TW200905394A - Negative resist composition and pattern forming method using the same - Google Patents

Abstract

A negative resist composition, includes: (A) an alkali-soluble polymer containing a specific repeating unit as defined in the specification; (B) a crosslinking agent capable of crosslinking with the alkali soluble polymer (A) under an action of an acid; (C) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (D) a specific quaternary ammonium salt as defined in the specification; and (E) an organic carboxylic acid, and a pattern forming method uses the composition.

Description

200905394 IX. INSTRUCTIONS: [Technical Field] The present invention relates to an ultra-micrography or other light system which is generally suitable for the manufacture of a sheet and a pattern for forming a pattern using the composition, by using an electron beam or X a light-blocking composition, and a form thereof for forming a composition having a specified base thereon. [Prior Art] In the manufacture of semiconductor devices (such as 1C3, the integration of lithography using photoresist compositions is becoming more and more high, and ultra-fine patterns in the meter range are required. To meet this short', for example, from g-line to In addition to excimer laser light, the i-ray or further front is undergoing the development of the technique. Specifically, 'electron beam lithography is patterned, and it needs to ensure the photoresist. Electron beam lithography is also because of its high resolution. Preparation of a reticle for exposure. A method of preparing a masking substrate by preparing a masking layer of a masking material (e.g., chrome), and a negative photoresist composition such as a VLSI or high-capacity microcrystal forming method. More particularly, the present invention forms a method of forming a negative pattern of a high resolution pattern. That is, in the method of the negative photoresist L L S I ) of the method for controlling the substrate of the film of the present invention, it is conventionally precision-treated. Recently, integrated circuits have been formed to have sub-micron or quarter-micro requirements, and the exposure wavelength has also tended to change to KrF excimer laser light. The method of using electron beam or X-ray lithography to locate the next generation or the next generation of high sensitivity and high resolution negative properties and widely used for semiconducting is as follows. It will be mainly included in a transparent substrate (such as a glass substrate layer formed thereon and selectively exposed on the shielding layer 200905394 to form a photoresist pattern. Then a photoresist pattern is used as a mask to transfer the pattern to the shielding layer to etch the unpatterned pattern. a masking portion, whereby a reticle including a transparent substrate on which a shielding layer of a predetermined pattern is provided is obtained. In the process using electron beam (which is a system different from block exposure), sensitivity is improved to shorten processing Time is very important, but in the case of negative photoresist used for electron beams, in the pursuit of higher sensitivity, in addition to lower resolution and degradation of pattern shape, line edge roughness is also deteriorated, and it is strongly required to simultaneously satisfy these properties. The line edge roughness used herein means that the photoresist edge at the interface between the pattern and the substrate irregularly fluctuates in the direction of the vertical line due to the photoresist characteristic, and the edge is generated when the pattern is viewed from directly above. Uneven appearance. This unevenness is transferred by the use of photoresist as an etch step of the mask, and the dimensional accuracy is compromised.超. In the ultra-fine area of 2 5 μm or less, the line edge roughness is an important problem to be solved. It is also known that when a photoresist pattern is formed on the mask layer for mask preparation, the pattern shape is degraded. When a negative photoresist is used, the pattern is disintegrated due to wear at the interface of the substrate, and the resolution is remarkably degraded, and it is a problem. High sensitivity to high resolution, good pattern shape, and good line edge roughness Degree is an exchange relationship, and how to satisfy these properties at the same time is very important. Regarding the photoresist suitable for use in electron beam or X-ray lithography, for high sensitivity, it mainly uses a chemically amplified photoresist using an acid-catalyzed reaction. And in the case of negative photoresist, it effectively uses a chemically amplified photoresist composition mainly comprising an alkali-soluble resin, a crosslinking agent, an acid generator, and an additive. 200905394 Various studies have been conducted so far to enhance the chemical amplification type negative The performance of the photoresist. The following investigations have been made on the additives (especially the ammonium salt type). For example, the patent discloses a tetraalkylammonium salt and a phenolic resin as disclosed in JP-A_4-5121. In combination, JP-A-8-ll〇6 3 8 discloses that tetraalkylammonium hydroxide, and JP-A-1 1 -1 4 9 1 5 9 discloses that a tetraalkylammonium salt has a side chain and has a side chain Combination of Polymers of Carboxylic Acids However, any combination of these known compounds cannot simultaneously satisfy all of the high sensitivity, high resolution, good pattern appearance, good line edge thickness, and good vacuum PED characteristics of the ultrafine regions. Further, JP-A-10-186660 discloses the use of an organic carboxylic acid, but does not describe the use of a specified resin and a specified ammonium salt. Further, JP-A-2003-295439 describes the use of an ammonium salt, but has no organic carboxylate. In addition, these patent publications all relate to improving the edge thickness of the wire to produce a good pattern appearance with less wear, which is an effect of the present invention. SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the technology for enhancing performance in precision processing of a semiconductor device or a photomask, and to provide a precision processing of a semiconductor device or a photomask in which an electron beam or an X-ray is used. At the same time, all of the negative photoresist compositions satisfying high sensitivity, high resolution, good pattern shape, good line edge roughness, and good vacuum PED characteristics, and a method of forming a pattern using the composition. As a result of intensive studies, the inventors have found that the object of the present invention is to use an alkali-soluble resin having a specified structure, a crosslinking agent, an acid generator, an ammonium salt having a specified structure, and a negative light of an organic carboxylic acid. Block the composition to achieve. 200905394 The present invention is as follows. (1) A negative photoresist composition comprising: (A) an alkali-soluble polymer containing a repeating unit represented by formula (1); (B) being capable of reacting with an alkali-soluble polymer (A) under the action of an acid Crosslinking (C) A compound which produces an acid upon irradiation with actinic rays or radiation; (D) a quaternary ammonium salt represented by formula (2); and (E) an organic carboxylic acid: formula (1):

Wherein A represents a hydrogen atom, an alkyl group, a halogen atom, or a cyano group; and 1 and R2 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group, or an alkoxy group. Or an alkylcarbonyloxy group; and η represents an integer from 1 to 3; Formula (2):

R4_ij|-Re B wherein R3 to R6 each independently represent an alkyl group, an alkenyl group, an aryl group, or an aralkyl group; 200905394 Β· represents an OH group, a halogen atom, a r7_c〇2- group, or an R7-S〇T Base: and R7 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. (2) The negative photoresist composition according to (1) above, wherein the crosslinking agent (B) is a phenol compound having two or more benzene rings in its molecule and containing no nitrogen atom. (3) A method of forming a pattern, comprising: forming a photoresist film from the negative photoresist composition described in (1) or (2) above; and exposing and developing the photoresist film. Further preferred embodiments of the invention are described below. (4) The negative photoresist composition according to (1) or (2) above, wherein the alkali-soluble polymer (A) further comprises at least one selected from the group consisting of formulas (3), (4) and (5) Repeating unit of the repeating unit: Formula (7): -(-ch2—〇-)-

X

200905394 Equation (4):

Equation (5):

A

Represents any base selected from the following structures: -10- 200905394

Wherein A has the same meaning as A in formula (1); X represents a single bond, -coo-group, 〇-yl' or _c〇N(Ri6)- group;

Rl6 represents a hydrogen atom or an alkyl group; the ruler to the R1S each independently have the same meaning as R1 in the formula (1); Rioi to Ri〇6 each independently represents a hydroxyl group, a dentate atom, a hospital group, a decyloxy group, an alkane A carbonyloxy group, an alkylsulfonyloxy group, an alkenyl group, an aryl group, a aryl group, or a fluorenyl group; and a to f each independently represent an integer of 〇 to 3. (5) The negative photoresist composition according to (1), (2), and (4) above, wherein the crosslinking agent (B) has a molecular weight of 1, 2 Å or less, and contains 3 in its molecule. Up to 5 benzene rings' and phenol derivatives having a total of two or more hydroxymethyl or alkoxymethyl groups, two or more hydroxymethyl or alkoxymethyl groups being concentrated or dispersed in benzene At least one benzene ring is bonded between the rings. (6) The negative photoresist composition according to (1), (2), (4), and (5) above, wherein the organic carboxylic acid (E) is selected from the group consisting of saturated or unsaturated aliphatic carboxylic acids and fats. At least one of a cyclodecanoic acid, an oxycarboxylic acid, an alkoxycarboxylic acid, a ketocarboxylic acid, and an aromatic carboxylic acid. The negative photoresist composition according to the above (6), wherein the organic acid (E) is selected from the group consisting of benzoic acid, 1-carbyl-2-naphthoic acid and 2-hydroxy-3-naphthoic acid. one. [Embodiment] The negative photoresist composition of the present invention will be described in detail below. Incidentally, when a group (atomic group) is represented by unsubstituted or unsubstituted, the group includes a group having no substituent and a group having a substituent. For example, r alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). (A) Alkali-soluble polymer The alkali-soluble polymer used in the present invention contains a repeating unit represented by the formula (1) as an important component. The alkyl group as A in the formula (1) is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the halogen atom as A include Cl, Br, and F. A is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group), more preferably a hydrogen atom or a methyl group.

Examples of the halogen atom as R] and R2 include Cl, Br, F, and I 〇 as an alkyl group of R1 and R2, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group. The group or the alkylsulfonyloxy group may have a substituent. Ri and R2 may also form a ring together. R] and R2 are each independently preferably a linear or branched alkyl group having 1 to 8 carbon atoms (which may have a substituent), an alkenyl group having 1 to 8 carbon atoms (which may have a substituent), and a carbon number of a 5- to 10-cycloalkyl group (which may have a substituent), a carbon-12-200905394 number 6 to 15 aryl group (which may have a substituent), and a carbon number of 7 to 16 aryl group (which may have The substituent), an alkoxy group having a carbon number of from 8 to 8 (which may have a substituent), or an alkylcarbonyloxy group having a carbon number of from 8 to 8 (which may have a substituent). Examples of the substituent include an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl), an aryl group (e.g., phenyl, naphthyl), an aralkyl group, a hydroxyl group, Alkoxy (eg methoxy, ethoxy, butoxy 'octyloxy, dodecyloxy), fluorenyl (eg ethyl, propyl, benzylidene), and pendant .

Ri and R2 are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms (which may have a substituent), an alkoxy group having 1 to 4 carbon atoms (which may have a substituent), Or an alkylcarbonyloxy group having a carbon number of 1 to 4 (which may have a substituent), still more preferably a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group) , ethyl, propyl, isopropyl), or an alkoxy group having a carbon number of 1 to 3 (e.g., methoxy, ethoxy, propoxy, isopropoxy). The polymer used as the component (A) of the present invention may have at least one repeating unit represented by the formulae (3) to (5), and a repeating unit represented by the formula (1) in the formula (3) to (5) Wherein 'A has the same meaning as a in the formula (1), X represents a single bond, -COO- group, -0-yl group, or -CON(R16)- group, and Ri6 represents a hydrogen atom or a carbon number of 1 to 3 An alkyl group (e.g., methyl, ethyl, propyl).乂 is preferably a single bond, -COO- or -CON(R16)-, more preferably -COO-based.

Rm to Ris each independently have the same meaning as R! in the formula (1). 200905394 101 to Ri〇6 each independently represent a radical, a halogen atom (Cl, Br, F τ \ a linear or branched base of 1 to 8 (which may have a substitution »), and a carbon number of 丨 to 8) Linear or branched alkoxy group (which may have a substituent) a linear or branched alkylcarbonyloxy group having a carbon number of 1 to 8 (which may have a substituent) or a linear or branched alkyl sulfonate having a carbon number of 1 to 8 a group (which may have a substituent), an alkenyl group having a number of 1 to 8 (which may have a substituent), an aryl group having a carbon number (which may have a substituent), and an aromatic group having a carbon number of 7 to 16 ( It may have a substituent) or a carboxyl group. Examples of the substituent are the same as the substituent of R t in the formula (1).

Rl01 to Rl6 are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms (which may have a substituent), or a carbon number of 1 An alkylcarbonyloxy group to 4 (which may have a substituent), more preferably a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a court having a carbon number of 1 to 3 (e.g., methyl, ethyl, propyl) , isopropyl), a carbon number of 1 to 3, such as methoxy, ethoxy, propoxy, isopropoxy, or a carbon number of 1 to 3 The base (e.g., anthryl, propyl) 〇a to f each independently represent an integer of 〇 to 3. The polymer used as the component (A) of the present invention may be any resin having only one repeating unit represented by the formula (1), a resin having two or more repeating units each represented by the formula (1), And a resin having a repeating unit represented by the formula (1) and at least one repeating unit selected from the repeating units represented by the formulas (3) to (5), and other polymerizable which can control film forming properties or alkali solubility The monomer is polymerized therein. -14- 200905394 Examples of such polymerizable monomers include, but are not limited to, styrene, alkyl-substituted styrene, alkoxy-substituted styrene, 0-alkoxystyrene, fluorenyl styrene, hydrogenated hydroxybenzene Ethylene, maleic anhydride, acrylic acid derivatives (such as acrylic acid, acrylate), methacrylic acid derivatives (such as methacrylic acid, methacrylic acid ester), N-substituted maleimide, acrylonitrile, And methacrylonitrile. The content of the repeating unit represented by the formula (1) in the polymer as the component (A) used in the invention is usually from 50 to 丨〇〇 mol%, preferably to 1 〇 莫 mol. /〇. In the polymer as the component (A), the ratio between the repeating unit represented by the formula (?) and the repeating unit represented by the formula (3) to (5) is preferably 100/0 to 50 in terms of molar ratio. /50, more preferably 100/0 to 60/40, still more preferably 100/0 to 70/30. The molecular weight of the polymer as the component (A) is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, by weight average molecular weight. The molecular weight distribution (Mw/Mn) of the polymer as the component (A) is preferably from 1.0 to 2.0, more preferably from 1.0 to 1.35. The amount of the polymer as the component (A) is from 30 to 95% by mass, preferably from 40 to 90% by mass, more preferably from 5 to 80% by mass, based on the total solid content of the composition. (In the present specification, the mass ratio is equal to the weight ratio.) The molecular weight and molecular weight distribution of the polymer are defined as polystyrene reduction oxime measured by GPC. The polymer as the component (A) can be synthesized by a known radical polymerization method or the 200905394 anionic polymerization method. For example, in a radical polymerization process, a vinyl monomer is dissolved in a suitable organic solvent, and a peroxide (for example, benzoyl peroxide), a nitrile compound (such as azobisisobutyronitrile), or oxidation is used. A reducing compound (e.g., cumene hydroperoxide) is used as the initiation reaction to carry out the reaction at room temperature or under heating, whereby a polymer can be obtained. In the anionic polymerization method, a vinyl monomer is dissolved in a suitable organic solvent, and a metal compound (e.g., butyllithium) is used as an initiator, and the reaction is usually carried out under cooling, whereby a polymer can be obtained. The following is a description of the designated examples of the alkali-soluble polymer used as the component (Α) of the present invention, but the present invention is not limited thereto. 200905394

200905394

f

0=?

CH2CH2-0-C

OH (20) ch3-fcH2-c4 0=C n I 0 ch2ch2- ch3-fcH2-c4 /-._Λ n O II -c- o=c I o

II

CH2-CH*CH2-〇-c OH 200905394

OH y

OH (25) -fCH2-Ci|f-CH2-CH)·

OH x

y (27) -fCH2-CH)- -(CH2-CH)- (26) -fCH2-Ctf -fCH2-CifL0y (28)

x

OH OCH3 (29)

-fCH2-C^ -fcH2-CH)-I x I

y h3c◦丫 och3 OH 〇CH3(31) -f CH2-Ch)-x -f ch2-ch)-

OH

Och3 y

(34) (33) 200905394 4cH2-CH)- -(CH2-CH)-

y HO' ^ H3ca ^ 〇ch3 (35) -(CH2-CH)- -f-CH2-CH)-

-fcH2-CH)- -fcH2-CH)-

x CH, OH

OH OH 〇-CH2- (38)

(37)

OH CH3 -f ch2-ch}-x -(ch2-ch}-

OH 〇-〇 (40) 0 4ch2-chHch2-ch>:

-o y (41) -fCH2-〇i(·αΗ2-αΗ)-I x y OH Cl (42)

-(-CH2-Cli——fCH2-CH)-I x I y

OH Br (43) OH NOo (44) -20 - 200905394

-fcH2-cp|——(ch2-ch)- I x I -fcH2-af -(ch2-ch)·

OH OH CN (45)

y -(ch2-ch)- -4ch2-ch)- (46) -fcH2-CH)- -f-CH2-CH}-

OH

OCH,

OH

(47) (48) o-ch2-

OH

y -(ch2-ch)- -(ch2-ch)- o-c-ch3 11 3 0

OH

(49) -fCH2-CI^--fCH2-CH)- (50)

x

OH

Ch3 y

OH

Cl y (51) (52)

I x I

y

OH

Br

OH

NO, y (53) (54) 200905394

OH

CN

(55) -(ch2-ch)- ~(-ch2-ch)-

OH (56),

OH (57)

-fCH2-CH)- -fcH2-CI-l)- -fcH2-CH)- -fCH2-CH)- -fCH2-CH)- -fcH2-CH}-ΦΧ...X... 〇H 〇CH3 (59) 〇 -f-CH3 (60)

-fCH2-CH)- -fcH2-CH)- -(-CH2-CH)- -fCH2-CH)- -{cH2-CH)- -(CH·ΦΧ y,Z O' 0 / -CH2 h3co och3

(61) (62) -(ch2-ch)- -(ch2-ch)- -(ch2-ch)- -(ch2-ch)- -fcH2-cH)- -(-ch2-ch)-^ y 12

OH 0, ck2 CI (63) h3co 〇ch3 OH Br (64) 22 - 200905394 -(CHj-CH^ -fCH2-CH)- ^-fCH2-CH)- ^ -fCH2-CHf -fcH2-CH)- CH2 -CH)-

, OH ΌΗ OCH,

〇-f-CH3 O (65) (66) -(CH2-CH)-X -fCH2-CH)- y-{CH2-CH)- χ -f-CHs-CHf -fCH2-Ch)- y-( -CH2

OH

O- 'CH, (67) HO, v H3CO^^〇CH3 (68)

-fCH2-CHf -fCH2-CH)- y-(cH2-(pH}- χ -fcH2-〇i)- y-(CH2-CH)-

x

OH

(69) HO' ^ H3CO^^OCH3 Cl Br (70)

OH -(ch2-ch)-o=c y O ch3

OH :h2-ch)-o=c y

CH2CH2OH (71) (72) -(ch2-ch)-

-fcH2-CH)-o=c y I -fCH2-CH)-x -fd

Ch2-o^- y

OH (73) CH2-CH-CH2OH T ch, in 0H ' (74)

23 - 200905394

(75)

OH OH (79) (80)

-24 - 200905394

-25 200905394 f

CH3 -(cH2-c4 -fCH2-CH)-0=C x CN y ch3 -c4 Λ x -fcH2-c4 -(CH2-CH)- o=c y I O O ch2-ch-ch2-o-c

OH (89)

OH

Ο Ο CH2-CH'CH2'〇-C

OH (90)

OH CH3 -fcH2-(p4^ ~fc , o ? ? ch2ch2-o-c ch2ch2oh o=c

OH :h2-ch)-o=c y

-fCH2-CH)- I Z CN (91)

(92) -26 - 200905394 In the above specified examples, the η table is not a positive integer, and χ, ^^, and z represent the molar ratio of the composition. In the case where the resin includes two components, the molar ratio is x = l 〇 to 95 and y = 5 to 90, preferably x = 40 to 90 and y = 10 to 60', and in the case where the resin includes three components, The molar ratio is χ=10 to 90, y=5 to 85, and ζ=5 to 85, preferably χ=40 to 80, y=10 to 50, and z=10 to 50. One of these polymers may be used singly or two or more thereof may be used in combination. [2] Acid crosslinking agent (ingredient (B)) In the present invention, a crosslinking agent which is crosslinkable under the action of an acid (hereinafter sometimes referred to as "acid crosslinking agent" or simply "crosslinking agent" It is used together with an alkali soluble polymer. Known acid crosslinkers are used here effectively. The acid crosslinking agent is preferably a compound or resin having two or more hydroxymethyl 'alkoxymethyl, methoxymethyl, or alkoxymethyl ether, or an epoxy compound. Further examples thereof include alkoxymethylated or decyloxymethylated melamine compounds or resins, alkoxymethylated or decyloxymethylated urea compounds or resins, hydroxymethylated or alkoxylated groups A phenolic compound or resin, and an alkoxymethylated-etherified phenol compound or resin. Component (B) is still more preferably a phenol derivative having a molecular weight of or less, having 3 to 5 benzene rings in the molecule and having a total of 2 or more hydroxymethyl or alkoxymethyl groups. The base or alkoxymethyl group is bonded to at least one of the benzene rings in a concentrated manner or distributed between the benzene rings. The use of this phenol derivative makes it more apparent that the effects of the present invention are produced. -27 - 200905394 The alkoxymethyl group of the bonded benzene ring is preferably an alkoxymethyl group having a carbon number of 6 or less, especially methoxymethyl, ethoxymethyl, n-propoxy Base, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, second butoxymethyl, or tert-butoxymethyl. Also preferred is an alkoxy-substituted alkoxy group such as 2-methoxyethoxy and 2-methoxy-1-propoxy. The crosslinking agent (B) is preferably a phenol compound having two or more benzene rings in the molecule and containing no nitrogen atom. Among these phenol derivatives, particularly preferred compounds are described below. -28 - 200905394

L4 OH

OH

OH -29 - 200905394

ο ο

OH L2 L3 -30 - 200905394

1 200905394

-32 - 200905394

(wherein L1 to L8 may be the same or different and each represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group). The phenolic derivative having a hydroxymethyl group can be obtained by reacting a corresponding phenol compound having no hydroxymethyl group (the compound of L1 to L8 in the above formula is a hydrogenogen-33 - 200905394 compound) with formaldehyde in the presence of a base catalyst. . At this time, in order to prevent resination or gelation, the reaction is preferably carried out at a temperature of 60 ° C or lower. In particular, the phenol derivative can be synthesized by a method described in, for example, JP-A-6-282067 and JP-A-7-64285. The phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. In this case, in order to prevent resination or gelation, the reaction is preferably carried out at a temperature of 100 ° C or lower. In particular, the phenol derivative can be synthesized by a method such as that described in the patent of E P - A - 63 2 0 0 3 . With respect to storage stability, a phenol derivative having a hydroxymethyl group or an alkoxymethyl group thus synthesized is preferred, but a phenol derivative having an alkoxymethyl group is particularly preferred for storage stability. One of these phenol derivatives having a total of two or more hydroxymethyl groups or alkoxymethyl groups bonded in a concentrated manner to at least one of the benzene rings or distributed between the benzene rings may be used alone or two or more thereof Can be used in combination. Preferred examples of the crosslinking agent further include (i) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-methoxymethyl group, and a (fluorene) epoxy group, which is described below. (i) Examples of compounds having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-methoxymethyl group include the EP-A-0 1 3 3 2 1 6 patent and the German patent 3,6 a monomer, an oligomer-melamine-formaldehyde condensate, a urea-formaldehyde condensate, and an alkoxy group disclosed in EP-A-0212482, the disclosure of which is incorporated herein by reference. A substituted compound and a benzoguanamine-formaldehyde condensate. More preferred examples include melamine-formaldehyde derivatives having at least 2 free N-hydroxymethyl groups, N-alkoxy-34 - 200905394 methyl groups or N-methoxymethyl groups, still more preferably N-alkoxy groups Methyl derivative. (ii) The epoxy compound includes a monomer, a dimer, an oligomer, or a polymer form epoxy compound containing one or more epoxy groups. Examples thereof include a reaction product of biphenol A and epichlorohydrin, and a reaction product of a low molecular weight phenol-formaldehyde resin and epichlorohydrin. Other examples include the epoxy resins described and used in U.S. Patent No. 4,0 2,6,058 and U.S. Patent No. 1,5,3,1,92. The crosslinking agent is preferably added in an amount of from 3 to 65% by mass, more preferably from 5 to 50% by mass. When the crosslinking agent is added in an amount of from 3 to 65% by mass, it can prevent the residual film ratio and the resolution from being lowered, while maintaining good stability of the photoresist solution during storage. In the present invention, one crosslinking agent may be used singly or two or more crosslinking agents may be used in combination. In addition to the phenol derivative, for example, in the case of using the other crosslinking agents of the above (i) and (ii), the ratio between the phenol derivative and the other crosslinking agent is converted to 100/0 to 20/80 in terms of molar ratio. Preferably, it is 90/10 to 40/60, more preferably 80/20 to 50/50 ° [3] A compound which can generate an acid upon irradiation with actinic rays or radiation (ingredient (C)) The photoresist composition includes a compound which can generate an acid upon irradiation with an actinic ray or a ray (hereinafter sometimes referred to as an "acid generator"). The acid generator which can be used is suitably selected from the group consisting of a photo-cationic polymerization light-curtain hair-curing agent, a photo-radical polymerization photoinitiator, a coloring matter photo-decoloring agent, and a light-changing agent, which is known to be in an actinic ray or A compound which produces acid when irradiated with radiation and is used for micro-35-200905394 photoresist, and mixtures thereof. Examples thereof include diazonium salts, iron salts, strontium salts, strontium salts, sulfonium imide sulfonates, sulfonium sulfonates, diazo two mills, two mills, and o-nitrobenzyl sulfonates. It is also possible to use a compound in which a group or a compound which can generate an acid upon irradiation with actinic radiation or radiation is introduced into the main or side chain of the polymer, such as U.S. Patent No. 3,849,137, German Patent No. 3,9 1 4,407, JP-A-63 -2 665 3 , JP-A - 5 5 - 1 64824 , JP-A - 62 - 6 92 6 3 , JP - A - 6 3 - 1 4 6 0 3 8 , JP - A - 6 3 - 1 6 3 4 5 2, JP - A - 6 2 - 1 5 3 8 5 3, and (' JP-A-63-146029 patent). A compound which produces an acid by the effect of light in the U.S. Patent No. 3,779,77 8 and the European Patent No. 1 2 6,7 1 2, preferably a compound which decomposes to generate an acid upon irradiation with actinic rays or radiation. It is a compound represented by the following formulas (ZI), (ZII), and (ZIII). μΐ 〇δ R201 R204—l+_R205 χ- R206' -R207 R202 『 R203

ZI ZII ZIII (in the formula (ZI), 'R2〇i, R2〇2 and 尺2〇3 each independently represent an organic group 〇 representing a non-nucleophilic anion, and preferred examples thereof include a sulfonic acid anion, a carboxylic acid An anion, anthracene (alkylsulfonyl) decyl anion, hexamethylene anion, BF4', PF 〆, and SbF 〆. The anion is preferably an organic anion containing a carbon atom. The organic anion includes an organic anion represented by the following formulas (AN1) to (AN4): -36- 200905394 RC3SO2

RcrS03®AN1

RcrC02®AN2

RC3SO2 02~yC /N θ R〇4S〇2~A Rc4S°2 RC5SO2 AN3 AN4 In the formulas (AN1) and (AN2), RCl represents an organic group. The organic group in the ft. to the organic group includes an organic group having a carbon number of 1 to 30, and preferably an alkyl group or an aryl group (which may be substituted), or a plurality of such groups are bonded via a single bond or a bond group (e.g. 0-, -C02-, -s-, -S03-, and -SC^NiRch)-) The base of the connection. f ;

Rih represents a hydrogen atom or an alkyl group, and may form a ring structure together with an alkyl group or an aryl group bonded to Rh.

The organic group of Rq is more preferably an alkyl group substituted by a fluorine atom or a fluoroalkyl group at the 1-position or a phenyl group substituted by a fluorine atom or a fluoroalkyl group. Since it has a fluorine atom or a fluoroalkyl group, the acidity of the acid generated upon irradiation with light increases and the sensitivity is enhanced. When Rq has 5 or more carbon atoms, at least one carbon atom is preferably such that a part of hydrogen atoms is retained instead of all hydrogen atoms are substituted by fluorine atom 1, and more preferably, the number of hydrogen atoms is larger than the number of fluorine atoms. Perfluoroalkyl groups having a carbon number of 5 or greater can reduce the toxicity to the environment.

The most preferred embodiment of Re is a group represented by the following formula. RC7—Αχ—Reg— In the formula, Re6 represents a perfluoroalkyl group having a carbon number of 4 or less, preferably 2 to 4, more preferably 2 to 3, or 1 to 4 fluorine atoms and/or Or 1 to 3 fluoroalkyl substituted phenyl groups. Αχ represents a single bond or a divalent bond (preferably -◦_, -C02-, -s_, -S03-, or -SOzNCRch)-). Rdi represents a hydrogen atom or an alkyl group, and -37 - 200905394 may combine R C 7 to form a ring structure.

Rc7 represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group (which may be substituted), a monocyclic or polycyclic cycloalkyl group (which may be substituted), or an aryl group (which may be substituted). The alkyl group, the cycloalkyl group and the aryl group which may be substituted each preferably have a fluorine-free atom as a substituent. In the formulae (AN3) and (AN4), RC3, ruler "and RC5 each independently represent an organic group. Preferred organic groups of Rc3, Rc4 and Rc5 in the formulas (AN3) and (AN4) and ": in Rq Preferred organic groups are the same.

Rc3 and RC4 can be combined to form a ring. The group formed by combining Rc 3 and R C4 includes an alkylene group and an extended aryl group, and is preferably a perfluoroalkylene group having a carbon number of 2 to 4. When the combination of rC3 and ?^ is formed into a ring, the acidity of the acid generated upon irradiation with light is increased and it is preferable because the sensitivity is enhanced. The carbon number of Rm ' Rm and the organic acid in the formula (ZI) is from 1 to 30, preferably from 1 to 20. (. _ R2〇i to R2〇3 may be combined to form a ring structure 'and this ring may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond, or a carbonyl group.) Combination R2 < u to R 2 〇 3 Examples of the group in which the member is formed include an alkylene group (e.g., a butyl group, a pentyl group). Specific examples of the organic group as R2 (M, R2〇2 and R2. 3 include the compound (ZI-1), (ZI) described later. -2) and a corresponding group in (ZI-3). The compound may be a compound having a plurality of structures represented by the formula (ZI). For example, the compound may be one having a -38 which is represented by the formula (ZI). - 200905394 A compound in which at least one of Rztn to R2〇3 is bonded to another compound of at least one of R2Q1 to R2〇3 in the compound represented by the formula (ZI). The component (ZI) is more preferably the following compound ( ΖΙ_ι), (zi-2) or (ZI-3) The compound (ZI-1) is an aryl sulfonium compound in which at least one of the sizing 2()1 to r2()3 of the formula (ZI) is an aryl group. , a compound having an aryl ruthenium as a cation. In the aryl ruthenium compound, R 2 G 1 to r 2 () 3 may each be an aryl group, or r 2 (a part of 11 to R 2 G 3 may be an aryl group) The rest are a yard base or a ring base. Examples of the aryl sulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an aryl group II. Cycloalkyl hydrazine compound. The aryl group in the aryl hydrazine compound is preferably an aryl group such as a phenyl group and a naphthyl group, or a heteroaryl group such as an anthracene residue and a pyrrole residue, more preferably a phenyl group or a fluorene group. In the case where the aryl hydrazine compound has two or more aryl groups, these two or more aryl groups may be the same or different. It is preferred that the alkyl group present in the aryl hydrazine compound is present if desired. It is a linear or branched alkyl group having a carbon number of 1 to 15, and examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, and a third butyl group. If present, if necessary, The cycloalkyl group in the oxime compound is preferably a cycloalkyl group having a carbon number of 3 to 15, and examples thereof include a cyclopropyl group, a cyclobutyl group and a cyclohexyl group. An aryl group or an alkyl group of R2〇1 to R2〇3 Each of the cycloalkyl groups may have an alkyl group (for example, an alkyl group having 1 to 15 carbon atoms) and a cycloalkyl group (for example, a carbon number of 3 to 15). An alkyl group, an aryl group (for example, an aryl group having 6 to 14 carbon atoms), an alkoxy group -39 - 200905394 (for example, an alkoxy group having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group, As the substituent, the substituent is preferably a linear or branched alkyl group having a carbon number of 丨 to i 2 , a cycloalkyl group having a carbon number of 3 to 12, or a linear, branched or cyclic alkoxy group having a carbon number of from 12 to 12. More preferably, it is a group having a carbon number of 1 to 4, or an alkoxy group having a carbon number of 1 to 4. The substituent may be substituted for the three members of R2qi to R2g3 or may be substituted for all of the two members. The aryl group to R2G3 The case 'substituent is preferably substituted at the opposite position of the aryl group. The compound (z I - 2) is described below. The chemical substance (ZI-2) is a compound in which the ruler 2()1 to R2Q3 in the formula (zi) each independently represents an aromatic ring-free organic group. The aromatic ring used herein includes a hetero atom-containing aromatic ring. As the htn to R2 < n no aromatic ring organic group usually carbon number is! Up to 3 〇, preferably 1 to 2 0. R2〇i to Ratn are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or an alkyl group, more preferably a linear, branched or cyclic 2 oxyalkyl group, or an alkoxycarbonylmethyl group. More preferably, it is linear or branched 2-oxoalkyl. The alkyl group as R2〇1 to R2〇3 may be linear or branched, and is preferably a linear or branched alkyl group having a carbon number of 1 to 10 (e.g., methyl, ethyl, propyl, butyl, pentyl). ). The alkyl group as R2^ to R2Q3 is more preferably linear or branched as a 2-oxyalkyl group or an alkoxymethyl group. The cycloalkyl group as R2〇1 to R2〇3 is preferably a cycloalkyl group having a carbon number of 3 to 10 (e.g., a cyclopentyl group, a cyclohexyl group, a norbornyl group). The cycloalkyl group as Rztn to R2〇3 is more preferably a cyclic 2-oxyalkyl group. The 2-oxoalkyl group as Ratn to R2〇3 may be linear, branched or cyclic -40 - 200905394 ' and preferably has a group of > c = 在 at the 2nd position of the above alkyl group or cycloalkyl group. The alkoxy group in the oxycarbonylmethyl group of R2 (n to R2〇3) is preferably an alkoxy group having a carbon number of 1 to 5 (e.g., an anthraceneoxy group, an ethoxy group, a propoxy group, a butoxy group). , pentyloxy). Each of the ruthenium 2 〇 1 to R 3 may be further substituted by a halogen atom, an alkoxy group (for example, an alkoxy group having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group. ZI-3) is a compound represented by the following formula (ZI-3), and it is a compound having a phenylhydrazine sulfonium salt structure.

Rx r\

In the formula (ZI-3), Rlc to RSc each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom. R6C and Rk each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.

Rx and R each independently represent an alkyl group, a ring-based group, an allyl group, or a vinyl group.

Rlc to R?. Any two or more members, or R X and Ry pairs, can be combined with each other

Examples of the group include a butyl group and a pentyl group.

The non-nucleophilic anions are the same. As R 1 . To R 7. The alkyl group of the alkane may be linear or branched, for example, a linear or branched base having a carbon number of -41 to 200905394 to 20, preferably a linear or branched alkyl group having a carbon number of 1 to 12 (for example, a methyl group, Ethyl, linear or branched propyl, linear or branched butyl, and linear or branched pentyl). As Rle to R7. The ring base is preferably a ring base having a carbon number of 3 to 8 (e.g., cyclopentyl or cyclohexyl). As R!. The alkoxy group to Rse may be linear, branched or cyclic, for example, a oxy group having a carbon number of 1 to 1 Å is preferably a linear or branched alkoxy group having a carbon number of 1 to 5 (e.g., methoxy, B) An oxy, linear or branched propoxy group, a linear or branched butoxy group, or a linear or branched pentyloxy group, or a cyclical oxy group having a carbon number of 3 to 8 (e.g., a cyclopentyloxy group, a cyclohexyloxy group) . It is preferably Ri therein. To R5. Any compound which is linear or branched, base, or linear, branched or cyclic alkoxy, and more preferably Ri. To R·5. The carbon number is a compound of 2 to 15. Thereby, the composition further enhances the solubility of the solvent and suppresses the generation of particles during storage. As the base of 1^ and Ry, as Rle to R7. The courtyard is the same. The alkyl group as Rx and Ry is preferably a linear or branched 2-oxoalkyl group or a polyoxycarbonylmethyl group. Linear, branched or cyclic 2-oxoalkyl groups are included as Rle to r7. The alkyl or cycloalkyl group has a > C = 〇 group at the 2-position. The alkoxy group in the alkoxycarbonylmethyl group is the same. To R5. The hospital has the same oxygen.

Rx and Ry are each preferably an alkyl group having a carbon number of 4 or more, more preferably 6 or more, still more preferably 8 or more. In the formulae (ZII) and (ΖΙΠ), 'R_204 to R2Q7 each independently represent aryl-42-200905394 (which may have a substituent), an alkyl group (which may have a substituent), or a ring-based group (which may have Substituent). The aryl group of R2〇4 to Κ·2〇7 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The base of R2〇4 to R2〇7 may be linear or branched, and is preferably a linear or branched alkyl group having a carbon number of 1 to 10 (e.g., methyl, ethyl, propyl, butyl, pentyl). . The cycloalkyl group of R2〇4 to R2〇7 is preferably a ring having a carbon number of 3 to 10 (e.g., a cyclopentyl group, a cyclohexyl group, a norbornyl group). Examples of the substituent which each of R 2 0 4 to R 2 0 7 may have include an alkyl group (e.g., an alkyl group having 1 to 15 carbon atoms), a cycloalkyl group (e.g., a ring having a carbon number of 3 to 15), An aryl group (e.g., an aryl group having 6 to 15 carbon atoms), an alkoxy group (e.g., an alkoxy group having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. X_ represents a non-nucleophilic anion and is identical to the non-nucleophilic anion of X- in the formula (ZI). Among the compounds which can generate an acid upon irradiation with actinic rays or radiation, the preferred compound further includes a compound represented by the following formulas (ZIV), (zv) and (ZVI):

In the formulae (ZIV) to (ZVI), Ar3 and ΑΓ4 each independently represent a substituted or unsubstituted aryl group. R2〇8 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkane-43 - 200905394 group, or a substituted or unprevious & 1-4 aryl group. R 2 0 9 and R 2 | n are unsubstituted or unsubstituted alkyl, substituted or substituted cycloalkyl, substituted # ± 赫 h substituted or unsubstituted aryl, or an electron attracting group. R2Q9 is preferably substituted aryl by substituting ggr Φ %, and R21. It is preferably an electron attracting group, more preferably a cyano group or a fluoroalkyl group. A is unsubstituted or unsubstituted alkylene, substituted or unsubstituted alkylene, or substituted or unsubstituted extended aryl. Among the compounds which generate an acid upon irradiation with actinic rays or radiation, preferred are compounds represented by the formulae (ZI) to (ZIII), more preferably compounds represented by the formulae (ZI) and (ZII), and still more Preferably, the compound is represented by the formula: ^^^^^. Further, it is preferably a compound which can produce an acid represented by any of the following formulas (AC 1) to (AC 3 ) when irradiated with actinic rays or radiation. RC3SO2 RC3SO2

Rc4S02-CH Rc5S〇2

Rd-S03H NH RC4SO2 AC1 AC2 AC3 is a preferred acid generator, wherein in the structure of formula (z I), X - is a compound selected from the group consisting of anions of the formulae (AN1), (AN3) and (AN4), and A more preferred compound is a compound wherein X' is an anion selected from the group consisting of formulas (AN3) and (AN4). A particularly preferred example of a compound which can produce an acid upon irradiation with actinic radiation or radiation is described below. -44 - 200905394 (Q^-s+ CF3SO3-3 (Of c·- (21) (22) (Of (4) 〇3- (Of ° full (z4) (25) cf3 (〇f+-〇3s^pH :( Of,〇3S^ cf3 (z7) (2δ) (〇3S+ CiiF23C00· (OKS+ C2F5-0-C2F4S03- (z1〇) (211) c8f17so3· 3(z3) (<Q^s+ c6f13so3-(26) /

<z13)

-S, CgF^yS〇3" (Z9) 卜+ 3 o3s (z12) 〇

O3S~^F (Of 〇N^0 F 0 (221)

(222) 200905394

ο ν2 〇 ιι .·* ι« -S-C-S' ο ρ (LpJ^N-〇-g-CF3 Ο tb-omO -ml·

(ζ33) (Ζ34) (Ζ35) (236) Ο

r 『-'c4h9c4F9so3- (Ζ46)

Γο γλyx«v ’C12H2S C4F9SO3 (247) C4F3SO3- (248) C4F9SO3' (ζ49) -46- 200905394 so3·

(〇rF

F OC12h^5 S〇3

f f SC12H25

SOa· (OrF丄F

F

F 〇今C12H25 o (252) (250) (z51) FFFF 3S+ As-n-〇44-c12H25 (.〇as44〇^-〇_^ (z53) o FFFF (Z54) -s* °S$ 3 ( 255)

OF / (z58)

Γ3 0 p F (z56) 〇-S-C2f5 -S+ -N 3 〇今 C2P5 O (Z59> OBu

OeS~C4F9 -S+ *N* 3 〇*S"C*F9 0 (z6〇) C4F9SO3- -S* 4U 辟 F〇 〇F 卜 F〇 l〇° (z61) (z62)

OBu -S+ -OaS-H-^ (265) OBu

F F -o3s-H" F F (Z66) <3>

〇X C4F9SO3' (ζβ7) 200905394

(209) (shed) ?p3o=s:oo Is©© c—s*cf3〇.lJ>CFs C2F5 -<Q-S0 0C-S-C2F5 b 〇,〇〇 c2F5

(Z72) (z70) (271)

(z73> 〇2h o-so〇 ©c- Io-s:ov C2Fs -S-C2Fs (z74) -48 - 200905394

(ζ75) (ζ7δ) (z77)

(z79) (z80)

-49 - 200905394 One of these acid generators may be used alone or two or more of them may be used in combination. In the case where two or more are used in combination, it is preferred to combine a compound which can produce two or more organic acids having a total number of atoms (excluding hydrogen atoms) which differ by two or more. The content of the acid generator in the composition is preferably from 0. 1 to 20% by mass, more preferably from 0.5 to 10% by mass, still more preferably from 1 to 7% by mass, based on the total solid content of the negative photoresist composition. . [4] The quaternary ammonium salt represented by the formula (2) (ingredient (D)) may have a substituent as a group, an alkyl group, an aryl group, and an aromatic group in the formula (2). Further, two or more of R3 to R6 may be combined to form an alicyclic or aromatic ring. R3 to each is preferably a carbon number! Linear or branched alkyl group to 3 Å, linear or branched alkenyl group having 1 to 30 carbon atoms, linear or branched aryl group having 6 to 8 carbon atoms, linear or branched aralkyl having 7 to 18 carbon atoms A group or a group comprising a combination of these groups. These substituents may have a substituent, and examples of the substituent include the formula (1). Further, each of these groups may have a substituent of 1^ in the linkage group, and a hydroxyl group. ΰ , such as ether groups, ester groups and guanamine groups. R3 to R6 are each preferably a linear or branched alkyl group having a carbon number of 丨 to 2 s, or a linear or branched alkenyl group having a carbon number of 25, and still more preferably a linear or branched alkyl group having a carbon number of 1 to 2 Å. . In the R7_c 〇 group and the R7_S〇3· group as Β·, r7 is preferably represented

A branched alkenyl group, a linear or branched aryl group having a carbon number of 6 to, a carbon number of 1 to 8, or a linear or branched aralkyl group having a carbon number of 7 - 50 - 200905394 to 18. B_ is preferably an OH group, a halogen atom (e.g., chlorine, bromine, iodine, fluorine), or an R7-C02_ group (wherein R7 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). More preferably, it is a fluorene atom, a halogen atom (e.g., chlorine, bromine, iodine, fluorine) or R7-C02$ (wherein R7 is preferably an alkyl group having 1 to 4 carbon atoms). Preferred examples are specified, but the invention is not limited thereto. / !. · 200905394 D-1 ^H3 OH" D-2 S 〇H H3C-N-CH3 C2H5-N-CgHg I CHa CaH5 nC^Hg-N-nQ^Hg H3C-N-n-CgH-jy 0G4H9 n-CaH-j7 calving · D-4 | '^8Hl7 〇h'

HaC-N-n-CflH17 D-5 n-C4H9.丨' IVC4H9- N a η·〇4Η9 D-6 ch3

Br H3CN—π-0〇Η·(7 CHg D-7 n-C12H25 qh H3C—N-n-C^2^25 ch3 D-8 CH,

OH

O H3C—N —CH2-0—O-C2 H5 ch3

D-10 n-C4H9 Br I + Λ .. 1VC4H9-N-n-C4H9 (VG4H9 D-11 D-12

200905394 D-13 D-14 Guang H9 o2c-ch3 π-〇4Η^一N一nC^g n-C4H9 丫2H5 '〇2C-CH3 C2H5-N- C2H5 C2H5 / k: D'15 CH3 OHh3c-n^ Ch2^ch=ch-c2h5 CHa D-16 CHg

OH H3C—N^CH2-^CH=CH2 ch3 D-17 D-19 c2h5 C2H5—N—CzH5 CH3 HgC—N—CH3 ch3 o3s-ch3 D-18 D-20

OH ch3U /CH3 H3C—N—CH2-CH

OH 〇2〇一π-C” H23 CH〇 h3c-^ch2)^Q ch3 D-21 〇H ch3 CH3 D-22

OH 2^O-C2H5 CH3 The content of the component (D) used in the present invention is preferably 〇. 01 to 1 〇% by mass, more preferably 〇. 〇3 to 5 by mass based on the total solid content of the negative photoresist composition. % is still more preferably 0.0 5 to 3% by mass. In the present invention, one of the quaternary ammonium salts as the component (D) may be used singly or two or more thereof may be mixed and used. [5] Organic carboxylic acid (ingredient (E)) The organic carboxylic acid compound as the component (E) is not particularly limited, and 200905394 such as a saturated or unsaturated aliphatic carboxylic acid, an alicyclic carboxylic acid, an oxycarboxylic acid, Alkoxycarboxylic acids, ketocarboxylic acids, and aromatic carboxylic acids can be used. Examples thereof include monovalent or polyvalent aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid, alicyclic carboxylic acid' Such as 1,1-cyclohexanedicarboxylic acid ' 1,2-cyclohexanedicarboxylic acid, hydrazine, 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and hydrazine, hydrazine _ Cyclohexyl diacetic acid, unsaturated aliphatic carboxylic acid 'such as acrylic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, methacrylic acid, 4-pentenoic acid, propynoic acid, 2-butenoic acid'-butene Diacid, fumaric acid, and acetylene carboxylic acid 'oxycarboxylic acid, such as oxyacetic acid, alkoxycarboxylic acid' such as methoxyacetic acid and ethoxy acetic acid, ketocarboxylic acid, such as pyruvic acid, Benzoic acid, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2-hydroxy-3-nitrobenzoic acid, 3,5-dinitrobenzoic acid, 2-nitrobenzoic acid, 2,4-dinitrobenzoic acid , 2,5-dinitrobenzoic acid, 2,6-dinitrobenzoic acid, 3,5-dinitrobenzoic acid, 2-vinylbenzoic acid, 4-vinylbenzoic acid, citric acid, paralysis Acid, isophthalic acid, 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, and 2-hydroxyl Base-3 -naphthoic acid. In the present invention, when a pattern is formed by using an electron beam in a vacuum, the organic carboxylic acid may evaporate from the surface of the photoresist film to contaminate the image forming chamber, and thus the preferred compound is an aromatic organic carboxylic acid. More preferably, for example, benzoic acid, hydrazine-hydroxy-2-naphthoic acid and 2-hydroxy-3-naphthoic acid. One of the organic citric acids may be used alone or in combination of two or more. The amount of the organic residual acid (E) blended is preferably from 0.01 to 10 parts by mass, more preferably from 5 parts by mass to 5 parts by mass, still more preferably 0.01%, per 1 part by mass of the test polymer (A). Up to 3 parts by mass. -54- 200905394 The blending ratio between the quaternary ammonium salt of the component (D) and the organic carboxylic acid as the component (E) is preferably (D) / (E) = 5 to 95 / 95 to 5 (mass More preferably, (D) / (E) = l 〇 to 90 / 90 to 10 (mass ratio). If desired, the negative photoresist composition of the present invention may further contain a known compound such as a nitrogen-containing organic basic compound, a dye, a surfactant, a photo-decomposable basic compound, and a photobase generator. Examples of such compounds include the respective compounds described in JP-A-2 0 02 - 6 0 0 0 patent. Further examples of the solvent which is used in the negative photoresist composition of the present invention include the solvent similarly described in JP-A-2208-605. Preferable examples of the solvent include ethylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether Acid ester, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone , ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone alcohol, N-methylpyrrolidone, hydrazine, hydrazine-dimethylformamide, butyrolactone , Ν, Ν dimethyl dimethyl acetamide, propyl carbonate, and ethylene carbonate acetal. One of these solvents may be used singly or some may be used in combination. The solid material of the photoresist composition is preferably a solid material concentration of 1 to 4% by mass, more preferably 1 to 30% by mass, still more preferably 3 to 2% by mass, dissolved in the above solvent. The negative photoresist composition of the present invention is coated on a substrate to form a film. The thickness of the coating film is preferably from 0.05 to 4.0 μm. If desired, a commercially available inorganic or organic antireflective film can be used in the present invention -55-200905394. Further, the antireflection film can be used by coating it on the upper layer of the photoresist. As the antireflection film, an antireflection film described in JP-A-2002-65 00 can be used. The mode of use of the negative photoresist composition of the present invention is described below. For example, in the fabrication of a precision integrated circuit, the step of forming a pattern on the photoresist film includes directly coating the negative photoresist composition of the present invention on a substrate (for example, a ruthenium/ruthenium dioxide film, a glass substrate, a metal substrate, nitrogen). On the antimony substrate, the titanium nitride substrate, or the chrome oxide substrate, or on the anti-reflection film provided by previously coating on the base f plate, irradiated with radiation or actinic rays from the light source directly or through the reticle The film is coated, and the photoresist film is heated, developed, washed, and dried, whereby a good photoresist pattern can be formed. In the present invention, the substrate is preferably a substrate other than ruthenium (bare 矽), and it is more preferable to provide a metal deposition film or a substrate containing a metal film on the surface thereof, and it is still more preferable to provide Cr, Mo, MoSi, TaSi on the surface thereof. Or a vapor deposited film of the oxide or nitride thereof, or a substrate containing a film of Cr, Mo, MoSi, TaSi, or an oxide or nitride thereof, more preferably providing Cr, MoSi, TaSi, or A substrate of a film of an oxide or a nitrogen oxide. The light source is preferably a light having a wavelength of 150 to 250 nm (especially a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), or an F2 excimer laser (157 Nai). M)), electron beam or X-ray source. It is preferable in the present invention to use an exposure light source that emits an electron beam or an X-ray. The developer used in the negative photoresist composition of the present invention may be a known developer, and examples thereof include the developer described in JP-A-2208-605. [Examples] -56 - 200905394 The present invention is described in detail below with reference to examples, but the invention should not be construed as being limited thereto. 1. Synthesis Example of Composition Material (1) Alkali-Soluble Polymer (Component A) Synthesis Example 1 (Synthesis of Resin (29)): 4-Ethyloxystyrene (3-9 g (0.024 mol)) and hydrazine • 8 g (0.006 mol) of 4-methoxystyrene dissolved in 30 ml of 1-methoxy-2-propanol and stirred in a stream of nitrogen at 7 (TC added to 70 over 2 hours) ML containing 50 mg of 2,2'-arsenazo (2,4-dimethylvaleronitrile) (V-65, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, 9.1 g (0.056 a solution of 4-acetoxystyrene with 1.9 g (0.014 mol) of 4-methoxystyrene in 1-methoxy-2-propanol. Add 50 mg after 2 hours. The initiator was further reacted for 2 hours. Then the temperature was raised to 90 ° C, and stirring was continued for 1 hour. The resulting reaction solution was cooled, and then poured into 1 liter of ion-exchanged water with vigorous stirring to precipitate white. Resin. The obtained resin is dried and then dissolved in methanol of 100 ml, and after the addition of 25% by weight of tetramethylammonium hydroxide to hydrolyze the ethyl oxy group in the resin, the solution is dissolved. The white resin was precipitated by neutralizing with an aqueous hydrochloric acid solution, and the resin was washed with ion-exchanged water and dried at a low pressure to obtain 11.6 g of the resin (29) of the present invention. The molecular weight of the obtained resin was measured by GPC and found to have 9,200. Weight average molecular weight (Mw, in terms of polystyrene) and dispersibility (Mw/Mn) of 2.0. A polymer which is used as the component (A) of the present invention is synthesized in the same manner. (2) Crosslinking agent (ingredient B) Synthesis of Synthesis 200905394 (HM-l): 1-[α-Methyl(4-hydroxyphenyl)ethyl]-4-[ot,cx-indole(4-phenylphenyl)ethyl] Benzene (Trisp-PA manufactured by Honshu Chemical Industry Co., Ltd.) (20 g) was added to a 1% by weight aqueous potassium hydroxide solution and stirred to dissolve, and gradually added to the mixture at room temperature for 1 hour while stirring the solution. ML 3 % formaldehyde aqueous solution. After further stirring at room temperature for 6 hours, the solution was poured into a dilute sulfuric acid aqueous solution, and the precipitate formed by filtration was collected, washed thoroughly with water, and then recrystallized from 30 ml of methanol. 2 0 " gram has the structure shown below hydroxymethylphenol derivative [HM-1] white End purity (as measured by liquid chromatography method) was 92%.

Synthesis of [HM-1] (MM-1): The hydroxymethylphenol derivative [HM-1] (2 g) obtained in the above Synthesis Example was added to 1 liter of methanol and stirred and dissolved under heating. Then, 1 ml of concentrated sulfuric acid was added to the resulting solution, and the mixture was refluxed under heating for 12 hours. After the end of the reaction, the reaction solution was cooled' and 2 g of potassium carbonate was added thereto. The mixture was sufficiently concentrated, and 300 ml of ethyl acetate was added thereto. The resulting solution was washed with water' and then concentrated to dryness to give 22 g of a methoxymethyl phenol derivative [MM·1] white solid having the structure shown below. Its purity is 90% (as determined by liquid chromatography). -58 - 200905394 ch3och2 〔MM-1〕H0 CH3OCH2

H3COH2C

Ch2och3 ch2och3 The phenol derivative shown below was synthesized in the same manner.

-59 - 200905394

-60 - 200905394 2. Example [Example 1] (1) Preparation and coating of negative photoresist coating solution (composition of negative photoresist coating solution) Component (A): Resin (2 9) 0.40 g component ( B): Crosslinking agent Μ Μ -1 0 · 1 2g Ingredients (C): Acid generator C-1 0·〇5g Ingredients (D): Ammonium salt D-1 0.002g Ingredients (Ε): Organic carboxylate Acid strontium-1 0.012 g The above coating solution was dissolved in 9.0 g of propylene glycol monomethyl ether acetate, and 0. 001 g of PF6320 (manufactured by OMNOVA 'hereinafter referred to as W-1) was added as a surfactant and dissolved. The resulting solution was microfiltered through a membrane filter having a pore size of 0.1 μm to obtain a photoresist solution. Using a spin coater Mark 8 manufactured by Tokyo Electron Ltd., the photoresist solution was coated thereon with a photomask. Using a masking film to treat the vapor deposited Cr oxide on a 6-inch wafer and drying it on a 1 1 〇 °C hot plate for 90 seconds to obtain a thick film of 3 μm. (2) Negative The photoresist pattern was produced by using an electron beam imaging apparatus (HL 75 0 manufactured by Hitachi, Ltd., accelerating voltage: 50 KeV) to receive the pattern of the photoresist film. After the irradiation, the photoresist film was irradiated at 120 ° C. The plate was heated for 90 seconds, immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMA®) for 60 seconds, washed with water for 30 seconds, and dried. The sensitivity, resolution, and resolution of the resulting pattern were evaluated by the following methods. The shape of the pattern and the thickness of the line edge. -61- 200905394 (2-1) Sensitivity The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), and the analysis was performed. · The exposure dose required for a 1 5 -micron line (line: gap = 1 : 1) is defined as sensitivity. (2 - 2) The resolution will produce the limiting resolution of the exposure dose of the sensitivity defined above (offline and The gap and the resolution are defined as the resolution force. (2 - 3 ) Pattern shape (0.1-micron line pattern of the irradiation dose which produces the sensitivity defined above using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.)) The cross-sectional shape is evaluated according to the three-point scale of rectangle, slightly worn and worn. (2-4) The line edge roughness is the radiation dose that produces the above sensitivity, and the longitudinal direction of the 0.1 5 -micron line pattern is 5 0 In any of the 30 points in the micron area The line width is evaluated by 3 σ. ((2-5) Vacuum PED characteristics The wafer is fixed in a vacuum chamber and irradiated with an electron beam that produces an irradiation dose of the above sensitivity, and immediately or 3 hours after the irradiation. The wafer was baked (heat treated) at 120 ° C for 90 seconds' and then developed as described above to obtain a line pattern. A 0.15-micron line pattern obtained by baking and developing immediately after electron beam irradiation, and a 0.15-micron line pattern obtained by baking and developing 3 hours after electron beam irradiation, by scanning electron microscope (S_922〇, manufactured by Hitachi, Ltd.) measures the line width 'and defines the difference therebetween as vacuum PED special 200905394. The results of Example 1 were good, ie sensitivity: 6.0 μ (:/cm 2 , resolution: 〇. 1 1 μm, pattern shape: rectangle, line edge roughness: 6.0 nm, and vacuum PED characteristics: 2.0 nm. [Examples 2 to 16] Preparation of a photoresist solution and formation of a negative pattern were carried out in the same manner as in Example 1, except that the components shown in Table 1 below were used. In Table 1, two or more components were used. The ratio is the mass ratio. The evaluation results are shown in Table 2. [Comparative Example 1] Preparation of a photoresist solution and formation of a negative pattern were carried out in the same manner as in Example 1, except that as shown in Table 1, it was not used as a component (Ε). The organic carboxylic acid. The evaluation results are shown in Table 2. [Comparative Example 2] The preparation of the photoresist solution and the formation of a negative pattern were carried out in the same manner as in Example 1, except that as shown in Table 1, the use of the formula (1) was not used. The phenolic resin of the repeating unit was used as a resin of the component (Α). The evaluation results are shown in Table 2. [Comparative Examples 3 and 4] Preparation of a photoresist solution and formation of a negative pattern were carried out in the same manner as in Example 1, except that As shown in Figure 1, only known nitrogen-containing organic basic compounds are used. Not used as the component (D) quaternary ammonium salts of the evaluation results are shown in Table 2. -63--200905394

I谳Μ Γ: Starting 13⁄4 S gd 1 1 (N 1 _« 1 爹(N —I 1—^ t 1 1 W-2 Solvent (9.0 g) 1 00 S-1/S-2: 80/20 1 1 cn Sl/S-2= 80/20 CN C/l :Sl/S-2= 80/20 rn Sl/S-2= 80/20 Sl/S-2= 80/20 Sl/S-2 = SO/20 Sl/S-2= 80/20 φ愁 chain燊¢1 ΨΡ E-1 0·012 gram E-3 0.012 gram Ε-3 0·012 gram E-3 0.012 gram E-1 0.012 gram E -3 0.012 g E-2 0.012 g 1 E-4 0.012 g E-3 0.024 g E-1 0.012 g E-1 0.012 g E-1 0.012 g other ingredients F-2 0.002 g Fl 0.002 g as ingredient (D) Ammonium salt D-1 0.002 g D-1 0.002 g D-3 0.003 g D-10 0.004 g D-1 0.002 g D-12 0.006 g D-2 0.002 g D-2 0.002 g D-1 0.002 g D- 1 0.002 g D-1 0.002 g D-1 0.002 g as the component (C) of the acid generator C-1 0.05 g C-1 0.05 g C-2 0.05 g C-3 0.05 g | C-2 0.05 g C- 2/C-4=50/50 0.05 g C-2 0.05 g 1 C-4 0.05 g C-2/C-3=50/50 0.05 g C-4 0·06 g C-1 0.05 g Z-85 0.04 g as a component (Β) crosslinker ΜΜ-1 0.12 g MM-1 0.12 gΜΜ-2 0.11 g MM-3 0.12 g MM-1 0.12 g MM-3 0.12 MM-1 0.12 g CL-1 0·12 g MM-1 0.12 g MM-1 0.12 g MM-1 0.12 g MM-1 0.08 g resin as a component (Α) (0.40 g) (29) Mw=9200 x /y=80/20 Mw/Mn=2.0 (2) Mw two 5000 Mw/Mn=1.18 (1) Mw=2500 Mw/Mn=1.15 (2) Mw=7000 Mw/Mn=1.3 (27) Mw-3500 x/y=85/15 Mw/Mn=1.2 (25) Mw=5000 x/y=60/40 Mw/Mn=ll (32) Mw=7500 x/y=80/20 Mw/Mn=1.6 (2 Mw-5000 Mw/Mn=1.18 (2) Mw=5000 1.1/ (1) Mw=2500 1.1=75/25 (58) Mw=3500 x/y=80/20 Mw/Mn two 2.0 (2) Mw =5000 Mw/Mn=1.18 (25) Mw=5000 x/y=60/40 Mw/Mn=ll Example <N inch OO Os o 1 1 CN - inch 9丨200905394 CN W-2 W-2 CN IS s Agricultural 5 1 1 1 1 ^ 1 耷Sl/S-2= 80/20 Sl/S-2= 80/20 Sl/S-2= 80/20 Sl/S-2= 80/20 Solvent (9_0克) ^1 ^ 1 Ο) \ 1 00 ι·Η 1 CO E-2 0.012 gram El 0.012 gram. _1 El 0.012 gram El 0.012 gram g φ 愁 chain invite E-1 0.012 gram El 0.012 gram El 0.012 gram other Ingredient D-1 0.002 g D-1 0.002 g D-1 0.002 g D-1 0.002 g ammonium salt or comparative compound 1_ Id-i ! 0.002 g D-1 1 0_002 g F-3 0-004 g Gl 0.002 g Z-85 0.04克 Z-87 0.02 g Z-88 0.02 g Z-87 0.02 g Z-88 0.02 g Z-88 0.04 g as the component (C) acid generator C-1 0.05 g C-1 〇.〇5 g C- 4 0.06 g 1 C-1 i 0.05 g MM-1 0.08 g MM-1 0.08 g MM-1 0.08 g MM-1 0.08 g as a component (Β) crosslinker MM-1 0.12 g MM-1 0.12 g MM -1 0.12 g MM-1 0.12 g (1) Mw=2500 Mw/Mn=1.15 (2) Mw=5000 Mw/Mn=1.18 (1)/(2)=25/75 (mass ratio) (1) Mw =2500 Mw/Mn=1.15 (2) Mw=5000 Mw/Mn=1.18 (1)/(2)=25/75 (mass ratio) (1) Mw=2500 Mw/Mn=1.15 (2) Mw=5000 Mw/Mn=1.18 (1)/(2)=25/75 (mass ratio) (1) Mw=2500 Mw/Mn=1.15 (2) Mw-5000 Mw/Mn=1.18 (1)/(2)= 25/75 (mass ratio) Resin (0.40 g) (29) Mw=9200 x/y=80/20 Mw/Ma=2.0 ml ό 1 stretch < .g know urn c · Bu ^ 〇ro ! (25) Mw = 5000 x / y = 60 / 40 Mw / Mn II 1.1 (29) Mw = 9200 x / y = 80 / 20 Mw / Mn = 2.0 cn inch comparison example (N m inch 丨 S 9 - .匡 ii_M 长嗽鹦鹉旮谳旮谳窍锲盘窍锲<10^旺赵坩* 200905394 The following is a shorthand for the table. (Crosslinking agent) CL-1 : ch2och3 ch2och3 ch3och〆 Ν γΝ γ" N, CH2OCH3 ΝγΝ cH [CH2OCH3 CH30 The acid generator used in Table 1 is as follows. c -1 : triphenylsulfonium hexafluorobutanesulfonate C - 2 : triphenylsulfonium C-3 of pentafluorobenzenesulfonate : triphenylsulfonium C-4 : 2,4-dimethylbenzenesulfonate The acid generator of the phenylbenzenesulfonate 4-phenylhexylphenyl hydrazine used in Table 1 is as follows. E-1 : Benzoic acid E - 2 : 2 -naphthoic acid E-3 : 2-hydroxy-3-carboxylic acid E-4 : o-hydroxybenzoic acid ei K 0 gy ο The other components used in Table 1 are as follows (both by Tokyo) Made by Kas Co., Ltd.). F-l: 2,4,5-triphenylimidazole F-2 :

F - 3 : Triphenylamine G-1 : Trimethylammonium hydrochloride -66- 200905394 The solvents used in Table 1 are as follows. S-1: propylene glycol monomethyl ether acetate S - 2 · propylene glycol monomethyl ether The surfactants used in Table 1 are as follows. W-1 : PF6 3 2 0 (manufactured by OMNOVA) W-2: Megafac F 1 76 (manufactured by Dainippon Ink & Chemicals, Inc.) Table 2 Example sensitivity (μθ/cm2) Resolution (micron) Pattern shape (press 3-stage scale evaluation) Line edge roughness (nano) PED characteristics in vacuum (nano) 1 6.0 0.11 Rectangular 6.0 2.0 2 5.0 0.10 Rectangular 5.0 1.7 3 6.0 0.12 Rectangular 6,0 2.0 4 7.0 0.12 Rectangular 6.5 1.8 5 5.0 0.10 Rectangular 5.5 1.5 6 6.0 0.13 Rectangular 7·0 1.6 7 7.0 0.12 Rectangular 6.5 1.5 8 6.0 0.14 Rectangular 7.0 1.9 9 5.0 0.10 Rectangular 5.0 1.6 10 5.0 0.10 Rectangular 5.0 1.8 11 7.0 0.14 Rectangular 6.5 1.9 12 7.0 0.12 Rectangular 6.5 2.0 13 6.0 0.10 Rectangular 6.0 1.8 14 5.0 0.10 Rectangular 5.5 1.7 15 6.0 0.11 Rectangular 6.0 1.6 16 5.0 0.11 Rectangular 6.0 1.8 Comparative sensitivity (μΟ/οιη2) Resolving power (μm) Pattern shape (by 3 scales) Line edge roughness (Nai m) PED characteristics in vacuum _ (nano) 1 6.0 0.22 wear 7.0 2.3 2 10.0 0.20 slightly worn 12.5 8.6 3 8.0 0.18 slightly worn 10.5 5.6 4 9.0 0.18 Slight wear 11.5 4.3 200905394 It can be seen from Table 2 that the negative photoresist composition of the present invention is excellent in sensitivity, resolution, pattern shape, line edge thickness, and vacuum PED characteristics, and ensures good performance. According to the present invention, a negative photoresist composition excellent in sensitivity, resolution, pattern shape, line edge thickness, and vacuum PED characteristics, and a method of forming a pattern using the composition can be provided. The entire disclosure of each of the foreign patent applications for which the priority of the priority is claimed in the present application is hereby incorporated by reference in its entirety. ' [Simple description of the diagram] 〇 j\w [Description of component symbols] Μ . -68 -

Claims (1)

200905394 X. Patent application scope: 1. A negative photoresist composition comprising: (A) an alkali-soluble polymer containing a repeating unit represented by formula (1); (B) a base and an alkali under the action of an acid a crosslinker crosslinked by a soluble polymer (A); (C) a compound which produces an acid upon irradiation with actinic radiation or radiation; (D) a quaternary ammonium salt represented by the formula (2); and (E) Organic carboxylic acid: Formula (1): Wherein A represents a hydrogen atom, an alkyl group, a halogen atom, or a cyano group; and the scales 1 and R2 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a ring-based group, an aryl group, an aromatic group, and an alkoxy group. Or 院基矿氧; and η represents an integer from 1 to 3; Formula (7): R4 - N-Re B k -69 - 200905394 wherein r3 to r6 each independently represent an alkyl group, an alkenyl group, an aryl group, or an aromatic group Alkyl; B — represents Ο Τ 、, halogen atom, R 7 —CO plant, or R 7 —S03 — group; and R 7 represents alkyl, alkenyl, aryl, or aralkyl. 2. The negative photoresist composition according to claim 1, wherein the crosslinking agent (B) is a phenol compound having two or more benzene rings in its molecule and containing no nitrogen atom. A method of forming a pattern, comprising: forming a photoresist film from the negative photoresist composition of claim 1; and exposing and developing the photoresist film. 4. The negative photoresist composition of claim 1, wherein the alkali-soluble polymer (A) further comprises at least one repeating unit selected from the group consisting of repeating units represented by formulas (3), (4) and (5) : Equation (3): A -70 - 200905394 Equation (4): A 5): ♦CH2-Juice 1 X J \ (Ri°1 ) d *"f Ri〇5 ) (r-)T^ tR1〇6)f represents any base selected from the following structures: 200905394 Wherein A has the same meaning as a in formula (1); X represents not a single bond, -COO-yl '-0-yl, or _c〇N(Ri6)-yl, and Ri6 represents a hydrogen atom or an alkyl group; Rii to R15 each independently has the same meaning as 1 in formula (1); Rioi to Ri〇6 each independently of the base, dentate atom, dean, oxime oxy, phenolic oxy group, sulfonate An oxy group, a stilbene group, an aryl group, a aryl group, or a carboxyl group; and a to f each independently represent an integer of 〇 to 3. 5. The negative photoresist composition of claim 1, wherein the crosslinking agent (B) has a molecular weight of 1,200 or less, contains 3 to 5 benzene rings in its molecule, and has a total of two or More phenolic derivatives of hydroxymethyl or alkoxymethyl groups, two or more hydroxymethyl or alkoxymethyl groups bonded to at least one of the benzene rings in a concentrated manner or dispersed between the benzene rings. 6. The negative photoresist composition of claim 1, wherein the organic carboxylic acid (E) is selected from the group consisting of saturated or unsaturated aliphatic carboxylic acids, alicyclic-72 - 200905394 carboxylic acids, oxycarboxylic acids, alkanes At least one of an oxycarboxylic acid, a ketocarboxylic acid, and an aromatic carboxylic acid. 7. The negative photoresist composition according to claim 6, wherein the organic carboxylic acid (E) is at least one selected from the group consisting of benzoic acid, 1-hydroxy-2-naphthoic acid and 2-hydroxy-3-naphthoic acid. -73 - 200905394 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: