hydrocarbon group which may have a substituent (form The ring bond may have an ester group or a carbonyl group). R11 represents an alkyl group which may have a substituent or a cyclic hydrocarbon group which may have a substituent (an ester-forming group or a carbonyl group may be contained in a ring-forming bond), and represents an alkyl group which may have a substituent. The above-mentioned divalent linking group of L1 is, for example, alone or two or more selected from an alkylene group, a replaceable alkylene group, a cycloalkylene group having a crosslinked structure, an ether group, a thioether group, a carbonyl group, an ester group, and fluorene. Amine, sulfonamide, urethane, and urea. The alkylene group and substitutable alkylene group of L1 are the same as those of the divalent linking group of L1 of the general formula (I I). Specific examples of the repeating unit represented by the general formula (I I I) are described below, but the present invention is not limited thereto. -61-This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page) Order

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 591336 A7 B7 V. Description of Invention (60 \ Z ^ ch3 ch3 C— 0— C ——CHo-Si ——CH3 II II o ch3 ch3 (III-1) ch3 ch3 ch3 C—〇 一 C— CH2— Si— C—CH3 II I 1 1 o ch3 ch3 ch3 (III-2) Q ch3c-o II o (p—ch2— ch3 ch3 h3c coc—ch2- II I o ch3

Si (CH3) 3 si-Si (CH3) 3 Si (CH3) 3 ch3 Si-ch3 (III-3)

CH 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

0) IT H2 c H3lH3 cIC-—c I 〇I, c = o 3 H c H3LH3 clsi-c (III-5) c = 〇clc-c Π3 Π3 HP c ΓΊ3 c H3LH3 c-silc (III-6) 2 6 (Please read the notes on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 591336 A7 B7 V. Description of the invention (61) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ch3 Si (CH3) 3 1 coc-ch2ch2- -Si—Si (CH3) 3 〇ch3 Si (CH3) 3 CH2CH3 Si (CH3) 3 c- o- c— CH2CH2 ~ Si— Si (CH3) 3 〇ch3 Si (CH3) 3 (!) Ch3 Si (CH3 ) 3 coc-ch2ch2_ -Si-Si (CH3) 3 〇ch3 Si (CH3) 3 (!) Ch3 Si (CH3) 3 coc-ch2ch2- -Si-Si (CH3) 3 0 ch3 Si (CH3) 3 ch3 Si (CH3) 3 HOOC C- 0- C-CH2CH2- Si- Si (CH ^ a 〇ch3 Si (CH3) 3 ch3 Si (CH3) 3 H3C00C C- 0- c-CH2CH2- Si- Si (CH3) 3 〇 ch3 Si (CH3) 3 -63- (III-7) (III-9) (Please read the precautions on the back before filling this page); Linyi ·

、 1T This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) Nai 336 A7 B7 V. Description of the invention (62 ch3

Si (CH3):

H3CH2CHNC C- 0- C— CH2CH2 ~ Si— Si (CH3) 3 OO ch3 Si (CH3) 3 ch3 Si (CH3) 3 HO-H2CH2CHNC c- o- c— CH2CH2- Si— Si (CH3) 3 O 〇CH3 Si (CH3) 3 (ΙΠ-14) ch3

Si (CH3) 3

H3C C—〇—C ——CH2CH2—〒 i ——Si (CH3) 3 O

CH 3

Si (CHa) 3 (π I-15) (Please read the precautions on the back before filling this page) s

ch3

Si (CH3) 3

C- 0- C— CH2CH2- Si— Si (CH3) 3 O CH3

Si (CH3) 3 (III-16)

CH2CH3

Si (〇H3):

Printed by the Consumers and Consumers Agency of the Intellectual Property Bureau of the Ministry of Economic Affairs C-0-C-CH2CH2-— i-Si (CH3) 3 〇 ch3

Si (CH3) 3 (in-17)

CH3 Si (CH3) 3 C- 0- C— CH2- Si— Si (CH3) 3 (III -18) II II 〇CH3 Si (CH3) 3 -64- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 591336 A7 B7 V. Description of the invention (63) The resin of the present invention preferably contains a repeating unit represented by the following general formula (iv). This can further improve the density correlation. General formula (IV)

(Where Z represents an oxygen atom or ζζN-ίί13. 3 represents a hydrogen atom, a hydroxyl group, an alkyl group having a linear or branched chain, or -〇_S02-R14. R14 represents an alkyl group or a trifluoromethyl group) In general formula (IV), the alkyl group of R13 and R14 is a straight or branched alkyl group having 1 to 10 carbon atoms, and more preferably a straight or branched alkyl group having 1 to 6 carbon atoms, Most preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, di-2-butyl, and 3-butyl. Specific examples of the repeating unit represented by the general formula (I V) are as follows. However, the present invention is not limited by these specific examples. (Please read the notes on the back before filling this page)

I

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -65- This paper is suitable for standard paper ® ® T ^ S.) A4 size (210 × 297 mm) 591336 A7 B7 V. Description of the invention (64

.’CH-Q

(IV-1) Ο0 CH-CH-

(IV-2) CT

CH * CH

(IV-3) (Please read the precautions on the back before filling this page) .1 Zero · σ Y, 0 I 0Η

(IV-4)

、 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -66- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 591336 A7 B7 V. Description of invention (65

(IV-5)

(IV-6) 〇—so2—cf3

Please read the memorandum before filling in this page (IV-7) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, the resin of the present invention may contain a repeating unit represented by the following general formula (V). General formula (V) v / 2 — ^ ch2—

L3-C〇2 ~ Q (where Y2 is a hydrogen atom, a methyl group, a cyano group, or a chlorine atom. L3 is a single bond or a divalent linking group. Q is a hydrogen atom or a group that can be decomposed to produce an acid. ) In the repeating unit (V), the base system that can be generated by acid decomposition is carboxylic acid generated by exposure from component (A) and generated from resin decomposition / detachment_ C00h 基 -67- This paper applies Chinese national standards (CNS) 8 4 specifications (2! 0X297 mm) 9 A7 B7 V. The base of invention description (66). Specifically, tertiary alkyl such as 3-butyl and 3-fluorenyl, isobornyl, 1-ethoxyethyl, 1-butoxyethyl, 1-isobutoxyethyl, 1 -1-alkoxyethyl such as cyclohexyloxyethyl, alkoxymethyl such as 1-methoxymethyl, 1-ethoxymethyl, tetrahydropyran, tetrahydromanganyl, trioxane Silyl, 3-carbonylcyclohexyl, 2-methyl-adamantyl, mevalonolactone residue, 2- (r-butyrolactyloxycarbonyl) -2-propyl, and the like. Specific examples of the repeating unit represented by the general formula (V) are as follows, but the present invention is not limited by these. (Please read the notes on the back before filling this page)

、 1T Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-68- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 9 5 3 3 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ( (Please read the notes on the back before filling out this page)

V. Description of the invention (67 • CH2—〒 叶 ** (v_ ”C〇2I c (ch3) 3 (v 一 2) 〇〇2 C (CH3) 2 (C2H5)-| -CH2—CH-^-( p02 Si (CH3) 3 -ch2-? Hi C〇2 h3c-c

(V-3) (V-5) CH-? H * y (V-7) f〇2 h3c-c-: 〇

69- • ch2- r10 C〇2 (V-4) 6 {-CH2—CH- |-(V-6) C〇2I CH2OC2H5 • CH2—〒 H ^ C02 h3c-

〇 0 (V-8) This paper size is applicable to Chinese National Standard (CNS) A4 specification (21〇X297 mm) 591336 A7 B7 V. Description of invention (68 c

CICIC—C

\)/ -9

? H ch2—c— f (V-10) C02 I c (ch3) 2 (c2h5) c c— o— o—s

i— i

h3) 02 I

CH (Please read the notes on the back before filling this page) • CH2-9 "

(V-13) C〇2

(V-15) 9〇2 h3c—c -CH2— (p ding ~ 1-14) (p〇2 CH20C2H5 〒H3-mouth

CH 2 (V-16) C〇2

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

〇 〇 70- This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 591336 A7 B7 5. Description of the invention (69) In addition to the above repeating units, the resin of the present invention may contain other repeating units. This other repeating unit is a repeating unit represented by the following general formula (V I). General formula (VI) R15 —fcH2—C-} —

B (wherein, R15 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms; several R 1 5 may each be the same or different. B series Represents a halogen atom, a cyano group, a group decomposed by an acid, -C (= 0) -WU-R16 or -COOR17) Here, W represents an oxygen atom, a sulfur atom, -NH-, -NHS〇2_ or _ NHS02NH-, R16 is-COOH, · -COOR18 (R18 is synonymous with R17, and represents the following lactone structure), -CN, hydroxyl, alkoxy which may have a substituent, CO-NH-R17 or The following lactone structure. Lactone structure

(Wherein Ra ~ Re each represents an independent hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and ι and η each represent an independent 0 ~ 3 and m + n is 2 ～ 6, -71-This paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page) Order

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 9 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (70) R17 represents an alkyl group which may have a substituent, and a cyclic hydrocarbon group which may have a substituent. U system means single bond, alone or in combination of two or more alkylene groups, substituted alkylene groups, ether groups, thioether groups, carbonyl groups, ester groups, amido groups, amido groups, carbamate groups, and urea Groups based on groups) The above-mentioned groups decomposed by acid interaction are shown as -c (= 0) 41. Among them, R «is a tertiary alkyl group such as 3-butyl and 3-fluorenyl, isobornyl, 1-ethoxyethyl, 1-butoxyethyl, and 1-isobutoxyethyl 1-alkoxyethyl such as 1-cyclohexyloxyethyl, alkoxymethyl such as 1-methoxymethyl, 1-ethoxymethyl, tetrahydropyran, tetrahydrofluorenyl , Trialkylsilyl, 3-carbonylcyclohexyl, 2-methyl-adamantyl, mevalonolactone residue, 2- (7-butyrolactyloxycarbonyl) -2-propyl, and the like. X1 represents an oxygen atom, a sulfur atom, -NH-, -NHS02HN-, and an oxygen atom is preferred. The above alkyl group is preferably a straight or branched alkyl group having 1 to 10 carbon atoms, more preferably a straight or branched alkyl group having 1 to 6 carbon atoms, and the most preferred are methyl, ethyl, N-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl. Examples of the cyclic hydrocarbon group include a cyclic alkyl group, a bridged hydrocarbon, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, an isobornyl group, a tricyclodecyl group, a dicyclopentenyl group, ortho Spinylenyl epoxy, 1-based, isocanyl, neocapryl, tetracyclododecenyl and the like. The alkoxy group is, for example, one having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The other substituents of the above-mentioned alkyl, cyclic alkyl, and alkoxy groups are, for example, hydroxy-72-. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back first (Fill in this page again)

591336 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (71) Group, halogen atom, carboxyl group, alkoxy group, fluorenyl group, cyano group, fluorenyl group, etc. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy groups having 1 to 4 carbon atoms. Examples of the fluorenyl group include methyl fluorenyl and ethino. Wait. Examples of the alkylene group and substituted alkylene group of A in the formula (V I) include a group represented by the following formula. -[C (Rr) (R5)] s- wherein Rr and R6 represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and the two may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl, or butyl, and more preferably selected from methyl, ethyl, propyl, and isopropyl. Examples of the substituent which may be substituted for the alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. S is an integer from 1 to 10. Examples of the halogen atom include a chlorine atom, a fluorine atom, and an iodine atom. The B is a base group represented by an acid-decomposable group and -COOR 16 (lactone structure). The acid-decomposable resin of the present invention preferably contains a repeating unit represented by the following general formula (VII) and / or (VI II). This can improve the hydrophobicity of the composition. General formula (VII) General formula (VIII) (r-^ ch2— 卞-COOH L4— R21—V— R22 -73-

(Please read the notes on the back before filling this page)

、 1T This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 A7 B7 V. Description of the invention (72) R2G in the above formulae (VII) to (VIII) is synonymous with the above general formula (VI) ° R21 and R22 each represent an independent hydrogen atom or an alkyl group which may have a substituent. L4 represents a divalent group of a single bond, an ether group, an ester group, an amidino group, an alkylene group, or a combination thereof. V represents any one of the functional groups shown below. ~ C — N Η— S〇2- 〇-so2—nh——c-II ο • ΝΗ—C—ΝΗ—S02 " 〇S02-NH-C-NH ^ 〇 · 〇-C-ΝΗ-S02- 〇 • so2 ~ nh-c-o-II 〇so2-nh-so2- In the general formulae (VII) and (VII I), the alkyl group of R21 and R22 may be linear or branched, or may have a substituent . The linear or branched alkyl group is preferably one having 1 to 12 carbon atoms, and more preferably 1 to 10. Specific examples are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl, pentyl, hexyl, heptyl, octyl, nonyl And decyl are preferred. The cyclic alkyl group of R22 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, for example, has 3 to 30 carbon atoms. Specifically, for example, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, Spinosyl, norbornyl, tricyclodecyl, dicyclopentenyl, orthospinyl epoxy, calyl, isocalyl, neocalyl, tetracyclododecenyl, steroids, etc. -74- (Please read the notes on the back before filling this page)

This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 591336 A7 B7 5. Description of the invention (73) For example, the aryl group of R22 has 6 to 20 carbon atoms, and may have a substituent. Specific examples include phenyl, tolyl, and naphthyl. (Please read the notes on the back before filling out this page.) For example, the aralkyl group of R22 has 7 to 20 carbon atoms, and it may have a substituent. Specific examples include benzyl, benzyl, cumyl, and the like. L4 represents a divalent group of a single bond, an ether group, an ester group, an amidino group, an alkylene group, or a combination thereof. R21 represents a single bond, an alkylene group, an alkylene group, or a divalent group combining these. • The aryl group in R21 has, for example, 6 to 20 carbon atoms, and may have a substituent. Specific examples include phenylene, tolyl, and naphthyl. The extension groups of L4 and R21 are synonymous with V of the above general formula (VI). The other substituents of the above-mentioned alkyl group, cyclic alkyl group, alkenyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group, and arylene group are, for example, carboxyl group, alkoxy group, cyano group, and substituted group. An alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, an ethylfluorenylamino group, an alkoxycarbonyl group, a fluorenyl group, and the like.

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Among them, the alkyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, cyclopropyl, cyclobutyl, or cyclopentyl. Examples of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of fluorenyloxy are ethoxyl and the like. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. In general formula (VI II), R21 is preferably a single bond, methyl, ethyl, propyl, butyl, etc. R22 is methyl, ethyl, or other carbon number i -75 -This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 591336

A7 B7 V. Description of the invention (74) to 10 Cycloalkyl groups such as alkyl, cyclopropyl, cyclohexyl, camphor residues, naphthyl and naphthylmethyl are preferred. Z is a single bond, an ether bond, an ester bond, an alkylene group having 1 to 6 carbon atoms, or a combination of these. The single bond or the ester bond is preferred. In the following, specific examples of the monomers of the repeating structural unit represented by the general formula (VIII) are shown, but they are not limited thereto.

CH2 = CH ^ c ~ nh-so2 ο ch3 (Please read the notes on the back before filling this page) CH2 = C (vill · 2) CH2 = CH (Vlll · 3) c-nh-so2 — ch3 C—NH — S02_CH3 0 0 ch3 ch3 CH2 = c λ L7 CH2 = ^ • S〇2 ^ ^ c-nh-so2 ″ C 一 NH— // 0 (VIII-4) 0 (VIII- 5) CH3 ch2 = c ^ co —Ch2ch2 · 0 -〇-c-ch2ch2—f—NH— 'SpfCH3 II 0 0 (νιιμ 6)

, 1T

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ch3 ch2-c ^ C—O—CH2CH2CH2-S〇2-NH-SG2—ch3 (vm-7) 〇-76- This paper standard applies to China National Standard (CNS) A4 Specifications (210X 297mm) 591336 A7 B7 V. Description of the invention (75 ch3 ch2 =? (VIII. 8) // C 一 ◦— CH2CH2CH2- S〇2— NH ~ S02 — CH (CH3) 2 〇ch3 CH2 = ? c- 0— CH2CH2CH2 — S02- NH- S02

0 CH3

CH2 = C ^ C— ◦ a CH2CH2— S02 — NH — S〇2— CH3 0 CH3

\ X (Please read the notes on the back before filling this page) # · CH2 =? C 1 ◦— CH2CH2- S02 — NH- S〇2

Order 〇 CH3 CH2 =? O— CH2CH2- NH— C-NH— S02- CH3 ch3 ch2 = c

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 々C— ◦— CH2CH2— NH— f-NH— S〇2- CH2 (CH2) 6CH3 (V1IM3) CH3 ch2 = c I // c II 0 77

(V1IM4) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 591336 A7 B7

V. Description of the invention (76 CH3 CH ^ C / C— 0— CH2CH2— 〇— C—ΝΗ— S〇r CH3 〇 ’0 (VIIH5) ch3. CH2 = C ^ c-NH-S〇2

CH3 CH2 = C yc— o- CH2CH2CH2- S02- NH— S02 〇〆

(VIIM7) In addition to the repetitive structural units, the acid-decomposable resin of the present invention printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs adjusts dry etching resistance or standard imaging solution suitability, substrate adhesion, external appearance, and general resistance. Various repetitive structural units may be included for the purpose of resolution, heat resistance, sensitivity, etc. of the necessary characteristics of the body. The repeating structural unit is, for example, a repeating structural unit of the following monomer, and 彳 隹 + is limited by these. This allows fine adjustment of properties required for acid-decomposable resins @ (1) solubility in coating solvents, (2) film-forming properties (glass transition temperature), (3) inspection imaging properties, (4) Membrane Peripheral (Hydrophobic, Alkali Soluble Group)--78 (Please read the precautions on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 __ 5. Description of the invention (77) (5) Adhesion to the substrate of the unexposed part, (6) Resistance to dry etching. This monomer has, for example, one addition polymerizable property selected from the group consisting of acrylates, methacrylates, ammonium acrylates, ammonium methacrylates, allyl compounds, vinyl ethers, and ethyl acetates. Unsaturated bond. Specifically, the following monomers are mentioned, for example. Acrylates such as alkyl (preferably alkyl acrylates having 1 to 10 carbon atoms in the alkyl group): methyl acrylate, ethyl acrylate, propyl acrylate, pentyl acrylate, cyclohexyl acrylate, ethyl acrylate Hexyl, octyl acrylate, 3-butyl acrylate, ethyl chloroacrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trihydroxy monoacrylate Methylpropane ester, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, methyl acrylate, tetrahydromethyl acrylate and the like. Methacrylates (preferably alkyl methacrylates having 1 to 10 carbon atoms in the alkyl group): methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate , Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, ethyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2, 2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, monomethacrylic acid Pentaerythritol Ester, Methyl Methacrylate, Methacene-79- This paper size applies to Chinese National Standard (CNS) A4 (210 X297 mm) (Please read the precautions on the back before filling this page)

9 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____ B7 V. Description of the Invention (78) Tetrahydromethylene ester and so on. Acrylic acid amines: Acrylic acid amine, N-alkyl methacrylic acid (The carbon number of the alkyl group is preferably 1 to 10, for example, methyl, ethyl, propyl, butyl, and 3-butyl , Heptyl, octyl, cyclohexyl, hydroxyethyl, etc.), N, N -dialkylammonium acrylate (alkyl group is 1 to 10 carbons, for example methyl, ethyl, butyl, isobutyl Group, ethylhexyl, cyclohexyl, etc.), N-hydroxyethyl-N-methacrylamide, N-2 -ethenylethylethyl-N-ethenylmethacrylate, and the like. Ammonium methacrylates: Ammonium methacrylate, N-alkyl methacrylate (alkyl groups such as those having 1 to 10 carbon atoms, such as methyl, ethyl, 3-butyl, ethylhexyl, Hydroxyethyl, cyclohexyl, etc.), N, N-dialkylmethacrylamide (the alkyl system is ethyl, propyl, butyl, etc.), N-hydroxyethyl-N-methylmethacrylic acid Amidine and so on. Allyl compounds: Allyl esters (eg allyl acetate, allyl hexanoate, allyl heptanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate Propyl ester, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol ester, etc. Vinyl ethers: Alkyl vinyl ethers (such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxy vinyl ether, ethoxy vinyl ether, chlorinated ethyl vinyl ether, 1 · Methyl-2, 2-dimethylpropyl vinyl ether, 2-ethyl-80- This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling (This page)

591336 A7 ____B7 V. Description of the invention (79) Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylamino ethyl vinyl ether, diethylamino ethyl vinyl ether, butyl Aminoethyl vinyl ether, benzyl vinyl ether, tetrahydromanganese vinyl ether, etc.). Vinyl esters: vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloride Esters, vinyloxyacetate, vinyloxybutyrate, vinylacetate, vinyl lactate, vinyl A-phenylbutyrate, vinyl cyclohexylcarboxylate, and the like. Dialkyl itaconates: dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc. Others include citric acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, and maleonitrile. Other addition-polymerizable unsaturated compounds that can be copolymerized with the monomers of the various repeating structural units described above are copolymerized. In the acid-decomposable resin, the repeating unit of each structural unit contains the molar ratio, and the dry etching resistance of the resist or the standard imaging solution suitability, the substrate adhesion, the outer shape of the resist, and the general properties of the resist must be resolved. , Sensitivity, etc. are set appropriately. In the resin of the present invention, the content of the repeating unit having a partial structure represented by the general formula (I) of the present invention is the oxygen plasma uranium etch resistance, sensitivity, pattern crack prevention, substrate adhesion, The outer shape of the barrier, and the resolution and heat resistance of the necessary elements of the general barrier are appropriately set. -81-This paper size applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) (Please read the notes on the back first) Please fill in this page again for matters) J: 印 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 591336 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (80). Generally speaking, the content of the repeating unit of the present invention having a partial structure represented by the general formula (I) (preferably the repeating unit represented by the general formula (II) and / or (III)) is contained in the entire unit of the resin. The volume repeating unit is 4 to 70 mole%, preferably 6 to 65 mole%, and more preferably 8 to 60 mole%. In addition, the content of the resin in the repeating units shown in the above general formulae (IV) to (VIII) is appropriately set depending on the desired barrier properties, but generally, S is 30 to 96 mol%, preferably It is 35 to 94 mole%, and more preferably 40 to 92 mole%. When repeating units other than these are included, the total repeating unit is 50 mol% or less, preferably 40 mol% or less, and more preferably 30 mol% or less. The resin of the present invention is obtained by copolymerizing a monomer of a repeating unit represented by the general formula (II) and / or the general formula (III) with the monomer of the copolymerization component when a copolymerization component is used in the presence of a polymerization catalyst. Polymerize to synthesize. When the weight average molecular weight of the resin of the present invention is 为 in terms of polystyrene by GPC method, it is preferably 1,000 to 20,000. If the weight average molecular weight is less than 1,000, it is not desirable because of poor heat resistance or dry etching resistance, and if it is more than 200,000, the developability is deteriorated and the viscosity is extremely high, so poor film forming properties are not desirable the result of. The following are specific examples of the acid-decomposable resin of the present invention, but the present invention is not limited thereto. -82- This paper size applies to Chinese National Standard (CNS) A4 (210X 297mm) (Please read the precautions on the back before filling this page)

591336 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ — 8, ^ V

a] ^ Ho)! s I! S Iχ " ο £ οιο— Ο —οΓΟπΗοο- 9 ί 一 I I I I3x0) ls £ ο4-0 丨 xo ^ _ ^ o—x " o_j_ —ο 丨 XQ. COHO £ 3COHO

Ο II ο ο II II • οCOH0I0 丨 ο

S (ε)

ΨΗΟ)! 00e 工 ο ^ ho)! s —! six " o £ oioio—o:; £ 0010—0; x3)! s £ 0 —ο- 丨 f4. -^--^ ο—ινηοΗχο $ HO)! s £ 0 Ο Ο; £ 0) 0} —α5ιΙ " 0.Η0 丨 0-0-0 0 £ 0 £ 00 £ 01010 £ ο—οιο: ^ Ho)! sχο 木 0_3 工 0 十 本 3— £ 3 ^ _ Winter 0_3 工 0 £ οΗ Η co (xo)! sCOHO Ο-Ο = co (xo)! s £ 0 £ 0

COHO ε

HO ^ Ho)! s £ 0 0 g ^ Ho)! s —! slc > 4Ho £ o—o—o—o Ο ο Jxoolo 10ο 」ΗΟ 十 -f 3-χ " ο4

8 This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

-? XJ 591336 A7 B7 V. Description of the invention (82 o (g) ^ 5)! s —! S — £ ◦ £ 0— 0-O — b HO — 3 elc 35) 05- £ 0-ben 0— ”workers.十 工 〇7xo £ o co (xo)! s co (£ o)! s (9)

CO (I0)! S ε

Ho

OII xo I To 5- / i, + 01 £ 0. COH0 o ^ Ho)! sίο (ο ^ Ηο ^ ιωι ^ ο ^ ο — οιοιό 3x0)! sx " 3-f3 」H3

(S

0 II Ηο ε

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -0—0 • ^ h ^ o—lh?

£ 0

0 — 0 XO '^ H / 2 0 Ιχ0 · £ 0 £ 00⑺ 工 3 丨! S—x'olo—0 丨 0 xoxo-4-olho

(Please read the precautions on the back before filling this page) -84- This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 591336 A7 B7 V. Description of the invention (83 s (OT-) m) εΗΪΡΗΟ 丨 phen 丨 0—0 = work. 0X0. work. Ben ~ o- ~ H.十 工 ◦ + £ 0 -Ho cnHo

oII o II 010 ο £ ο〇 £ o 丨! slxo 丨 0- · —010 = 5. £ ° .hoohoioioHO Ben-0 | ~ 5 ten Γ a I, £ 0 £ 0 ^ Ho)! co—

£ oI xo -4 ~ oLH3 + xo " (£ o)! s £ o〇 co (coho)! si! sicnh ° .ho— r ΨΗ3) β ^ H3)! s

VHO ε Ηο 〇,

Ben 3 丨 34- COHO 〇-(Please read the notes on the back before filling this page)

Printed by 1T Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs

ο = ό — ο -01 £ 0 · -I COHO 0 λ

-85- This paper size applies to China National Standard (CNS) Α4 specification (210X 297 mm)

591336 Α7 Β7 V. Description of the invention (84

CSJ ΨΗΟ) ω £ 0 〇 ^ Ho) is I! S LH0.H0 —01〇 i £ 0- ^ Ho)! s ^ Ho)! sis ^ s) li

^ Ho)! s £ o〇 ^ H3)! s 丄 S lhonhu — 3 — 〇 —o = ^ 5) 卜 δ- ^ Ho)! sxo (· inch) ^ Ηο)! ςο—! α) ιχο ^ ο—0—0 ^ 5)! co- ~. O--

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇 〇

〇 ο 〇 HO 4 o II 0—p

-86- (Please read the notes on the back before filling this page)

This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 Α7 Β7 V. Description of invention (85

LO < 〇 co (£ o)! s £ oo 0 I I II IIJo)! s is lh ° .ho—oi〇 —oίο—os 丨 Hf 0 ^ ho) oq-ε55- j

o ^ Ho)! s xo j jxo)! sxoo o ^ HO)! s is 1cnho £ oioio —0χο.ηοο £ 0ιο —0 o 〆 ^, 00 CO 〇ο £ i X £ I x 〇—CO—〇I 〇— CO—CJ | 1 1 ^ CN ο o £ 1 £ £ 1 X ο— 0—0 I oo—o I 1 〇1 1 o L | • —〆, Ο o Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

C -Λc, > (Μ 〇 -87 (Please read the precautions on the back before filling this page)

This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 591336 A7 B7 V. Description of the invention (86 (s (bo co (xo)! S

COHOXO

ro (coHO)! s-! S —OJHOCNHO —olo—ooi NHOCVIHOCOH ro (xo)! s roHo

O II

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

^ Ho)! sxoo I I II ^ Ho)! s 丨! S 1 £ 0 □ = " 0—01010 1 Two co (To)! sCo 工 o

^ H3)! s

COHO

0 co (coHo)! s 丨! S—CNHOCSIHOlO—010 ro (To)! s £ o

-88- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling this page) 591336 A7 B7 V. Description of the invention (87 ⑺ (xo)! S exoο II II (· ει) co (xo)! s —! sicvjhod? oioioio Jl- £ 0-

ο 10ο I I II £ ο £ οοχ " ο— ο 10co (xo)! s —! S — (NHOCVJHO—O 丨 013 (· η)-{-0—-Χ04— 荖 |-£ 0 I. Η

([〇0 Ξ0 ^ 50 丨 08 ΗΟ

xo ^ Ho)! s ^ Ho)! s —! S lcvlHO £ olo— Ο —ο: £ 0 Ο ^ Ho)! sxoo ^ Ho)! s —! s ”Ηϋ.Ηοιο 丨 0 丨 0 ^ Η. ) 』Ίο-- ο ο ο

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

C 〇 -Λ 〇 «^, > (〇 -89 〇 〇 (Please read the notes on the back before filling in this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (2ΐοχ297 mm) 591336 A7 B7 5. Description of the invention (88) In the positive photoresist composition of the present invention, the composition of the resin (polymer) of the present invention The compounding amount in the whole object is preferably 40 to 99.99% by weight of the total solidified solid body, and more preferably 50 to 99.97% by weight. [3] The organic basic compound as the component (c) in the positive-type photoresist composition of the present invention will be described. This organic basic compound has, for example, the following builders. R ^ -N-R252 (A) (wherein R25Q, R251 and R 2 5 2 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, carbon A hydroxyl group of 1 to 6 or a substituted or unsubstituted aryl group of 6 to 20 carbons, and R2 ^ and r252 can be bonded to each other to form a ring) N ~~ C = N- (B) (Please read the back first (Please note this page before filling in this page): C-N'—Ο (C) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs: C—N- R255 .C——R256 -9 0-(D) (E) This Paper size applies Chinese National Standard (CNS) A4 specification (210'〆297 mm) 591336 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (89) R253, r254 in the above formula (E) Carbon number 1 ~ Alkyl of 6 ) The preferred compound is a nitrogen-containing test compound with two or more nitrogen atoms in different chemical environments in the molecule, and more preferably two kinds of ring structures containing substituted or unsubstituted amine groups and nitrogen atoms. A compound or a compound having an alkylamine group. Preferred examples are, for example, substituted or unsubstituted veins, substituted or unsubstituted amino groups, steeper ratios, substituted or unsubstituted amino groups, substituted or unsubstituted amino groups Laluyuan, substituted or unsubstituted miton, substituted or unsubstituted mile, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine , Substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperidine, substituted or unsubstituted morpholine, substituted or unsubstituted amine Morpholine and the like. Preferred substituents are amine, amine, amine, amine, amine, aryl, aryl, aryl, alkyl, amine, aryl, aryl, aryl, aryloxy, nitrate And cyano. Preferred specific compounds are, for example, vein, 1,1-dimethyl vein, 1 1 3 3 tetramethyl vein, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-methyl Aminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, aminomethyl) pyridine, 2-amino-3_methylpyridine, 2-aminomethylpyridine, 2- Amino-5-methylpyridine, 2-amino-6-methylpyridine, [aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperine, aminoethyl) Piperin, N- (2-aminoethyl) piperidine, 4-amino_2,2,6,6_tetramethyl-91-

R255 and R 2 56 can be the same or different paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm (Please read the precautions on the back before filling this page)

591336 Α7 Β7 V. Description of the invention (90) (Please read the precautions on the back before filling out this page) Pyridine, 4-pyranylpiperidine, 2-iminopiperidine, 1-(2-amine Ethyl) pyrrolidine, pyrazole, 3-amino-5 -methylpyrazole, 5-amino-3 -methyl-1 -p-tripyrazole, pyrenol, 2- (aminomethyl) ) -5 -methylpyridine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N-( 2-aminoamino) morpholine, 1,5-diazobicyclo [4 · 3 · 0] -5 -nonene, 1,8-diazobicyclo [5.4.0] -7 -ten Monoene, 2,4,5-triphenylimidazoline, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinylethylthiourea (CHMETU) Class 3 morpholine derivatives, hindered amines described in Japanese Patent Application Laid-Open No. 11-5257 (including those described in [0050] in the publication), and the like are not limited thereto.

More specific examples are 1, 5-diazobicyclo [4.3.0] -5-nonene, 1,8-diazobicyclo [5.4.0] -7-undecene (DBU) , 1,4-diazobicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrrole, pyridine Class 3 morpholines such as azoles, imidazoles, pyridamines, pyrimidines, CHMETU, hindered amines such as bis (1,2,2,6,6-pentamethyl-4-piperidinyl) decanoate Wait. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, including 1,5-diazobicyclo [4.3.0] · 5-nonene, 1,8-diazobicyclo [5.4.0] -7 -ten Monoene, 1,4-diazobicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, CHMETU, bis ( 1,2,2,6,6-pentamethyl-4-piperidinyl) decanoate is preferred. These organic basic compounds can be used alone or in combination of two or more. The amount of organic basic compound used is generally 0.001 to 10 parts by weight, preferably 0.01 to -92 for 100 parts by weight of the solid composition of the barrier composition. This paper size applies Chinese National Standard (CNS) Α4 Specifications (2 丨 0'〆297mm) 591336 A7 B7 V. Description of the invention (91) (Please read the precautions on the back before filling this page) 5 parts by weight. If it is less than 0.01 parts by weight, the effect of adding an organic basic compound cannot be obtained. When it is more than 10 parts by weight, the sensitivity tends to decrease and the developability of the non-exposed portion tends to deteriorate. [4] The surfactant system as the component (D) in the positive photoresist composition of the present invention will be described. The component (D) contains at least one fluorine-based surfactant, a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom, and a nonionic surfactant. Among them, fluorine-based surfactants, silicon-based surfactants, and surfactants containing both fluorine atoms and silicon atoms are preferred, which can improve the density correlation. Such surfactants include, for example, JP 6 2-3 6 6 6 3, JP 6 1-226746, JP 6 1-226745, JP 62-1 70950, and The surfactants described in Sho 63-34540, JP 7-230 1 65, JP 8-628 34, and JP 9-5988 can also be used directly as described below. Commercially available surfactants that can be used by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, for example, Yebei Dunpu (transliteration) EF30 1, EF303 (by Shin Akita Kasei Co., Ltd.), Floraton FC430, FC43 1 (Sumitomo Shriyem (transliteration) (stock system), Mekafak F171, F173, F176, F189, R08 (Danish Ink (stock) system), Safron S-382, SC101, SC102, SCI 03, SC104, SCI 05, SC 1 06 (made by Asahi Glass Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant. Specific examples of non-ionic surfactants such as polyethylene oxide lauryl ether, polycyclo-93- This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) 591336 A7 B7 V. Description of the invention (92) Polyethylene oxide alkyl ethers such as alkylene stearyl ether, polyethylene hexadecyl ether, polyethylene oxide oleyl ether, polyethylene oxide octylphenol ether, polyethylene oxide nonyl Polyethylene oxide alkyl aryl ethers such as phenol ethers, polyethylene oxide · polypropylene oxide block copolymers, sorbitol monolaurate, sorbitol monopalmitate, sorbose Alcohol monostearate, sorbitol monooleate, sorbitol trioleate, sorbitol fatty acid esters such as sorbitol monostearate, polyethylene oxide sorbitol monolaurate Acid esters, polyethylene oxide sorbitol monopalmitate, polyethylene oxide sorbitol monostearate, polyethylene oxide sorbitol trioleate, polyethylene oxide sorbitol Non-ionic surfactants such as polyepoxide sorbitol fatty acid esters such as alcohol tristearate. The compounding amount of the surfactant is usually 0.001 to 2 parts by weight, preferably 0.01 to 1% by weight based on the solid content in the composition of the present invention. These surfactants may be used singly or in combination. [5] Next, the relevant solvents are explained. The positive-type photoresist composition of the present invention can make at least one kind of propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like as a solvent, methyl lactate, and ethyl lactate. Alkyl lactates, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc., ethylene glycol monoalkyl ethers, ethylene glycol monomethyl ether, ethylene glycol monoether, etc. Ethylene glycol monoalkane ether acetates such as monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 2-heptanone, r-butyrolactone, methyl ethyl ketone, methyl methoxypropionate , Alkyl alkoxy propionates such as ethyl ethoxy propionate, alkyl pyruvate esters such as methyl pyruvate, ethyl pyruvate, N-methyl-94- This paper size applies to Chinese national standards (CNS) 8 4 specifications (210X297 mm) (Please read the precautions on the back before filling this page}

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 591336 A7 B7 V. Description of the Invention (93) Solvents such as pyrrolidone, N, N-dimethylformamide, dimethylimine, etc. shall be applied. In addition, the use of a specific solvent or a mixed solvent ((E) component) can improve the edge roughness and the stability of the body fluid over time. (E) The component system contains at least one propylene glycol monoalkyl ether carboxylic acid ester (referred to as Group A solvent), and at least one propylene glycol monoalkyl ether, alkyl lactate, and alkoxyalkyl propionate (referred to as Group B solvent) ) And / or ^ — a mixed solvent of butyrolactone, ethylene carbonate and propylene carbonate (referred to as group C solvent). In other words, the (E) component is a combination of a group A solvent and a group B solvent, a combination of a group A solvent and a group C solvent, and a combination of a group A solvent and a group B solvent and a group C solvent. When a group A solvent and a group B solvent are combined, edge roughness is particularly excellent. When a group A solvent and a group C solvent are combined, the stability of the body fluid over time is particularly excellent. When the group A solvent, the group B solvent and the group C solvent are combined, the edge roughness and the stability of the body fluid over time are particularly excellent. As the propylene glycol monoalkyl ether carboxylate, for example, propylene glycol monomethyl ether acetate, glycerol monomethyl ether propionate, propylene glycol monoethyl ether acetate, and propylene glycol monoacetate propionate are preferable. Examples of the propylene glycol monoalkyl ether are propylene glycol monomethyl ether and propylene glycol monoethyl ether. As the alkyl lactate, for example, methyl lactate and ethyl lactate are preferred. Examples of alkoxyalkyl propionates include propionate 3-ethoxyethyl ester, propionate 3-methoxymethyl ester, propionate 3-methoxyethyl ester, and propionate 3-ethoxylate. Methyl methyl is preferred. The weight ratio (A: B) of the A group solvent and the B group solvent is preferably 90: 10 ~ 15: 85, more preferably 80: 20 ~ 20: 80, and the most preferable is -95-. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page), 1T printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 591336 A7 _-~-'- ---_ V. Description of the invention (94) 70: 30 ~ 25: 75 ° The weight ratio (A ·· C) of the A group solvent to the C group solvent is preferably 99.9: 0.1 to 75: 25, more The best is 99: 1 ~ 80: 20, and the best is 97: 3 ~ 85: 15. When the three solvents are combined, the weight ratio of the group C solvent is 0.1 to 25% by weight, more preferably 1 to 20% by weight, and most preferably 3 to 17% by weight for all solvents. . A preferred combination of the mixed solvent containing propylene glycol monoalkyl ether carboxylate in the present invention is propylene glycol monomethyl ether acetate + propylene glycol monomethyl etherpropylene glycol monomethyl ether acetate + ethyl lactate propylene glycol monomethyl ether acetate + 3 -ethoxyethylpropionate propylene glycol monomethyl ether acetate + r-butyrolactone propylene glycol monomethyl ether acetate + vinyl carbonate propylene glycol monomethyl ether acetate + propylene carbonate propylene glycol monomethyl ether ethyl Acid ester + propylene glycol monomethyl ether + r-butyrolactone propylene glycol monomethyl ether acetate + ethyl lactate + r-butyrolactone propylene glycol monomethyl ether acetate + 3-ethoxyethyl propionate + r -Butyrolactone propylene glycol monomethyl ether acetate + propylene glycol monomethyl ether + vinyl carbonate propylene glycol monomethyl ether acetate + ethyl lactate + vinyl carbonate propylene glycol monomethyl ether acetate + 3-ethoxyethyl Propionate + ethylene carbonate propylene glycol monomethyl ether acetate + propylene glycol monomethyl ether + propylene carbonate propylene glycol monomethyl ether acetate + ethyl lactate + propylene carbonate -96- This paper size applies to Chinese national standards (CNS ) A4 size (210X297mm) (Please read the notes on the back before filling this page)

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 9

/ C Printed by A7 _ B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (95) Propylene glycol monomethyl ether acetate + 3-ethoxyethyl propionate + propylene carbonate. A better solvent combination is , Propylene glycol monomethyl ether acetate + propylene glycol monomethyl ether + 7-butyrolactone propylene glycol monomethyl ether acetate + ethyl lactate + r-butyrolactone propylene glycol monomethyl ether acetate + 3-ethoxyethyl Propionate + r-butyrolactone propylene glycol monomethyl ether acetate + propylene glycol monomethyl ether + vinyl carbonate propylene glycol monomethyl ether acetate + ethyl lactate + vinyl carbonate propylene glycol monomethyl ether acetate + 3 -Ethoxyethyl propionate + vinyl carbonate propylene glycol monomethyl ether acetate + propylene glycol monomethyl ether + propylene carbonate propylene glycol monomethyl ether acetate + ethyl lactate + propylene carbonate propylene glycol monomethyl ether acetate Ester + 3 -ethoxyethylpropionate + propylene carbonate In addition, the component (E) of the present invention is a solvent containing at least one alkyl lactate (solvent called (1)), an ester solvent and at least one alkyl Mixed solvent of oxyalkyl propionate (solvent called (2)). When the solvent of (1) and the solvent of (2) are used in combination, especially the edge roughness is excellent. The alkyl lactate is preferably methyl lactate or ethyl lactate. As the ester solvent, for example, butyl acetate, pentyl acetate, hexyl acetate, and butyl propionate are preferable, and butyl acetate is more preferable. Examples of alkoxyalkylpropionates are 3-ethoxyethylpropionate, 3-methoxymethylpropionate, 3-methoxyethyl'propionate, and 3-ethoxymethyl Propionate is preferred. The weight ratio of the solvent of (1) to the solvent of (2) ((1): (2)) is 90: 10 to 15: 85, and more preferably 80: 20 to 25: 75. In the present invention, the mixed solvent of (E) contains at least one additional r-Ding-97- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling (This page)

591336 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (96) Lactone, ethylene carbonate and propylene carbonate (solvents called (3)) are preferred. By adding the solvent of (3), the generation of particles in the barrier composition solution can be suppressed, and the generation of particles in the solution over time can be further suppressed. (3) The use weight ratio of the solvent is 0.1 to 25% by weight, more preferably 1 to 20% by weight, and most preferably 3 to 15% by weight for all solvents. The present invention contains Preferred combinations of mixed solvents of alkyl lactate such as alkyl lactate + butyl acetate, alkyl lactate + butyl acetate + T-butyrolactone, alkyl lactate + butyl acetate + vinyl carbonate, alkyl lactate + acetic acid Butyl ester + propylene carbonate, alkyl lactate + 3-ethoxyethyl propionate + τ-butyrolactone, alkyl lactate + 3-ethoxy ethyl propionate + ethylene carbonate, alkyl lactate +3 -ethoxyethylpropionate + propylene carbonate, more preferably alkyl lactate + butene acetate + r -butyrolactone, alkyl lactate + butyl acetate + vinyl carbonate, alkyl lactate + Butyl acetate + propylene carbonate, alkyl lactate + 3-ethoxyethyl propionate + 7-butyrolactone, alkyl lactate + 3-ethoxy ethyl propionate + vinyl carbonate, lactic acid Alkyl ester + 3-ethoxyethyl propionate + propylene carbonate. The (E) component of the present invention is a solvent containing heptone (a solvent referred to as (4)). Examples of heptone include 2-heptanone, 3-heptanone, and 4-heptanone, and 2-heptanone is preferred. When the heptone-based solvent is used, the edge roughness of the resist pattern can be improved. Moreover, it is preferable that (E) component contains another at least 1 type of propylene-glycol-monoalkyl-ether, alkyl lactate, and an alkoxy alkyl propionate (solvent called (5)). This can further improve the edge roughness of the resist pattern. Propylene glycol monoalkyl ether is preferably propylene glycol monomethyl ether or propylene glycol monoethyl ether -98- (Please read the precautions on the back before filling this page) ♦ Order

This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 591336 A7 B7 V. Description of the invention (97). As the alkyl lactate, for example, methyl lactate and heptone are preferred. Examples of alkoxyalkyl propionates include propionate 3-ethoxyethyl ester, propionate 3-methoxymethyl ester, propionate 3-methoxyethyl ester, and propionate 3-ethoxylate. Methyl methyl is preferred. The amount of the solvent used in the above (4) is usually 30% by weight or more, preferably 40% by weight or more, and more preferably 50% by weight or more for all solvents. (5) The amount of the solvent used is usually 5 to 70% by weight, preferably 10 to 60% by weight, and more preferably 15 to 50% by weight for the total solvent. (5) If the amount of the solvent used is less than the above range, the addition effect will decrease, and if it is more than 70% by weight, the problem of coatability will be reduced. Therefore, it is not intended in the present invention. It is preferable that the solvent further contains at least one kind of r-butyrolactone, ethylene carbonate, and propylene carbonate (a solvent referred to as (6)). By adding the solvent of (6), the generation of particles in the solution of the barrier composition can be suppressed, and the generation of particles in the solution over time can be suppressed. (6) The use weight ratio of the solvent is 0.1 to 25% by weight, more preferably 1 to 20% by weight, and most preferably 3 to 15% by weight for all solvents. The present invention contains Preferred combinations of heptone mixed solvents such as 2-heptanone + butyl acetate, 2-heptanone + butyl acetate + r-butyrolactone, 2-heptanone + butyl acetate + ethylene carbonate, 2-heptanone Ketone + butyl acetate + propylene carbonate, 2-heptanone + 3-ethoxyethylpropionate + r-butyrolactone, 2-heptanone + 3-ethylethoxyethylpropionate + ethylene carbonate Ester, 2-heptanone + 3-ethoxyethylpropionate + propylene carbonate, more preferably 2-heptanone + butenyl acetate + r-butyrolactone, 2-heptanone + butyl acetate- 99- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297mm) (Please read the precautions on the back before filling this page)

591336 A7 B7 V. Description of the invention (98) Ester + vinyl carbonate, 2-heptanone + butyl acetate + propylene carbonate, 2-heptanone + 3-ethoxyethylpropionate + r-butyrolactone , 2-heptanone + 3-ethoxyethylpropionate + ethylene carbonate, 2-heptanone + 3-ethoxyethylpropionate + propylene carbonate. In the present invention, the solid content of the barrier composition containing the above-mentioned components is preferably 3 to 25% by weight in the upper solvent, more preferably 5 to 22% by weight, and most preferably 7 to 20% by weight. The positive-type photoresist composition of the present invention may further contain an acid-decomposable dissolution preventing compound, a dye, a plasticizer, a surfactant other than the above, a photosensitizer, and an accelerator for the developing solution, as necessary. Soluble compounds. 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 50 nm to 1.5 / m (1500 nm). The above composition is coated on a substrate (for example, silicon / silicon dioxide coating) used in the manufacture of a precision electronic integrated circuit by a suitable coating method such as a spinner or a coater, and then passed through a predetermined method. The photomask is exposed and baked to develop, and a good photoresist pattern is obtained. Here, the exposure light is far ultraviolet rays having a wavelength of preferably 250 nm or less and more preferably 220 nm or less. Specific examples include KrF excimer laser (248nm), Ai * F excimer laser (193nm), F2 excimer laser (157nm), X-ray, electron beam, etc., especially ArF excimer laser (193nm) ) Better. The developing solution of the positive photoresist composition for far-ultraviolet exposure of the present invention may use inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, ammonium water, ethylamine, Primary amines such as n-propylamine, diethylamine, di-n-100- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 9 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ____B7 ____ V. Description of the Invention (99) Secondary amines such as propylamine, tertiary amines such as triethylamine, methyldiethylamine Alkaline aqueous solutions such as alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and piperidine. An appropriate amount of a surfactant can be added to the alkaline aqueous solution. When the positive-type photoresist composition of the present invention is used as a two-layer resist, the resist is used as a photomask to protect the upper resist pattern, and is carried out by the oxygen plasma of the upper organic polymer film. Etching, but the upper resistor has sufficient resistance to oxygen plasma. The oxygen plasma resistance of the positive photoresist composition of the present invention is related to the silicon content of the upper resist, or the etching device, and the etching conditions. The etching selection ratio (the etching speed ratio of the lower resist to the upper resist) is 1 0 ~ 100 is extremely sufficient. Furthermore, in the pattern forming method of the positive-type photoresist composition of the present invention, an organic polymer film is first formed on a substrate to be processed. The organic high-molecular film can be various conventional photoresist, such as various series such as Fujifilm's FH series, FHi series or OiR series made by Olin, PFI series made by Sumitomo Chemical. The organic polymer film is formed by dissolving it in an appropriate solvent, and applying the obtained solution by a spin coating method, a spray method, or the like. Then, the positive-type photoresist composition of the present invention is formed on the first layer of the organic polymer film. This is to dissolve the same photoresist material in the first layer in an appropriate solvent, and apply and apply the obtained solution by a spin coating method, a spray method, or the like. The obtained 2 layers of resistors are then applied to the pattern formation project. The first stage is to make -101- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling in this page)

591336 A7 B7 V. Description of the invention OO) The second layer, that is, the upper layer of the photoresist composition film is subjected to a pattern forming process. If necessary, a photomask is combined to make the photoresist composition of the irradiated part soluble in an alkaline aqueous solution, and developed with an alkaline aqueous solution to form a pattern. Next, in the second stage, the organic polymer film is etched. This operation is performed by using the pattern of the resist composition film as a photomask by oxygen plasma etching to form a fine pattern with a high aspect ratio. The etching of the organic polymer film by the oxygen plasma etching is performed by a conventional thermal etching operation using the same technique as the plasma action when the resist film is peeled off after the substrate etching process is completed. This operation can be performed, for example, using a cylindrical plasma etching apparatus or a parallel plate plasma etching apparatus using oxygen as a reactive gas, that is, an etching gas. In addition, the photoresist pattern is used as a photomask to process the substrate, and a dry etching method such as sputtering etching, gas plasma etching, or ion beam etching can be used as a processing method. In the present invention, the etching treatment by a two-layer film resist method including a photoresist film is completed by a peeling operation of the resist film. The peeling of the barrier layer can be performed simply by dissolving the organic polymer material in the first layer. The organic polymer material can be any photoresist, and there is no deterioration (hardening, etc.) at all in the above-mentioned photoetching operation. Therefore, conventionally known organic solvents for photoetching can be used. Alternatively, it can be peeled without using a solvent when it is processed by plasma etching or the like. [Example] In the following, the present invention will be described more specifically by way of examples, but the present invention -102- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the note on the back first Matters refill this page} Order

Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 591336 A7 B7 V. Invention Description (ιοί) is not subject to these restrictions. The resin (1) is synthesized such that the repeating unit (II-8) of the present invention is a monopolymer, methyl acrylate, 3-butyl acrylate, and maleic anhydride at a molar ratio of 15/1 0/35/40 It was added to a reaction vessel and dissolved in tetrahydrofuran to prepare a solution with a solid content of 50%. It was heated to 60 ° C under a stream of nitrogen. Stabilize the reaction temperature ′ Add 1 mol% of Wako Pure Chemicals (strand) starter V-60 to start the reaction. After heating for 15 hours, the reaction mixture was diluted twice with THF, and then poured into a large amount of hexane to crystallize a white powder. The precipitated powder was filtered, taken out, and dried to obtain a resin (1). The molecular weight of the obtained resin (1) was measured by GPC, and polystyrene was used as a standard sample. The weight average was 1,400. Moreover, the composition of the resin (1) by the NMR spectrum is that of the repeating unit (II_8) / maleic anhydride / methyl acrylate (repeating unit 1) / the 3rd-butyl acrylate (repeating unit 2) of the present invention. The ear ratio is 14/41/10/35. In the same manner as the synthesis of the above-mentioned resin (1), the resins (2) to (1 2) having the above-mentioned structures were synthesized. The composition ratio (molar ratio) of the repeating units of the resins (2) to (12) is shown in Table 1 below. (Please read the notes on the back before filling this page)

, 1T

Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -103- This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) 591336

7 B V. Description of the invention (102) Table 1 Resin maleic anhydride repeating unit 1 Repeating unit 2 Repeating unit of the present invention Mw ⑵ 45 12 30 13 1 5300 (3) 40 25 21 14 14 200 (4) 42 16 28 14 16400 (5) 46 30 10 14 14700 (6) 43 27 15 15 15400 (7) 44 26 14 16 15800 (8) 50 50 193C0 (9) 27 20 53 18300 (10) 31 15 54 19700 (11) 40 45 15 19500 (12) 34 50 16 19900 (Please read the precautions on the back before filling out this page) Duplicate Units 1 and 2 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, which are duplicate units representing anhydrous objects except for the above resin structure In addition to the repeating units of the present invention, the repeating units from left to right. The synthesis of the resin (1 ') enables the monopolymer, orthospinene and maleic anhydride of the repeating unit (III-7) of the present invention to be added to the reaction vessel at a molar ratio of 3 5/1 5/50 and dissolved in tetrahydrofuran Medium to 60% solid solution. It was heated to 60 ° C under a stream of nitrogen. The reaction temperature was stabilized, and 2 mol% of Wako Pure Chemical Industries, Ltd.'s starting agent V-60 was added to start the reaction. After heating for 20 hours, the reaction mixture was diluted twice with THF, and then put into a large amount of hexane to crystallize -104- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 printed by the Intellectual Property Bureau's Consumer Cooperative Fifth, the invention description (103) white powder. The precipitated powder was filtered, taken out, and dried to obtain a resin (1,). The molecular weight of the obtained resin (1 ') was measured by GPC, and polystyrene was used as a standard sample. The weight average was 8,700. In addition, the composition of the resin (1 ′) by the NMR spectrum is a molar ratio of the repeating unit (III-7) / maleic anhydride / orthospine (alicyclic olefin-based repeating unit) of the present invention to 36/50/1 4 . In the same manner as in the synthesis of the above-mentioned resin (1 '), the resins (2') to (16 ') having the above-mentioned structures are synthesized. The composition ratio (molar ratio) of the repeating units of the resins (2 ') to (16,) is shown in Table 2 below. -105- This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

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Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (104) Table 2 Resin anhydride repeat unit alicyclic olefin repeat unit Acrylate repeat unit Mw (2,) 50 18 32 8500 (3 ·) 50 17 33 8400 (4 丨) 50 34 16 8100 (5 丨) 50 19 ——___ 31 8600 (6 ·) 50 15 35 8700 (7 丨) 50 50 8800 (8) 50 50 8300 ( 9 ·) 50 50 9300 (10Ί 50 18 32 9700 ⑴,) 50 30 20 .9500 (12 ·) 50 32 18 8900 (13 ') 50 24 26 7900 (14 丨) 50 35 15 1 3900 (15,) 50 37 13 14500 (16 ') 50 36 14 12900 The alicyclic olefin-based repeating unit and the acrylate-based repeating unit represent repeating units from left to right except the anhydrous repeating unit of the resin structure and the repeating unit of the present invention. -10 6- This paper size applies to Chinese National Standard (CNS) A4 (210X 297mm) (Please read the precautions on the back before filling this page)

591336 A7 ____ B7_ __ 5. Description of the invention (105) Examples 1a-28a and Reference Examples 1a-2a (Preparation and evaluation of the positive photoresist composition of the first type) 2 g of each of the above synthesis examples The synthesized resin shown in Table 3 was compounded with 120 mg of the above-mentioned PAG (4-6) as a photoacid generator, 8 mg of an organic basic compound, and 5 mg of a surfactant, each dissolved in a solid content of 10% by weight. After the propylene glycol monoethyl ether acetate (PGMEA) was filtered through a 0.1 / m micro filter, the positive photoresist composition of Examples 1a to 28a was prepared. Further, in Reference Examples U to 2a, except that the organic basic compound and the surfactant were not used, a positive-type photoresist composition was prepared in the same manner as in Examples 1a and 1a described above. The surfactants used are described below. W-1: Mekafak (Transliteration) F 1 76 (made by Dainippon Ink Co., Ltd.) (fluorine-based) W-2: Mekafak (translated) by Dainippon Ink (Stock) Fluoride System and polysiloxane system) W-3: Polysiloxane polymer-KP-3 4 1 (made by Shin-Etsu Chemical Industry Co., Ltd.) W-4: Polyethylene oxide nonylphenyl ether organic test compound As follows. 1: DBU (1,8-diazobicyclo [5.4 · 0] -7-undecane) 2: DMAP (4-dimethylaminopyridine) 3: TP 1 (2, 4, 5-tris (Phenylimidazole) (evaluation test) F Ken 028D resistor (coated by Fujifilm Olin Corporation, 1-line resistor) was coated on a silicon wafer using a Kennon-made applicator CDS-650, and at- 107-This paper size applies to China National Standard (CNS) A4 (210X 297 mm) (Please read the notes on the back before filling out this page) Order the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives to print 591336 Intellectual Property of the Ministry of Economic Affairs A7 B7 printed by the Bureau's Consumer Cooperative. V. Description of the invention (106) Dry at 90 ° C for 14 seconds at 14CTC to make a uniform film of about 0.8 3 / zm. After it was heated at 200 ° C for 3 minutes, a film thickness of 0.71 // m was formed. A positive photoresist composition solution adjusted as described above was coated thereon, and baked at 90 ° C for 90 seconds, and the coating thickness was 0 to 0.20 // m. The thus-obtained wafer was exposed by mounting a photomask in an ArF excimer laser stepper and changing the exposure amount and focus. Then, after heating in a greenhouse at 130 ° C for 90 seconds, development was performed with a tetramethylammonium hydroxide developer solution (2.38%)) for 60 seconds. Wash and dry with distilled water to make patterns. The resist pattern of the obtained silicon wafer was observed with a scanning electron microscope, and evaluated as follows. The results of these evaluations are shown in Table 3. [Sensitivity change rate]: Regarding the positive photoresist composition solution (coating liquid) prepared above, evaluate the sensitivity (exposure amount before storage) after adjusting the liquid as described above, and evaluate the composition solution to be left at 23t. The sensitivity (exposure after storage) after 1 week, and the sensitivity change rate was evaluated by the following formula. Sensitivity change rate (%) = {(exposure before saving)-(exposure after saving)} / (exposure before saving) X 100 [density correlation]: line width 0. 1 5 // m From the line and the gap (dense pattern) and the isolated line pattern (sparse pattern), obtain the allowable depth of focus overlap range of 0.1 5 A m ± 10%. The larger the range, the better the sparse correlation. -10 8- The size of this paper applies to Chinese National Standard (CNS) A4 (210 × 297 cm) (Please read the precautions on the back before filling this page)

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7 B V. Description of the invention (107) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 3 Example Sensitivity change rate of resin organic basic compound surfactant (%) Density correlation (/ Ο 1 a (1) 1 W-4 9 0.6 2a (2) 2 W-3 7 0.8 3a (3) 3 W-2 5 0.9 4a (4) 2 Wl 5 0.9 5a (5) 1 W-3 5 0.9 6a (6) 2 W- 2 5 0.9 7a (7) 3 Wl 5 0.9 8a (8) 1 W-3 8 0.8 9a (9) 2 W-2 5 0.9 10a, (10) 1 Wl 5 0.9 11a (11) 2 W-3 5 0.9 12a (12) 3 W-2 5 0.9 13a (Γ) 1 W-4 9 0.7 14a (21) 2 W-3 5 1.0 15a (3,) 3 W-2 5 1.0 16a (4 丨) 2 Wl 5 1.0 17a (5 ') 1 W-2 5 1.0 18a (6') 2 W-3 5 1.0 19a (7 ·) 3 W-3 6 0.9 20a (8 ·) 1 W-2 6 0.9 21a (9,) 2 Wl 5 1.0 22a (10,) 3 W-2 5 1.0 23a ⑴,) 1 W-3 5 1.0 24a (12 ') 2 Wl 5 1.0 25a (13,) 3 W-2 5 1.0 26a (14 丨) 1 W-3 5 1.0 27a (15 ') 2 Wl 5 1.0 28a (16 丨) 1 W-2 5 1.0 Reference example la (1) Μ J \ te jw \ 50 0.1 Reference example 2a (Γ) ίΚJWS te j \ w 40 0.2 -109- (Please read the precautions on the back before filling this page),-?

This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 A7 __B7 V. Description of the invention (108) As can be seen from Table 3, the positive photoresist composition of the first type of the present invention has Excellent resolution, excellent stability over time of the composition solution, and excellent density and density. Examples lb to 28b and Reference Examples lb to 6b (preparation and evaluation of the second type of positive photoresist composition) 2 g of each of the resins shown in Tables 4 and 5 synthesized in the above Synthesis Example were added to a 150 mg table Photoacid generators shown in 4 and 5; 15 mg of the organic basic compound described in Tables 4 and 5; 10 mg of the surfactant described in Tables 4 and 5; each dissolved in propylene glycol monoethyl ether at a solid content of 10% by weight After the acetate (PGMEA), it was filtered through a 0.1 / 1 m micro-filter to prepare the positive photoresist composition of Examples lb to 28b. In addition, except that the second type of photoacid generator shown in Table 5 was not used in Reference Examples 1 b to 6b, a positive type photoresist composition was prepared in the same manner as in Examples 1 b to 2 8 b. Surfactants 1, 2, 3 and 4 are each the same as W-1, W-2, W-3, and W-4. The 5 series is Dunron Irolu S-3 3 6 (made by Dunlong Chemical). The organic basic compounds 1, 2, and 3 are the same as those in the above examples. (Evaluation test) FH 1-028D resistors (Fuji Negative Co., Ltd., i-line resistors) were coated on a silicon wafer with a CDS-6 50 manufactured by Kennon Coater, at 140 ° Dry at 90 ° C for 90 seconds to form a uniform film of about 0.8 3 # m. It was further heated at 200 ° C for 3 minutes to form a film thickness of 0.71 m. Apply the positive photoresist composition solution adjusted above and bake at 140 ° C for 90 seconds -1 10- This paper size applies to China National Standard (CNS) A4 size (210X297 mm) I-- -I '. II ϋ, pain,' 彳 (please read the precautions on the back before filling out this page), 1T% printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 591336 A7 __B7 V. Description of the invention (109) Set the film thickness of 0. 20 // m. (Please read the precautions on the back before filling in this page.) The wafer thus obtained is exposed in an ARF excimer laser stepper with a reticle and varying exposure and focus. Then, after heating in a greenhouse at 130 ° C for 90 seconds, development was performed with a tetramethylammonium hydroxide developer solution (2.38%)) for 60 seconds. Wash and dry with distilled water to make patterns. The resist pattern of the obtained silicon wafer was observed with a scanning electron microscope, and evaluated as follows. The results of these evaluations are shown in Tables 4 and 5. [Sensitivity]: The exposure amount that can reproduce the contact hole size of 0.18 // m and the peak width of 1/10 is used as the sensitivity, and the relative exposure amount when the exposure amount of the resist in Example 1 is 1.0 It is expressed as a relative sensitivity (exposure amount of other resists / exposure amount of Example 1 b). [Resolution power]: The resolution power of the contact hole is a critical contact hole size (// m) which is the exposure amount that can be reproduced with a contact hole size of 0.18 // m and a groove width of 1/1. Printed by the Bureau ’s Consumer Cooperatives [Number of particles and increase in particles after storage over time]: Regarding the positive photoresist composition solution (coating liquid) prepared as described above, after evaluating the liquid adjustment (initial particle size), After standing at 23 ° C for 1 week (number of particles over time), the number of particles in the liquid was calculated by Lynn (transliteration). Evaluate the initial particle size and the increase in particles calculated by (number of particles over time)-(particle size). -111- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 591336

7 B V. Description of the invention 〇1〇) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 4 Example Resin Photoacid Generator Organic Alkaline Compound Surfactant Sensitivity Resolution (_ Initial particle 値 Increase in particles lb 1 PAG4- 5 1 1 1.0 0.14 5 10 2b 2 PAG4-6 2 2 1.1 0.14 5 10 3b 3 PAG4-28 3 4 0.9 0.14 5 10 4b 4 SI-2 2 5 0.9 0.13 < 5 5 5b 5 SI-4 1 3 0.9 0.13 < 5 5 6b 6 SI-8 / PAG3-5: 4 / l 2 1 0.9 0.13 < 5 5 7b 7 PAG4-6 / PAG3-28 = 5 / l 3 2 1.1 0.14 5 10 8b 8 PAG4-7 / PAG7-1 2 8/1 1 3 1.1 0.14 5 10 9b 9 SI-8 / PAG7-2 = 10 / l 2 5 0.9 0.13 < 5 5 10b 10 SI-3 / PAG6-19 2 6/1 3 2 1.0 0.13 < 5 5 lib 11 SI-9 / PAG7-1 2 8/1 1 1 0.9 0.13 < 5 5 12b 12 SI-3 2 3 1.0 0.13 < 5 5 13b Γ PAG4-7 3 5 1.1 0.14 5 10 14b 2, PAG4-18 2 1 1.1 0.14 5 10 15b 3 'SI-3 1 3 1.0 0.13 < 5 < 5 16b 4' SI-5 2 2 1.0 0.13 < 5 < 5 17b 5 'SI- 8 3 5 0.9 0.13 < 5 < 5 18b 6 'SI-9 3 1 0.9 0.13 < 5 < 5 19b 7' SI-14 2 2 1.0 0.13 < 5 < 5 20b 8 'SI-17 2 3 1.0 0.13 < 5 < 5 -112- (Please read the back first Note: Please fill in this page again.) This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297 mm) 591336 7 Β Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (111) Table 5 Examples Resin photoacid generator Organic basic compound Surfactant Sensitivity resolution (" m) Initial particle size increase of particles 21b 9 'SI-3 / PAG3-29 2 3/1 1 3 1.0 0.13 < 5 < 5 22b 10 'SI-3 / PAG6-19 2 5/1 2 3 1.0 0.13 < 5 < 5 23b 1Γ SI-9 / PAG7-1 = 9/1 3 5 0.9 0.13 < 5 < 5 24b 12' SI -14 / PAG7-3 = 10/1 1 5 1.0 0.13 < 5 < 5 25b 13 · SI-3 / PAG7-2: 9 / l 2 1 1.0 0.13 < 5 < 5 26b 14 'PAG4-6 / PAG7-1 = 6/1 3 2 1.1 0.14 5 10 27b 15 'PAG4-6 / SI-5 = l / 3 1 5 1.0 0.13 < 5 < 5 28b 16' SI-3 / SI-9 = 2 / l 2 5 0.9 0.13 < 5 < 5 Reference example lb 1 PAG7-1 1 1 5.5 0.18 70 130 Reference example 2b Γ PAG3-5 2 3 2.3 0.17 105 560 Comparative example lb 2 PAG6-19 jw \ Μ y \ n \ 4.8 0.18 135 330 Comparative example 2b T PAG7-2 M y \ \\ te y \\\ 3.9 Unresolvable 310 570 Comparative example 3b 3 PAG3-5 M y \\\ 2 2.5 0.17 310 730 Comparative example 4b 4 PAG7-2 1 te • M, 4.0 Unresolvable 230 370 Comparative example 5b 3 'PAG7-1 te y \\\ 4 5.8 Unresolvable 130 260 Comparative example 6b 4' PAG6-19 3 M j \ w 4.9 0.18 260 480 -113- (Please read the notes on the back before filling this page)

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This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 591336 A7 B7 V. Description of the invention (112) PAG7-1 PAG7-2 IIso2—c—s〇2 CH, h3c S02-C-so2hQ > -PAG7-3

CH, Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. As shown in Tables 4 and 5, the positive photoresist composition of the second type of the present invention has excellent contact hole resolution. In addition, the preservability is particularly small (with an increase in examples) over time at 23 ° C. Example 1 c to 9 6 c and reference example 1 c to 6 c and comparative example 1 c (preparation and evaluation of a positive photoresist composition of the third type) 2 g each of the tables synthesized by the above synthesis example The resin shown in 6 to 12 is compounded with 140 mg of the photoacid generator shown in Tables 6 to 12, 12 mg of the organic test compound described in Tables 6 to 12, and 10 mg of the surfactant described in Tables 6 to 12, each with A solid content of 10% by weight was dissolved in the solvents shown in Tables 6 to 12 and then filtered through a 0.1 μm micro filter to prepare the positive photoresist composition of Examples 1c to 96c. In addition, in Reference Examples 1 c to 9 6 c and Comparative Example 1 c, except that a specific solvent of the third type was not used, a positive type photoresist composition was prepared in the same manner as in Examples 1 c to 9 6 c described above. Solvent is used -114- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page) 591336 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (113) S1: propylene glycol monomethyl ether acetate 52: propylene glycol monomethyl ether propionate 53: ethyl lactate 54: butyl acetate 55: 2-heptanone 56: propylene glycol monomethyl ether 57: Ethoxyethyl propionate 58: r-butyrolactone 59: ethylene carbonate S 1 0: propylene carbonate S1 1: cyclohexanone surfactants 1, 2, 3 and 4 are each W-1 , W-2, W-3, and W-4 are the same. The 5 series is Dunron Irolu S- 3 3 6 (made by Dunlong Chemical Co., Ltd.). The organic basic compounds 1, 2 and 3, and PAG7-1 and 7-2 are the same as those in the above examples. -115- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

591336

AB 5. Description of the invention⑴ 4) Table 6 Example (B) Resin composition (A) Photoacid generator (C) Solvent (E) Surfactant (D) Organic test compound lc Purpose (1) PAG3-5 Sl / S3 = 70/30 1 1 2c resin (2) PAG4-31 Sl / S3 / S8 = 70/27/3 2 2 3c resin (3) PAG4-5 S1 / S6- 80/20 3 3 4c resin (4) PAG3-28 Sl / S7 = 75/25 4 1 5c resin (5) PAG4-18 SI / S6 / S9 68/28/4 5 2 6c resin (6) PAG4- 37 S1 / S6 / S10-69 / 27/4 3 3 7c resin (7) PAG3-29 Sl / S3 / S9 = 70/25/5 2 1 8c resin (8) PAG4-7 Sl / S3 / S10 = 70 / 23/7 1 2 9c resin (9) PAG4-36 / PAG6-3 = 5 / l Sl / S8 = 90/10 5 3 10c resin (10) PAG3-29 / PAG7-1 = 4/1 Sl / S10 = 85/15 1 1 11c resin⑴) PAG4-6 Sl / S6 / S8 = 70/21/9 2 2 12c resin (12) PAG4-6 / PAG4-5 = 6 / l S1 / S9-88 / 12 3 3 13c resin ⑴ PAG4-35 Sl / S7 / S10 = 80/17/3 5 1 14c resin (2) PAG4-36 Sl / S7 / S8 = 80/16/4 5 2 15c resin (3) PAG4-6 / PAG6-19 = 4/1 S2 / S6 = 82/18 2 3 16c resin (4) PAG4-37 / PAG7-2 = 6 / l S2 / S7 / S9 = 77/20/3 3 1 17c resin (5) PAG4-6 / PAG7-1 2 7/1 SI / S7 / S9 2 78/18/4 1 2 18c resin (6) PAG4-35 / PAG7-2 2 6/1 S 2 / S10 = 80/20 5 3 -116- (Please read the precautions on the back before filling this page)

This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 591336

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7 B Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (115) Table 7 Example (B) Resin composition (A) Photoacid generator (C) Solvent (E) Surfactant (D) Organic base Compound 19c resin (1) PAG3-28 S3 / S4 = 60/40 1 3 20c resin (2) PAG4-6 S3 / S4 / S8 two 70/27/3 2 1 21c resin (3) PAG4-35 S3 / S7 / S9-70 / 25/5 3 2 22c resin (4) PAG3-29 S3 / S7 two 70/30 4 3 23c resin (5) PAG4-6 / PAG7-1 two 8/1 S3 / S7 / S8 two 80 / 17/3 5 3 24c, resin (6) PAG4-36 / PAG6-3 = 5 / l S3 / S4 / S10-60 / 36/4 1 1 25c resin (7) PAG3-29 / PAG6-19: 6 / l S3 / S7 / S10 = 70/23/7 2 1 26c resin (8) PAG4-5 S3 / S4 = 70/30 3 2 27c resin (9) PAG4-35 / PAG7-2 = 5 / l S3 / S4 / S9 = 70/26/4 1 1 28c tent (10) PAG4-37 S3 / S4 / S8 2 60/35/5 5. 3 29c resin⑴) PAG4-36 / PAG3-5: 4 / l S3 / S4 / S9 = 60/32/8 5 2 30c Shed purpose (12) PAG4-18 S3 / S7 = 80/20 2 1 -117- (Please read the precautions on the back before filling this page)

、 1T This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 591336

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7 B Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (116) Table 8 Example (B) Resin composition (A) Photoacid generator (C) Solvent (E) Surfactant (D) Organic base Compound 31c (1) PAG4-6 S5 / S6 / S9 68/27/5 5 3 32c resin (2) PAG3-5 S5 4 2 33c resin (3) PAG4-5 S5 / S8 = 90/10 3 3 34c resin (4) PAG4-37 S5 / S3 / S8 = 70/25/5 2 1 35c resin (5) PAG3-28 S5 / S3 = 80/20 1 1 36c resin (6) PAG3-28 / PAG7- 1-6 / 1 S5 / S6 / S8-70 / 20/10 2 2 37c resin (7) PAG4-6 / PAG7-2 2 5/1 S5 / S3 / S8-70 / 22/8 3 2 38c resin ( 8) PAG3-29 S5 / S6 = 78/22 2 3 39c resin (9) PAG4-35 / PAG7-2 2 8/1 S5 / S6 / S10-70 / 18/12 1 3 40c resin (10) PAG4- 18 S5 / S9 two 92/8 5 3 41c resin (11) PAG4-31 S5 / S7 two 70/30 5 3 42c resin (12) PAG4-36 / PAG6-19 two 6/1 S5 / S7 / S10 = 72 / 20/8 1 2 43c resin (1) PAG4-36 S5 / S10 = 85/15 2 2 44c resin (2) PAG4-5 / PAG4-6 2 1/5 S5 / S7 / S9 = 80/16/4 5 1 45c resin (3) PAG4-35 S5 / S3 / S10 = 60/33/7 3 1 46c resin (4) PAG3-28 / PAG4-6 two 1/3 S5 / S7 / S8 = 7〇 / 22 / 8 5 1 -118- (Please read the notes on the back before filling this page)

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This paper size applies to China National Standard (CNS) A4 (210X297 mm) 591336

A B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (117) Table 9 Example (B) Resin composition (A) Photoacid generator (C) Solvent (E) Surfactant (D) Organic base Compound 47c Note U ') PAG4-6 Sl / S3 / S8 = 75/22/3 1 2 48c Resin (21) PAG3-5 Sl / S3 = 75/25 4 3 49c Resin (31) PAG4-18 Sl / S6 / S10 = 68/25/7 3 3 50c resin (41) PAG4-35 S1 / S7 / S8 two 70/20/10 2 1 51c resin (51) PAG3-28 / PAG4-5 = l / 2 Sl / S6 = 80/20 5 1 52c resin (6 ') PAG4-31 S1 / S3 / S9-72 / 23/5 2 3 53c resin (7,) PAG4-5 S2 / S6 = 80/20 1 3 54c resin ( 8 ') PAG4-6 / PAG7-2 = 5 / l S1 / S8 85/15 3 1 55c resin (9J PAG4-36 Sl / S6 / S8: 75/20/5 2 2 56c resin (10') PAG4 -31 / PAG7-1 = 5/1 Sl / S3 / S10 = 80/17/3 5 3 57c resin⑴ ') PAG3-28 Sl / S7 = 70/30 5 1 58c Box (12') PAG4-37 Sl / S6 / S9 = 72/20/8 1 2 59c resin (13J PAG4-29 Sl / S9 = 88/12 3 3 60c resin (141) PAG4-35 / PAG7-2-6 / 1 Sl / S7 / Sl 〇 = 70/22/8 2 1 61c Test purpose (15J PAG4-36 / PAG6-19 = 6/1 S2 / S9 = 88/12 3 2 62c Turn purpose (16 ') PAG4-35 / PAG7-l = 8 / l S1 / S10-82 / 18 2 3 63c Shed Purpose (1 ') PAG4-31 / PAG7-1 = 5/1 Sl / S7 / S9 = 65/30/5 5 1 64c resin (2 ') PAG4-37 / PAG7-2 = 10 / l Sl / S3 / S9 = 80/16/4 1 2 -119- (Please read the precautions on the back before filling out this page). One paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 591336

7 7 AB Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (118) Table 10 Example (B) Resin composition (A) Photoacid generator (C) Solvent (E) Surfactant (D) Organic Base compound 65c (1 ') PAG4-35 S3 / S4 / S9 = 58/35/7 5 1 66c resin (2〇PAG4-6 S3 / S4 / S10-55 / 40/5 1 2 67c 3 ') PAG4-36 S3 / S7 / S8 = 72/20/8 2 3 68c resin (4') PAG4-18 S3 / S4 / S8 = 60/35/5 3 1 69c resin (5 ') PAG4-6 / PAG7-1 = 9/1 S3 / S7 / S9 = 70/21/9 3 2 70c resin (6,) PAG4-37 S3 / S7 / S8 = 70/23/7 2 3 71c resin (7 ') PAG4 -5 S3 / S4 = 68/32 4 2 72c resin (8 ') PAG3-28 / PAG4-6 two 1/1 S3 / S4 / S8 = 70/27/3 5 1 73c resin (91) PAG3-28 S3 / S4 / S10 = 60/32/8 5 1 74c resin (KΠ PAG4-35 / PAG7-2 2 8/1 S3 / S7 / S10 = 63/27/10 1 2 75c resin (1Γ) PAG3-5 S3 / S7 = 73/27 2 3 76c resin (12 ') PAG4-6 / PAG6-19 2 6/1 S3 / S4 / S9 = 60/30/10 3 1 77c resin (13') PAG4-7 S3 / S7 / S9 = 72/20/8 2 2 78c resin (14J PAG4-36 / PAG6-3 = 10 / l S3 / S4 / S10-60 / 33/7 1 3 79c resin (15 ') PAG3-29 S3 / S7 / S10 = 70/20/10 5 2 80c resin (16 ') PAG4-37 / PAG3-5 = 4 / l S3 / S4 / S9 = 60/32/8 2 1 • 120- (Please read the notes on the back before filling this page)

、 11 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 591336

A

7 B Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (119) Table 1 1 Example (B) Resin component (A) Photoacid generator (C) Solvent (E) Surfactant (D) Organic 81c resin (1Ί PAG4-35 S5 / S6 / S10 = 72/20/8 1 2 82c resin (2 ') PAG3-28 S5 / S9 = 90/10 2 2 83c resin (3,) PAG4-36 S5 / S7 / S10 = 69/29/2 3 1 84c resin (4J PAG3-5 S5 4 3 85c resin (5 ') PAG4-37 S5 / S3 / S10 = 80/16/4 5 1 86c resin (6') PAG4-18 S5 / S7: 80/20 1 3 87c resin (71) PAG4-7 S5 / S3 70/30 2 2 88c resin (8 ') PAG4-6 / PAG6-19 = 6/1 S5 / S6 / S9 = 75/18/7 1 1 89c Resin (91) PAG4-5 S5 / S10-92 / 8 2 3 90c Resin (10 ') PAG3-29 S5 / S3 / S8 = 7〇 / 20/10 5 3 91c Resin⑴ ') PAG3-29 S5 / S6 2 75/25 3 1 92c Resin (12J PAG4-35 / PAG7-1 = 6/1 S5 / S7 / S8 = 65/30/5 3 2 93c Test purpose (13' ) PAG4-36 / PAG7-2 2 7/1 S5 / S3 / S9 72/19/9 5 3 94c resin (14 ') PAG4-31 S5 / S8 = 80/20 5 1 95c resin (15') PAG4 -6 / PAG3-29 = 7 / l S5 / S6 / S8-77 / 20/3 3 2 96c resin (16 ') PAG4-37 / PAG6-19-6 / 1 S5 / S7 / S9 70/26 / 4 1 3 -121-(Please read the notes on the back first Complete this page)

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This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 A7 B7 V. Description of the invention (12) Table 12 (B) Resin composition (A) Photoacid generator (C) Solvent (E) interface Active agent (D) Reference example of organic base compound lc Resin (1) PAG3-5 S11 1 1 Reference example 2c Resin (2) PAG4-5 S1 2 2 Reference example 3 c Resin (3) PAG6-19 S2 3 3 Reference example 4c resin (P) PAG7-2 S3 4 1 Reference example 5c resin (2 丨) PAG4-7 S1 and 2 Reference example 6c resin (4 丨) PAG4-6 S1 te te ^ \ w Comparative example lc resin (3 丨) PAG3-28 S11 5 None (Please read the precautions on the back before filling out this page) -1 ^^. (Evaluation test) Use Kennon-made applicator CDS-650 to coat FHi-〇28D resistor on silicon wafer Body (made by Fujifilm Olin Co., Ltd., i-line resistive body), and dried at 1 40 ° C for 90 seconds to form a uniform film of about 0 · 8 3 // m. After it was heated at 200 ° C for 3 minutes, a film thickness of 0 · 7 1 / z m was formed. A positive photoresist composition solution adjusted as described above was applied thereon, and baked at 130 ° C for 90 seconds, and a film thickness of 0.20 // m was applied. The wafer thus obtained was exposed by mounting a photomask in an ARF excimer laser stepper, and changing the exposure amount and focus. Then, after heating in a greenhouse at 130 ° C for 90 seconds, development was performed with a tetramethylammonium hydroxide developer solution (2.38%)) for 60 seconds. Wash and dry with distilled water to make patterns. The resist pattern of the obtained silicon wafer was observed with a scanning electron microscope, and evaluated as follows. -122- This paper size applies to China National Standard (CNS) A4 (210X 297mm)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 9 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 _ V. Description of the Invention (121) The results of these evaluations are shown in Tables 1 to 19. [Edge Roughness]: The edge roughness is measured by measuring the edge roughness of the 0.14 / zm line and gap (line / gap = 1 / 1.2) pattern using a length-measuring scanning electron microscope (SEM), and the line pattern is measured in the display. Several edges can be detected at the edge, and the dispersion (3 σ) of the detected positions is used as an index of edge roughness. The smaller the value, the better. [Number of particles and increase of particles after storage over time]: Regarding the positive photoresist composition solution (coating solution) prepared as described above, evaluate the solution adjustment (initial particle size), and leave it at 4 ° C for 1 After the week (the number of particles over time), the number of particles in the liquid is calculated by Lynn (transliteration). Evaluate the initial particle size and the increase in particles calculated by (number of particles after time)-(particle size). -123- This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

591336

7 B Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (122) Table 13 Example of the f f (nm) Initial particle size and particle increase number 1 c 12 10 15 2c 9 < 5 5 3c 12 10 15 4c 12 10 10 5c 9 < 5 5 6c 8 < 5 < 5 7c 9 < 5 < 5 8c 9 < 5 5 9c 13 5 10 10c 14 5 10 11c 8 < 5 5 12c 13 5 10 13c 8 < 5 < 5 14c 8 < 5 < 5 15c 13 10 20 16c 10 5 10 17c 8 < 5 5 18c 14 15 20 -124- (Please read the notes on the back before filling this page )

、 11 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 591336

A Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (123) Table 14 Example roughness (nm) Initial particle number of particles 19c 11 5 10 20c 7 < 5 5 21c 7 < 5 < 5 22c 11 5 10 23c 7 < 5 5 24c 7 < 5 < 5 25c 8 < 5 5 26c 11 5 10 27c 7 < 5 < 5 28c 7 < 5 < 5 29c 7 < 5 < 5 30c 11 5 10 -125- (Please read the notes on the back before filling this page)

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This paper size applies to China National Standard (CNS) A4 (210X297 mm) 591336

V. Description of the invention (124) Table 15 Example printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics Roughness (nm) Initial increase of particles and particles 31c 7 < 5 5 32c 14 15 20 33c 13 5 10 34c 7 < 5 < 5 35c 11 10 10 36c 8 < 5 < 5 37c 7 < 5 5 38c 11 10 10 39c 7 < 5 < 5 40c 13 5 10 41c 11 10 15 42c 7 < 5 < 5 43c 12 5 10 44c 7 < 5 5 45c 7 < 5 < 5 46c 8 < 5 5 -126- (Please read the notes on the back before filling this page)

This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 591336

A Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (125) Table 16 Example Crude sugar content (nm) Initial particle number of particles 47c 8 < 5 5 48c 12 10 15 49c 9 < 5 5 50c 8 < 5 < 5 51c 12 10 15 52c 9 < 5 '5 53 c 13 15 20 54c 13 10 10 55c 8 < 5 < 5 56c 9 < 5 5 57c 12 10 15 58c 9 < 5 < 5 59c 13 5 10 60c 8 < 5 < 5 61c 14 10 15 62c 13 5 10 63c 9 < 5 5 64c 11 5 5 -127- (Please read the notes on the back before filling this page) 、 -mouth

This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (126) Table 17 Example roughness (nm) Initial particle increase in particles 65c 7 < 5 < 5 66c 7 < 5 5 67c 7 < 5 < 5 68c 8 < 5 5 69c 7 < 5 5 70c 7 < 5 < 5 71c 11 5 10 72c 8 < 5 < 5 73c 8 < 5 < 5 74c 7 < 5 < 5 75c 11 10 10 76c 7 < 5 5 77c 8 < 5 5 78c 7 < 5 < 5 79c 8 < 5 < 5 80c 7 < 5 < 5 -128- (Please read the notes on the back before filling this page)

、 11 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 591336

7 B Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (127) Table 18 Example Crude sugar content (nm) Initial increase of particles and particles 81c 7 < 5 < 5 82c 13 5 10 83c 7 < 5 < 5 84c 14 15 20 85c 7 < 5 < 5 86c 12 10 15 87c 12 10 15 88c 7 < 5 5 89c 13 10 15 90c 8 < 5 < 5 91c 12 10 10 92c 7 < 5 < 5 93c 7 < 5 < 5 94c 13 5 10 95c 7 < 5 5 96c 7 < 5 < 5 -129- (Please read the notes on the back before filling out this page) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 591336 V. Description of invention (128) Table 19 Thickness (nm) Initial number of particles 値 Increase of particles Reference example 1 025 25 910 Reference example 2c 22 80 510 Reference example 3 c 24 210 1250 Reference example 4c 21 70 260 Reference example 5 c 25 130 660 Reference example 6c 30 810 1780 Comparative example 1 c 28 260 1010 (Please read the precautions on the back before filling out this page) Staff of the Intellectual Property Bureau of the Ministry of Economic Affairs As printed in the consumer cooperatives, as shown in Tables 1 to 19 above, it can be seen that the evaluation of the positive photoresist composition of the third type of the present invention is evaluated. Currently, all the respective fields excellent performance. Further, in Reference Examples 5 and 6, when the storage temperature over time was 2 3 ° C, and the same evaluation was performed, the initial particle size was 15 in Reference Example 5, the number of particles was increased by 35, and the initial particle size was 20 in Reference Example 6. Number of particles and 55 particles. [Effects of the Invention] The present invention provides a positive photoresist composition having a high resolution of 0.15 / zm or less, a composition solution with excellent storage stability over time, and excellent density and density correlation in manufacturing a semiconductor device. Positive photoresist composition with high sensitivity, high resolution of less than 0.1 5 // m, and good stability of the composition solution over time, the edge roughness of the resist pattern is improved, and preserved A positive photoresist composition having excellent stability. -130- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

591336 Gongtai VI. Patent Application No. 8 9 1 2 7 1 9 5 "Positive Photoresist Composition" Patent Case (Amended on July 15, 1992) Six Patent Application Scope: 1. A positive type A photoresist composition comprising: (A) 0.00 1 to 40% by weight of a compound that generates an acid by irradiation with active light or radiation; (B) 40 to 99.99% by weight having a formula represented by the following general formula (I) (C) 0.001 to 10% by weight of an organic basic compound; and (D) 0. (H to 2% by weight of at least one Fluorine-based surfactants and / or silicon-based surfactants and non-ionic surfactants; General formula (I) c—〇—〇 ′ 〇R2 / f \ c- \ R4 / • Si——R6 In formula (I), m is an integer of 1 to 6; R1 and R2 each represent an alkyl group or a cyclic alkyl group, or R1 and R2 are bonded to each other to form a cyclic alkyl group; R3 and R4 each represent a hydrogen atom , Alkyl or cyclic alkyl, or R3 and R4 are mutually bonded: a cyclic alkyl group is formed; R5 to R7 each represent an alkyl group, a cyclic alkyl group, an aryl group, and a tricyclic group. Silyl group or trialkylsilyloxy group. For example, the positive photoresist composition of the first patent application range, in which the resin (A) which increases the solubility to the alkali developing solution by the action of acid contains the following: _ 591336 VI. The repeating unit shown in the general formula (II) of the patent application general formula (II). C——〇—C • CHo-C where R1 ~ R7 and m are as defined in formula (I); γΐ is a nitrogen atom, a methyl group, a helium group or a gas atom; L1 is a single bond or a divalent linking group. For example, the positive photoresist composition of the first patent application range, in which the resin (A) which increases the solubility in the alkali developing solution by the action of an acid contains a repeating unit represented by the following general formula (III), General formula (III) Among them, R1 ~ R7 and m are as defined by formula (I); M1 represents an atomic group having two carbon atoms bonded to form an alicyclic structure which may have a substituent 591336 t, patent application scope; η represents 1 Or 2; L2 represents a single bond or η + 1-valent bonding group bonded to a carbon atom forming a ring. 4. A positive-type photoresist composition comprising: (A) a manganese salt compound represented by general formula (PAG4) of 0.01 to 20% by weight to generate an acid by irradiation with active light or radiation; (B) 40 to 9 9. 99% by weight of a resin having a partial structure represented by the following general formula (I) and increasing the solubility in an alkali developing solution by an acid action; (PAG4) (Where Rsl ~ Rs3 each represents an independent alkyl group which may have a substituent, and an aryl group which may have a substituent; and two of Rsl ~ Rs3 may each be bonded via a single bond or a substituent; each represents a relative ion) General formula (I) (Wherein in general formula (I), m is an integer of 1 to 6; Ri & R2 each represents an alkyl group or a cyclic alkyl group, or R1 and R2 are bonded to each other to form a ring ^ 1336 Alkyl; R3 and R4 each represent a hydrogen atom, alkyl or cyclic alkyl, or R3 and R4 are bonded to each other to form a cyclic alkyl; R5 to R7 each represent an alkyl, cyclic alkyl, aryl, Trialkylsilyl or trialkylsilyloxy). 5. The positive photoresist composition according to item 4 of the scope of the patent application, wherein the phosphonium salt of (A) is a compound represented by the following general formula [s I] which generates an acid by irradiation with active light or radiation, (Where Rs4 ~ Rs6 each represent an independent alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and a substituent which may have a substituent Fluorenyl group, fluorenyloxy group which may have a substituent, nitro group, halogen atom, hydroxyl group, carboxyl group; 1 ·· 1 ～ 5 m: 0 ～ 5 η ·· 0 ～ 5; 1 + m + η-1, Rs4 It means an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, a fluorenyl group which may have a substituent, and a substituent which may have a substituent X · R-S 〇3; R: represents an aliphatic hydrocarbon group which may have a substituent, an aromatic 591336 which may have a substituent 6. Aromatic hydrocarbon group in the scope of patent application). 6. A positive photoresist composition comprising: (A) 0.001 to 40% by weight of a compound that generates an acid by irradiation with active light or radiation relative to the solid content of all the photoresist; (B ) 40 to 99.99% by weight of the solid content of the entire photoresist, a resin having a partial structure represented by the following general formula (I) and capable of increasing the solubility in an alkali developer by the action of an acid; (E) A mixed solvent having a solid content concentration of 3 to 25% by weight, which contains at least one solvent of the following group A and at least one solvent of the following group B or at least one solvent of the following group A and the following group C Solvents; Group A: Propylene glycol monoalkyl ether carboxylic acid ester Group B: Propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate Group C: r-butyrolactone, ethylene carbonate and propylene carbonate General (I) R 'C-— C " FT In the general formula (I), m is an integer of 1 to 6; R1 and R2 each represent an alkyl group or a cyclic alkyl group, or R1 and R2 are bonded to each other to form a cyclic alkyl group; R3 and R4 are each Represents a hydrogen atom, an alkyl group or a cyclic alkyl group, or R3 and R4 are bonded to each other to form a cyclic alkyl group; R5 to R7 each represent an alkyl group, a cyclic alkyl group, an aryl group, a trialkylsilyl group, or a trioxane Silyloxy. 591336 VI. Application patent scope 7-A type of positive photoresist composition, which includes: (A) relative to the solid content of all photoresist, 〇〇〇 丨 ~ 40% by weight of active light Or a compound that generates an acid by radiation irradiation; (B) 40 to 99.99% by weight with respect to the solid content of all the photoresist, has a partial structure represented by the following general formula (I) and can be acted by an acid (E) A mixed solvent having a solid content concentration of 3 to 25% by weight, which contains at least one solvent of group A below, at least one solvent of group B below, and at least A solvent of the following group C; group A: propylene glycol monoalkyl ether carboxylic acid ester B group: propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate group C: 7-butyrolactone, ethylene carbonate And propylene carbonate-general formula (I) Wherein in the general formula (I), m is an integer of 1 to 6; R1 and R2 each represent an alkyl group or a cyclic alkyl group, or R1 and R2 are bonded to each other to form a cyclic alkyl group; R3 and R4 are each Represents a hydrogen atom, an alkyl group or a cyclic alkyl group, or R3 and R4 are bonded to each other to form a cyclic alkyl group; R5 to R7 each represent an alkyl group, a cyclic alkyl group, an aryl group, a trialkylsilyl group, or a trioxane Silyloxy. 8. A type of positive photoresist composition, which includes: (A) 0.001 to 40 weights 591336 relative to the solid content of all photoresists 6. Application for patent scope Stomach% irradiation with active light or radiation Acid-producing compounds; (B) 40 ~ 99.99% by weight with respect to the solid content of the entire photoresist, having a partial structure represented by the following general formula (丨), and the increase in the ratio by the action of acid Resin for solubility in alkali developing solution; (E) A mixed solvent having a solid content concentration of 3 to 25% by weight, which contains at least one lactate ester, at least one ester solvent, and an alkoxyalkyl propionate; (I) CMMNO In the general formula (I), m is an integer of 1 to 6; R1 and R2 each represent an alkyl group or a cyclic alkyl group, or R1 and R2 are bonded to each other to form a cyclic alkyl group; R3 and R4 are each Represents a hydrogen atom, an alkyl group or a cyclic alkyl group, or R3 and R4 are bonded to each other to form a cyclic alkyl group; R5 to R7 each represent an alkyl group, a cyclic alkyl group, an aryl group, a trialkylsilyl group, or a trioxane Silyloxy. 9. A positive-type photoresist composition comprising: (A) 0.001 to 40% by weight of a compound that generates acid by irradiation with active light or radiation relative to the solid content of all photoresists; (B) Relative to the solid content of all photoresist, 40 to 99.99% by weight of a resin having a partial structure represented by the following general formula (I) and capable of increasing the solubility in an alkali developer by the action of an acid (E) a mixed solvent having a solid content concentration of 3 to 25% by weight, which 591336 6. Scope of patent application Solvent containing heptanol; General formula (I) In the general formula (I), ra represents an integer of 1 to 6; Ri and R2 each represent an alkyl group or a cyclic alkyl group, or Ri and R2 are bonded to each other to form a cyclic alkyl group; R3 and R4 are each Represents a hydrogen atom, an alkyl group or a cyclic alkyl group, or R3 and R4 are bonded to each other to form a cyclic alkyl group; R5 to r7 each represent an alkyl group, a cyclic alkyl group, an aryl group, a trialkylsilyl group, or a trioxane Silyloxy. 10. The positive photoresist composition according to item 9 of the application, wherein the solvent of (E) further contains at least one kind of propylene glycol monoalkyl ether, alkyl lactate, and alkoxy alkyl propionate. 1 1. The positive photoresist according to any one of claims 8 to 10 in the scope of patent application, wherein the solvent of (E) further contains at least one kind of r-butyrolactone, ethyl carbonate and propylene carbonate .