SPECIFICATION COMPOUND FOR PHOTORESIST, PHOTORESIST LIQUID, AND ETCHING
METHOD USING THE SAME
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001 ] This application claims the benefit of priority to Japanese Patent Application Nos. 2007-054289 filed on March 5,2007,2007-196756 filed on July 27, 2007, 2007-212149 filed on August 16,2007,2007-267664 filed on October 15,2007, 2007-267665 filed on October 15,2007,2008-047243 filed on February 28, 2008, 2008-047127 filed on February 28, 2008, 2008-047130 filed on February 28,2008, 2008-047237 filed on February 28,2008, and 2008-047238 filed on February 28, 2008, which are expressly incorporated herein by reference in their entirety. TECHNICAL FIELD
[0002] The present invention relates to a compound for photoresist and a photoresist liquid, that permits the formation of minute patterns. The present invention fijrther relates to a method of etching a surface being processed using the photoresist liquid. BACKGROUND TECHNIQUE
[0003] In the process of manufacturing electronic components such as semiconductor elements, magnetic bubble memories, and integrated circuits, the technique of forming a minute pattem and employing it as an etching mask to etch the layer beneath it is widely employed.
In recent years, light-emitting elements such as LEDs have been utilized in various applications. The LED is comprised of a semiconductor element, in which multiple layers of semiconductive films, including a light-emitting layer, are laminated on a substrate (also referred to as a "chip" hereinafter) and packaged with resin or the like. Since the refractive index of the uppermost layer (or outermost layer) of the light outlet of the chip differs fi-om that of the resin of the package, reflection occurs at the boundary between the two, diminishing light-emitting efficiency. Thus, to prevent such reflection at boundaries and achieve the goal of improving light-emitting efficiency, it has been proposed that a minute irregular structure be provided on the surface of the light outlet of the chip (see, for example, Japanese Unexamined Patent Publication (KOKAI) No. 2003-174171 or English language family member US2002/0195609A1 and Japanese Unexamined Patent Publication (KOKAI) No. 2003-209283 or English language family member US2003/0132445A1, which are expressly incorporated herein by reference in their entirety. [0004] The fifth embodiment in Japanese Unexamined Patent Publication (KOKAI)

No. 2003-174191 discloses a method of providing an antireflective film as the topmost layer constituting the above-mentioned light outlet of the light-emitting diode by manufacturing in advance a mold of minute irregular shape to form a minute irregular shape on the surface of the antireflective film, and press molding the surface of the antireflective film with the mold to impart an irregular shape to the surface of the light outlet. It also discloses, as a modification example thereof, the method of roughing in random directions with a grinder the surface of the antireflective film instead of press molding it with a mold. However, the former method requires an onerous process of fabricating a mold, as well as presenting a drawback in the form of the cost associated with fabricating the mold, while the latter method makes it difficult to consistently achieve a surface of uniform rouglmess, creating the problem of variation in product performance.
On the other hand, Japanese Unexamined Patent Publication (KOKAI) No. 2003-209283 discloses a method of forming a line and space pattern of triangular cross-section on a current diffusion layer constituting the topmost layer of the light outlet of a semiconductor element by blade processing, and then conducting treatment with hydrochloric acid at elevated temperature to form submicron irregularities on the surface of the current diffusion layer. It also discloses a method of employing photoresist on a current diffusion layer to form a line and space pattern, and then conducting reactive ion etching (RIE) to form minute irregularities similar to the above on the surface of the current diffusion layer. However, both of these methods present problems in the form of onerous processes.
[0005] Photolithography is a conventionally known technique employed to fabricate minute irregular structures, semiconductor devices, and the like. In photolithography, a resist composition containing a lijjht-sensitive compound is coated on the surface of a substrate or the like, pattern exposed through a photomask, and developed. Thus, either exposed portions or unexposed portions are selectively removed to form a resist pattern. Subsequently, the resist pattern is employed as an etching mask to form a minute irregular pattern or semiconductor elements on the surface of the substrate or the like.
[0006] However, in conventional photolithography employing a photoresist liquid containing a light-sensitive compound, a developing step is required after pattern exposure, thereby increasing the steps. [0007] DISCLOSURE OF THE INVENTION
Accordingly, it is an object of the present invention to provide a novel compound for photoresist, employed for minute processing by means of

photolithography, and more particularly, a novel compound for photoresist making it possible to omit the developing step following pattern exposure.
A further object of the present invention is to provide a photoresist liquid employing the above compound for photoresist.
A still further object of the present invention is to provide a method of etching a desired surface employing the above photoresist liquid.
[0008] The present inventors conducted extensive research into achieving the above-stated objects, resulting in the discovery that the pattern exposure of a dye film containing a dye compound selected from the group consisting of a compound comprising an oxonol dye skeleton, a cyanine dye, a styryl dye, a compoimd comprising a merocyanine dye skeleton, a compound comprising a phthalocyanine dye skeleton, an azo compound, and a complex compound of an azo compound and a metal ion generated a chemical and/or physical change in the physical properties of the portion irradiated with light by heating of the dye, permitting the use of the dye film as an etching mask following pattem exposiu-e. The present invention was devised on that basis.
[0009] The present invention relates to a compound for photoresist, selected from the group consisting of a compound comprising an oxonol dye skeleton, a cyanine dye, a styryl dye, a compound comprising a merocyanine dye skeleton, a compound comprising a phthalocyanine dye skeleton, an azo compound, and a complex compound of an azo compound and a metal ion.
[0010] According to one embodiment, the above compound for photoresist is selected from the compound (also referred to as "oxonol dye", hereinafter) comprising an oxonol dye skeleton, denoted by the following general formula (I). [0011] [Chem. 1] General formula (I)


B

m

X

[In general formula (I), each of A, B, C, and D independently denotes an electron-withdrawing group, witli a total of a Hammett's Op value of the electron-withdrawing group denoted by A and that of the electron-withdrawing group

denoted by B being equal to or greater than 0.6 and a total of a Hammett's Op value of the electron-withdrawing group denoted by C and that of the electron-withdrawmg group denoted by D being equal to or greater than 0.6, A and B may be linked together to form a ring, C and D may be linked together to form a ring, R denotes a substituent on a methine carbon, m denotes an integer of equal to or greater than 0 but equal to or less than 3, n denotes an mteger of equal to or greater than 0 but equal to or less than (2m+l), plural Rs present may be respectively identical or different and may be linked together to form a ring when n denotes an integer of equal to or greater than 2, and X denotes a counter ion that neutralizes a charge of the compound denoted by general formula (I).]
[0012] The above oxonol dye is preferably selected from those having a thermal decomposition temperature of equal to or higher than 100 °C but equal to or lower than 500 "C.
[0013] According to one embodiment, the above compound for photoresist is selected from the cyanine dye denoted by the following general formula (IV): [0014] [Chem.23

[In general formula (IV), each of Z' and l} independently denotes a group of nonmetal atoms required to form an optionally condensed, five- or six-membered nitrogen-containing hetero ring, each of L', \}, and \} independently denotes a methine chain, m denotes an integer ranging from 0 to 2, each of R and R independently denotes a substituent, plural L^s and L^s present may be identical or different when m^ denotes 2; each of p and q independently denotes 0 or 1, each of R'\ R^^, R'^, and R^'* independently denotes a hydrogen atom or a substituent; and X' denotes a counter ion neutralizing a charge of the compound denoted by general formula (IV).] [0015] According to one embodiment, the above compound for photoresist is selected from the styryl dye denoted by the following general formula (V): [0016] [Chem. 3] General formula (V)


R16 R16 X' (R°)„
[In general formula (V), Z^ denotes a group of nonmetal atoms required to form an optionally condensed, five- or six-membered nitrogen-containing hetero ring, each of L'* and L^ independently denotes a metliine chain, each of R^, R'*, R^ and R^ independently denotes a substituent, n' denotes an integer ranging from 0 to 4, plural R s present may be identical or different when n' is equal to or greater than 2; r denotes 0 or 1, each of R'^ and R^^ independently denotes a hydrogen atom or a substituent; and X^ denotes a counter ion neutralizing a charge of the compound denoted by general formula (V).] [0017] The above cyanine dye and styryl dye are preferably selected fi*om those having a thermal decomposition temperature of equal to or higher than 100 °C but equal to or lower than 600 °C.
[0018] According to one embodiment, the compound for photoresist is selected from the compound (also referred to as "merocyanine dye", hereinafter) comprising a merocyanine dye skeleton, denoted by the following general formula (VI). [0019] [Chem.4] General formula (VI)

[In general formula (VI), Z^' denotes a group of atoms forming a five- or six-membered hetero ring with X'^ and X'^, each of X'' and X'^ independently denotes a carbon atom or a hetero atom, with at least either of X^' or X'^ denoting a hetero atom, each of Y' and Y^ independently denotes a substituent, with at least either of Y^ and Y^ denoting a cyano group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, alkylsulfone group, arylsulfone group, alkylsulfonyl group, arylsulfonyl group, or aminosulfonyl group, Y^ and Y^ may be linked together to form a ring, each of L" and 'iP' independently denotes a methine group, and n denotes an integer ranging from 0 to 2.]
[0020] The above merocyanine dye is preferably selected fi-om those having a thermal decomposition temperature of equal to or higher than 150 °C but equal to or lower than

500 "C.
[0021] According to one embodiment, the above compound for photoresist is selected
from the compoimd (also referred to as "phthalocyanine dye", hereinafter) comprising a
phthalocyanine dye skeleton, denoted by the foUowdng general formula (VII).
[0022] [Chem. 5]
General formula (VII)

[In general formula (VII), R^' denotes a substituent, n'^ denotes an integer ranging from 1 to 8, plural R^'s present may be identical to or different from each other when n"' is an integer of equal to or greater than 2, and M denotes two hydrogen atoms, a divalent to tetravalent metal atom, a divalent to tetravalent oxymetal atom, or a divalent to tetravalent metal atom comprising a ligand.]
[0023] The phthalocyanine dye denoted by general formula (VII) is preferably selected from the compound denoted by the following general formula (VIII). [0024] [Chem. 6] General formula (VIII)
RP1 RP2

RP6 RP5
[In general formula (VIII), each of R"^ to R"* and R^^ to R^* independently denotes a hydrogen atom, halogen atom, cyano group, nitro group, formyl group, carboxyl group, sulfo group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 14 carbon atoms, substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms, substituted or

unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 14 carbon atoms, substituted or unsubstituted acyl group having 2 to 21 carbon atoms, substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, substituted or unsubstituted arylsulfonyl group having 6 to 14 carbon atoms, heterylsulfonyl group having 1 to 10 carbon atoms, substituted or unsubstituted carbamoyl group having 1 to 25 carbon atoms, substituted or unsubstituted sulfamoyl group having 0 to 32 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, substituted or unsubstituted aryloxycarbonyl group having 7 to 15 carbon atoms, substituted or unsubstituted acylamino group having 2 to 21 carbon atoms, substituted or unsubstituted sulfonylamino group having 1 to 20 carbon atoms, or substituted or unsubstituted amino group having 0 to 36 carbon atoms, with at least 8 from among R°' to R"^ and R^' to R*^^ being hydrogen atoms, but without all of R"' to R"* being hydrogen atoms; and M is defined in the same manner as in general formula (VII).]
[0025] According to one embodiment, in general formula (VIII), either R"' or R"^, either R"^ or R"\ either R"^ or R°^ and either R"^ or R"* are not a hydrogen atom. [0026] The above phthalocyanine dye is preferably selected from those having a thermal decomposition temperature of equal to or higher than 150 °C but equal to or lower than 500 °C.
[0027] According to one embodiment, the above compound for photoresist is selected from the compound denoted by the following general formula (IX) or the complex compound of the compoimd and a metal ion: [0028] [Chem. 7] General formula (IX)
Q^-N=N-Q2
[In general formula (IX), Q' denotes an aryl group or a heterocyclic group, Q^ denotes
an aryl group, heterocyclic group, or CR'^'R'*'^, each of R'" and R'*^ independently
denotes a substituent with a total value of a Hammett's ap value of the substituent
denoted by R'*' and that of the substituent denoted by R'*^ being equal to or greater than
O.6.]
[0029] Among the compounds denoted by general formula (EX), one particularly
preferred group includes the azo compound denoted by the following general formula
(X-1) and the complex compound of the azo compound and a metal ion.
[0030] [Chem. 8]
General formula (X-1)

N
[hi general formula (X-1), A' denotes a group of atoms forming a hetero aromatic ring with a carbon atom and nitrogen atom to which this is bonded, and Q is defined in the same manner as Q in general formula (IX).]
[0031] Among the compounds denoted by general formula (IX), another particularly preferred group includes the azo compound denoted by the following general formula (X-2) and the complex compound of the azo compound and a metal ion. [0032] [Chem.9] General formula (X-2)
[In general formula (X-2), A denotes a group of atoms forming a hetero aromatic ring with a carbon atom and nitrogen atom to which this is bonded, and Q is defined in the
'y
same manner as Q in general formula (IX).]
[0033] The above azo compound ;and the complex compound of the azo compound and a metal ion are preferably selected from those having a thermal decomposition temperature of equal to or higher than 150 °C but equal to or lower than 500 °C. [0034] Another aspect of the present invention relates to a photoresist liquid, comprising at least one of the compound for photoresist of the present invention. [0035] According to one embodiment, the above photoresist liquid comprises the above compound for photoresist in a quantity of equal to or greater than 50 mass percent based on total solid component comprised in the photoresist liquid. [0036] Another aspect of the present invention relates to a method of etching a svirface being processed, comprising forming a photoresist film by coating the photoresist liquid of the present invention on a surface being processed; pattern exposing the photoresist film; and subjecting at least a portion of the surface being processed on which is present the photoresist film following the pattern exposure to etching, to etch at least a portion of the surface being processed in an area corresponding to the portion that has been exposed in the pattem exposure.
[0037] According to one embodiment, a light employed for the pattem exposure is a laser beam having a wavelength, Xnm, the compound for photoresist comprised in the

photoresist film is a compound selected from the group consisting of a oxonol dye, a cyanine dye, a styryl dye, a merocyanine dye, an azo compound, and a complex compound of an azo compound and a metal ion, and the compound has a maximum wavelength: A,max within a range of X±150 nm.
[0038] According to one embodiment, a light employed for the pattern exposure is a laser beam having a wavelength, X,nm, the compound for photoresist comprised in the photoresist film is a phthalocyanine dye, and the phthalocyanine dye has a maximum absorption within a range of H: 15 0 nm.
[0039] According to the present invention, since an etching mask can be formed only by pattern exposure, that is to say, without conducting a developing step with a developer, each developing step in a photolithography process, that is carried out plural times in a process of fabricating various semiconductor devises, can be omitted, thereby achieving significant simplification. Furthermore, according to the present invention, minute irregularities can be formed on a surface being processed. [0040] BEST MODE FOR CARlEiYING OUT THE INVENTION [Compound for photoresist]
The compound for photoresist of the present invention is a compound selected from the group consisting of a compound comprising an oxonol dye skeleton, a cyanine dye, a styryl dye, a compound comprising a merocyanine dye skeleton, a compound comprising a phthalocyanine dye skeleton, an azo compound, and a complex compound of an azo compound and a metal ion.
The present inventors discovered that when a dye fihn comprising a compound (also referred to as "dye compound", hereinafter) selected from the group consisting of a compound comprising an oxonol dye skeleton, a cyanine dye, a styryl dye, a compound comprising a merocyanine dye skeleton, a compound comprising a phthalocyanine dye skeleton, an aj^o compound, and a complex compound of an azo compound and a metal ion was pantially irradiated with light, the physical properties of the irradiated portions changed locally, and that resistance to etching decreased relative to the dye film prior to light exposure. They also discovered that the dye film could function as an etching mask. The present inventors have presumed the following with regard to this phenomenon.
When the dye film comprising the above dye compound is irradiated with spots of light by a laser beam, for example, the dye compound in the irradiated portions heats up. This heating causes the dye compound to midergo a change in physical properties, such as thermal decomposition, wWch is thought to result in localized physical and/or chemical change in the light-irradiated portions of the dye fihn, forming pits (openings)

(I I (J, I ' ■■■■ , - > L ' ^ fj
or portions of locally reduced durability (low-durability portions). The dye film in wWch the pits have been formed will function as an etching mask, of course. Since the low-durability portions are readily etched away in tlie etching step, a dye film in which low-durability portions have been fonned by pattern exposure will also function as an etching mask. The dye film itself that contains the o?eenM~dye also has good resistance ~-to etching and was found to function well as a fihn durable to etching. In this context, the etching method may be either a dry or wet etching method. In particular, application to dry etching is desirable because the step of washing away the wet etching liquid is unneeded.
In particular, the present inventors observed the behavior of the dye film containing the above dye compound during irradiation with a laser beam. As the temperature of the center portion of the area irradiated with a laser beam rose, a phenomenon whereby the temperatiare of the surrounding portions dropped was confirmed. Although the reason for the drop in temperature in surrounding portions was not determined, the drop in temperat"ure of the surrounding portions inhibits spreading of the change in physical properties to surrounding portions despite the formation of low-durability portions and the formation of pits due to thermal decomposition in the center portion of areas irradiated by the laser beam. Thus, in pattern exposure with a laser beam, it is thought that a pattern of smaller diameter than the diameter of the laser beam can be formed in the dye film. Accordingly, pattern exposure of a dye film with a laser beam causes just a small diameter exposure area that is even narrower than the area irradiated by the laser beam diameter to become a low-durability portion. As a result, minute pattern exposure can be achieved that is similar to pattern exposure with a fine beam smaller in diameter than a laser beam.
Further, the dye film containing the above dye compound forms pits or low-durability portions in areas irradiated in pattern exposure. Thus, the developing process after pattern exposure is xmnecessary and thus it is possible to conduct the etching step as a subsequent step of the pattern exposure.
The "photoresist" in the present invention includes embodiments that form a resist pattern by means of heat generated by such pattern exposure.
The compound for photoresist of the present invention will be described in greater detail below.
[0041] The compound for photoresist of the present invention can be a compovmd comprising an oxonol dye skeleton. In the present invention, the phrase "compound comprising an oxonol dye skeleton" means a methine dye, characterized in that an alternating conjugate system constituting a chromophore is terminated by a hetero atom
10

or a carbon atom having a negative charge, thereby causing the negative charge to be
present in a nonlocalized manner throughout the entire conjugated system.
[0042] Among compounds comprising an oxonol dye skeleton, from the perspectives
of light absorption characteristics, thermal decomposition characteristics, and the like,
the oxonol dye denoted by general formula (I) below can be given by way of example.
[0043] [Chem. 10]
General formula (I)
A C

B

m

X

Rn
[0044] In general formula (I), each of A, B, C, and D independently denotes an electron-withdrawing group, with a total of a Hammett's Op value of the electron-withdrawing group denoted by A and that of the electron-withdrawing group denoted by B being equal to or greater than 0.6 and a total of a Hammett's Op value of the electron-withdrawing group denoted by C and that of the electron-withdrawing group denoted by D being equal to or greater than 0.6, A and B may be linked together to form a ring, C and D may be linJced together to form a ring, R denotes a substituent on a methine carbon, m denotes an integer of equal to or greater than 0 but equal to or less than 3, n denotes an integer of equal to or greater than 0 but equal to or less than (2m+l), plural Rs present may be respectively identical or different and may be linked together to form a ring when n denotes an integer of equal to or greater than 2, and X denotes a counter ion that neutralizes a charge of the compound denoted by general formula (I).
The oxonol dye denoted by general formula (I) will be described below. [0045] In general formula (I), each of A, B, C, and D independently denotes an electron-withdrawing group. Hov/ever, the total of the Hammett's substituent constant Op value (referred to as "op value", hereinafter) of the electron-withdrawing group denoted by A and that of the eleclxon-withdrawing group denoted by B is equal to or greater than 0.6, and the total of the Hammett's Op value of the electron-withdrawing group denoted by C and that of the electron-withdrawing group denoted by D is equal to or greater than 0.6. When the total of the Hammett's Op values is equal to or greater than 0.6, absorption characteristics and heat decomposition properties suitable as a
11

compound for photoresist can be achieved. Each of A, B, C, and D may be respectively identical or different. Further, A and B, or C and D, may be linked together to form a ring.
[0046] The total of the Hammett's Op values of the electron-withdrawing group denoted by A and the electron-withdrawing group denoted by B, and the total of the Hammett's Op values of the electron-withdrawing group denoted by C and the electron-withdrawing group denoted by D, are each desirably 0.6 to 1.7, preferably 0.7 to 1.6. Further, the Hammett's Op value of each of the electron-withdrawing groups denoted by A, B, C, and D independently desirably falls within a range of 0.30 to 0.85, preferably within a range of 0.35 to 0.80.
[0047] The Hammett's Op value is described, for example, in Chem. Rev. 91, 165 (1991) and in references sited therein. The Hammett's Op value of items not described therein can be calculated by the method described in these documents. When A and B (or C and D) are linked to form a ring, the Op value of A (or C) means the Op value of the -A-B-H (or -C-D-H) group, and the Op value of B (or D) means the Op value of the -B-A-H (or -D-C-H) group. In that case, the Op values differ because the bond orientation of the two differs.
[0048] Desirable specific examples of the electron-withdrawing groups denoted by A, B, C, and D are: cyano groups, nitro groups, acyl groups with 1 to 10 carbon atoms (such as acetyl groups, propionyl groups, butyryl groups, pivaloyl groups, and benzoyl groups), alkoxycarbonyl groups having 2 to 12 carbon atoms (such as methoxycarbonyl groups, ethoxycarbonyl groups, isopropoxycarbonyl groups, butoxycarbonyl groups, and decyloxycarbonyl groups), aryloxycarbonyl groups having 7 to 11 carbon atoms (such as phenoxycarbonyl groups), carbamoyl groups having 1 to 10 carbon atoms (such as methylcarbamoyl groups, ethylcarbamoyl groups, and phenylcarbamoyl groups), alkylsulfonyl groups having 1 to 10 carbon atoms (such as methanesulfonyl groups), arylsulfonyl groups having 6 to 10 carbon atoms (such as benzenesulfonyl groups), alkoxysulfonyl groups having 1 to 10 carbon atoms (such as methoxysulfonyl groups), sulfamoyl groups having 1 to 10 carbon atoms (such as ethylsulfamoyl groups and phenylsulfamoyl groups), alkylsulfinyl groups having 1 to 10 carbon atoms (such as methanesulfmyl groups and ethanesulfinyl groups), arylsulfmyl groups having 6 to 10 carbon atoms (such as benzenesulfmyl groups), alkylsulfenyl groups having 1 to 10 carbon atoms (such as methanesulfenyl groups and ethanesulfenyl groups), arylsulfenyl groups having 6 to 10 carbon atoms (such as benzenesulfenyl groups), halogen atoms, alkynyl groups having 2 to 10 cai-bon atoms (such as ethynyl groups), diacylamino groups having 2 to 10 carbon atoms (such as diacetylamino groups), phosphoryl groups.
12

carboxyl groups, and five-membered and six-membered heterocyclic groups (such as 2-benzothiazolyl groups, 2-benzooxazolyl groups, 3-pyridyl groups, 5-(lH)-tetrazolyl groups, and 4-pyrimidyl groups).
[0049] Examples of the substituent on the methine carbon denoted by R in general formula (I) are: chain or cyclic alkyl groups having 1 to 20 carbon atoms (such as methyl, ethyl, n-propyl, isopropyl, and n-butyl groups), substituted or unsubstituted aryl groups having 6 to 18 carbon atoms (such as phenyl, chlorophenyl, anisyl, toluyl, 2,4-di-t-amyl, and 1-naphthyl groups), alkenyl groups (such as vinyl and 2-methylvinyl groups), alkynyl groups (such as ethynyl, 2-methylethynyl, and 2-phenylethynyl groups), halogen atoms (such as F, CI, Br, and I), cyano groups, hydroxyl groups, carboxyl groups, acyl groups (such as acetyl, benzoyl, salicyloyl, and pivaloyl groups), alkoxy groups (such as methoxy, butoxy, and cyclohexyloxy groups), aryloxy groups (such as phenoxy and 1-naphthoxy groups), alkylthio groups (such as methylthio, butylthio, benzylthio, and 3-methoxypropylthio groups), arylthio groups (such as phenylthio and 4-chlorophenylfhio groups), alkylsulfonyl groups (such as methanesulfonyl and butanesulfonyl groups), arylsulfonyl groups (such as benzenesulfonyl and paratoluenesulfonyl groups), carbamoyl groups having 1 to 10 carbon atoms, amido groups having 1 to 10 carbon atoms, imido groups having 2 to 12 carbon atoms, acyloxy groups having 2 to 10 carbon atoms, alkoxycarbonyl groups having 2 to 10 carbon atoms, and heterocyclic groups (such as aromatic heterocyclic rings such as pyridyl, thienyl, furyl, thiazolyl, imidazolyl, and pyrazolyl groups, and aliphatic heterocyclic rings such as pyrrolidine rings, piperidine rings, morpholine rings, pyran rings, thiopyran rings, dioxane rings, and dithiolane rings). [0050] R is desirably a halogen atom, chain or cyclic alkyl group having 1 to 8 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 8 carbon atoms, aryloxy group having 6 to 10 carbon atoms, or heterocyclic group having 3 to 10 carbon atoms; preferably a chlorine atom, alkyl group having 1 to 4 carbon atoms (such as a methyl group, ethyl group, or isopropyl group), phenyl, alkoxy group having 1 to 4 carbon atoms (such as a methoxy or ethoxy group), phenoxy group, or mtrogen-containing heterocyclic group having 4 to 8 carbon atoms (such as a 4-pyridyl group, ben2oxazole-2-yl group, or benzothiazole 2-yl group).
[0051] n denotes an integer of equal to or greater than 0 but equal to or less than (2m+l). Further below m will be described in detail. When n is an integer of equal to or greater than 2, plural Rs present may be respectively identical or different, and may be linked together to form a ring. In that case, the ring is desirably comprised of 4 to 8 members, preferably 5 or 6 members. The constituent atoms of the ring are
13

desirably carbon atoms, oxygen atoms, and/or nitrogen atoms, preferably carbon atoms. [0052] A, B, C, D, and R may further comprise substituents. Examples of such substituents are the examples given above for monovalent substituents denoted by R in general formula (I). In the present invention, the "carbon number" of a given group comprising substituents refers to the number of carbon atoms of the portion not including any substituent.
[0053] In the oxonol dye denoted by general formula (I), it is desirable from the perspective of thermal decomposition for A and B, and/or C and D, to be linked to form a ring. Examples of such rings are given below. In the examples, each of Ra, Rb, and Re independently denotes a hydrogen atom or a substituent. The details of the substituents denoted by Ra, Rb, and Re are as set forth above for R. Ra, Rb, and Re may be linked together to form a carbon ring or a heterocyclic ring. Examples of carbon rings are cyclohexyl, cycloheptyl, cyclohexene, and benzene rings, and other saturated or unsaturated 4- to 7-merabered carbon rings. Examples of heterocylic rings are piperidine, piperazine, morpholine, tetrahydrofiiran, furan, thiophene, pyridine, and pyrazine rings, and other saturated or imsaturated 4- to 7- membered heterocyclic rings. These carbon rings and heterocyclic rings may be further substituted. Examples of groups that can further substitute ai'e the groups given above by way of example for the substituent denoted by R. [0054] [Chem. 11]

laser with a center oscillation wavelength of 405 nm), m desirably denotes 0 or 1, preferably 0.
[0065] In general formula (I), the counter ion denoted by X neutralizes the charge of the compound denoted by general ibrmula (I). It can be an anion, cation, single ion species, or combination of multiple ion species. It is normally a cation, and may be an inorganic cation or an organic cation. Examples of inorganic cations are: hydrogen ions, metal ions, and ammonium ions (NH4 ). Metal ions are desirable; alkali metal ions (such as Li^, Na*, and K^) and transition metal ions (such as Cu^^ and Co'^^) are preferred. Transition metal ions may be coordinated with organic ligands. [0066] An onium ion is desirable and the ion denoted by general formula (III) below is preferred as the organic cation denoted by X. These compounds are readily obtained by the Menshutkin reaction of a corresponding dipyridyl and a halogen compound containing the target substitute (for example, see Japanese Unexamined Patent Publication (KOKAI) Showa No. 61-148162), or by an arylation reaction based on the method described in Japanese Unexamined Patent Publication (KOKAI) Showa No. 51-16675 and Japanese Unexamined Patent Publication (KOKAI) Heisei No. 1-96171. [0067] [Chem.20] General formula (III)

[0068] In general formula (III), each of R and R independently denotes an alkyl group, alkenyl group, alkynyl group, aryl group, or heterocyclic group, R denotes a substituent, and s denotes an integer falling within a range of 0 to 8. When s is an integer of equal to or greater than 2, plural R s present may be respectively identical or different, and may be linked together to form a ring.
[0069] In general formula (III), the alkyl group denoted by R or R may be linear, branched, or cyclic; it desirably comprises 1 to 18 carbon atoms, and preferably comprises 1 to 8 carbon atoms. Specific examples of these alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, isoamyl, n-hexyl, cyclohexyl, 2-ethylhexyl, and n-octyl groups.
19

[0070] In general formula (III), the alkenyl group denoted by R^' or R'^^ desirably
comprises 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms. Specific examples
are vinyl, 2-propenyl, 2-methyl, propenyl, and 1,3-butadienyl groups.
[0071] In general formula (III), the alkynyl group denoted by R or R desirably
comprises 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms. Specific examples
are ethynyl, propynyl, and 3,3-dimethylbutynyl groups.
[0072] In general formula (III), the aryl group denoted by R or R desirably
comprises 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms. Specific examples
are phenyl, 1 -naphthyl, and 2-naphthyl groups.
[0073] In general formula (III), the heterocyclic group denoted by R^' or R'^^ is
desirably a saturated or unsaturated heterocyclic group comprising 4 to 7 carbon atoms,
with the hetero atoms contained desirably being nitrogen, oxygen, or sulfiir atoms.
Specific examples are 4-pyridyl., 2-pyridyI, 2-pyrazyl, 2-pyrimidyl, 4-pyrimidyl,
2-imidazolyl, 2-furyl, 2-tliiophenyl, 2-benzooxazolyl, and 2-benzothioxazolyl groups.
[0074] In general formula (III), the alkyl group, alkenyl group, alkynyl group, aryl
group, or heterocyclic group denoted by R or R may be further substituted.
Examples of the substituents are those given by way of example of the substituent
denoted by R in general formula (I).
[0075] In general formula (III), R^^ denotes a substituent. The details of the
-IT
substituent denoted by R are as set forth for the substituent denoted by R in general formula (I). A substituted or unsubstituted alkyl group having 1 to 18 carbon atoms is desirable, and an unsubstituted alkyl group having 1 to 8 carbon atoms is preferred. [0076] In general formula (III), s denotes an integer falling within a range of 0 to 8, desirably an integer falling within a range of 0 to 4, preferably an integer falling within a range of 0 to 2, and more preferably, 0. When s is an integer of equal to or greater than
-IT
2, plural R s present may be respectively identical or different, and may be linked
together to form a ring. The two pyridine rings in general formula (III) may be linked
at any position, are desirably linked at the 2 position and 4 position of the pyridine rings,
and are preferably linked at the 4 positions of the two pyridine rings.
[0077] The oxonol dyes denoted by general formula (I) may be bonded at any position
to form a polymer. In that case, the various units may be identical or different, and
may be bonded to polymer chains of polystyrene, polymethacrylate, polyvinyl alcohol,
cellulose, or the like.
[0078] General formula (I) includes multiple tautomers based on differences in the
notation of the localized position of the anion. In particular, when one from among A,
B, C, and D denotes -CO-E (E being a substituent), the common practice is to denote
20

the negative charge as being localized on the oxygen atom. For example, when D is -CO-E, the notation is generally as given in general formula (II) below; compounds represented by such notation are included in general formula (I). [0079] [Chem.21] General formula (II)


B

m

X

[0080] The definitions of A, B, C, R, m, n, and x in general formula (II) are identical to those in general formula (I).
[0081] Specific examples of the oxonol dye denoted by general formula (I) are the specific examples of oxonol dyes given in Japanese Unexamined Patent Publication (KOKAI) Showa No. 63-209995 or English language family member U.S. Patent No. 4,968,593; Japanese Unexamined Patent Publication (KOKAI) Heisei No. 10-297103 or English language family member U.S. Patent No. 6,670,475; Japanese Unexamined Patent Publication (KOKAI) Heisei No. 11-348420; Japanese Unexamined Patent Publication (KOKAI) No. 2000-52658 or English language family member U.S. Patent No. 6,225,024; and Japanese Unexamined Patent Publicafion (KOKAI) No. 2000-272241. Some of these compounds will be given as examples below. [0082] [Chem.22]
21

with respect to the synthesis method.
[0089] The compound for photoresist of the present invention can be a compound selected from the group consisting of a cyanine dye and a styryl dye. In the present invention, the term "cyanine dye" means a methine dye characterized in that the alternating conjugation system comprised of chromophores is terminated by a hetero atom having a positive charge, thereby causing the positive charge to be present in nonlocalized manner throughout the entire conjugated system. The term "styryl dye" means a dye having a structure in which a hetero atom having a positive charge and a carbon ring-type aromatic ring are bonded by a dimethine chain or a polymethine chain. [0090] Among compounds selected from the group consisting of a cyanine dye and a styryl dye, from the perspective of light absorption characteristics, thermal decomposition characteristics, and the like, desirable examples of the compovmd for photoresist of the present invention are the cyanine dye denoted by general formula (IV) and the styryl dye denoted by general formula (V). [0091] [Chem.26] General formula (IV)

[In general formula (IV), each of Z and Z independently denotes a group of nonmetal atoms required to form an optionally condensed, five- or six-membered nitrogen-containing hetero ring, each of L , L , and L independently denotes a methine chain, m denotes an integer ranging from 0 to 2, each of R and R independently
9 T • ■ 1
denotes a substituent, plural L s and L s present may be identical or different when m
11 1^ 1^ \ A
denotes 2; each of p and q independently denotes 0 or 1, each of R , R , R , and R independently denotes a hydrogen atom or a substituent; and X denotes a counter ion neutralizing a charge of the compound denoted by general formula (IV).] [0092] [Chem.27] General formula (V)


[In general formula (V), l} denotes a group of nonmetal atoms required to form an optionally condensed, five- or six-membered nitrogen-containing hetero ring, each of L and L^ independently denotes a methine chain, each of R^, R'*, R^, and R^ independently denotes a substituent, n' denotes an integer ranging from 0 to 4, plural R^s present may be identical or different when n' is equal to or greater than 2; r denotes 0 or 1, each of R'^ and R'^ independently denotes a hydrogen atom or a substituent; and X^ denotes a counter ion neutralizing a charge of the compound denoted by general formula (V).] [0093] The compounds denoted by general formulas (IV) and (V) will be described below. [0094] General formula (IV)
In general formula (IV), each of Z and Z independently denotes a group of nonmetal atoms required to formi an optionally condensed, five- or six-membered nitrogen-containing hetero ring, and each of p and q independently denotes 0 or 1. The nitrogen-containing hetero ring fonned by Z and Z may be substituted or unsubstituted. The substituents are not specifically limited. Specific examples thereof are the examples of the substituent denoted by R and R , described fiirther below. [0095] Specific examples of the above nitrogen-containing hetero ring are: when p or q is 0, benzothiazole, benzooxazole, benzoimidazole, indolenine, thiazole, thiazoline, oxazole, oxazoline, imidazole, imidazoline, 2-pyridinium, 2-quinolinium, and condensed rings thereof; when p or q is 1, 4-pyridinium, 4-quinolinium, and condensed rings thereof. Desirable examples are benzothiazole, benzooxazole, benzoimidazole, and indolenine; preferred examples are benzooxazole and indolenine; and an optimal example is indolenine.
[0096] Each of R' and R^ independently denotes a substituent. Examples of desirable substituents are given below:
substituted or unsubstituted linear, branched chain, or cyclic alkyl groups having 1 to 18 carbon atoms (desirably, 1 to 8 carbon atoms) (such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, cyclohexyl, methoxyethyl, ethoxycarbonylethyl, cyanoethyl, diethylaminoethyl, hydroxyethyl, chloroethyl.

acetoxyethyl, and trifluoromethyl groups); alkenyl groups having 2 to 18 carbon atoms
(desirably, 2 to 8 carbon atoms) (such as vinyl groups); alkynyl groups having 2 to 18
carbon atoms (desirably, 2 to 8 carbon atoms) (such as ethynyl groups); substituted or
unsubstituted aryl groups having 6 to 18 carbon atoms (desirably, 6 to 10 carbon atoms)
(such as phenyl, 4-methylphenyI, 4-methoxyphenyl, 4-carboxyphenyl, and
3,5-dicarboxyphenyl groups); substituted or unsubstituted aralkyl groups having 7 to 18
carbon atoms (desirably, 7 to 12 carbon atoms) (such as ben2yl and carboxybenzyl
groups); substituted or unsubstituted acyl groups having 2 to 18 carbon atoms (desirably,
2 to 8 carbon atoms) (such as acetyl, propionyl, butanoyl, and chloroacetyl groups);
substituted or unsubstituted alkyl or arylsulfonyl groups having 1 to 18 carbon atoms
(desirably, 1 to 8 carbon atoms) (such as methanesulfonyl and p-toluenesulfonyl
groups); alkylsulfinyl groups having 1 to 18 carbon atoms (desirably, 1 to 8 carbon
atoms) (such as methanesulfinyl, ethanesulfmyl, and octanesulfinyl groups);
alkoxycarbonyl groups having 2 to 18 carbon atoms (desirably, 2 to 8 carbon atoms)
(such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups);
aryloxycarbonyl groups having 7 to 18 carbon atoms (desirably, 7 to 12 carbon atoms)
(such as phenoxycarbonyl, 4-methylphenoxycarbonyl, and 4-methoxyphenylcarbonyl
groups); substituted or unsubstituted alkoxy groups having 1 to 18 carbon atoms
(desirably, 1 to 8 carbon atoms) (such as methoxy, ethoxy, n-butoxy, and
methoxyethoxy groups); substituted or unsubstituted aryloxy groups having 6 to 18
carbon atoms (desirably, 6 to 10 carbon atoms) (such as phenoxy and
4-methoxyphenoxy groups); alkyltliio groups having 1 to 18 carbon atoms (desirably 1
to 8 carbon atoms) (such as methylthio and ethyltliio groups); arylthio groups having 6
to 10 carbon atoms (desirably, 1 to 8 carbon atoms) (such as phenylthio groups);
substituted or unsubstituted acryloxy groups having 2 to 18 carbon atoms (desirably, 2
to 8 carbon atoms) (such as acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy,
benzoyloxy, and chloroacetyloxy groups); substituted or unsubstituted sulfonyloxy
groups having 1 to 18 carbon atoms (desirably, 1 to 8 carbon atoms) (such as
methanesulfonyloxy groups); substituted or unsubstituted carbamoyloxy groups having
2 to 18 carbon atoms (desirably 2 to 8 carbon atoms) (such as methylcarbamoyloxy and
diethylcarbamoyloxy groups); unsubstituted amino groups or substituted amino groups
having 1 to 18 carbon atoms (desirably 1 to 8 carbon atoms) (such as methylamino,
dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino,
pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino,
phenoxycarbonylamino, phenylcarbamoylamino, ethylthiocarbamoylamino,
methylsulfamoylamino, phenylsulfamoylamino, ethylcarbonylamino,
29

ethylthiocarbonylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, methanesulfonylamino, and benzenesulfonylamino groups); amido groups having 1 to 18 carbon atoms (desirably, 1 to 8 carbon atoms) (such as acetamide, acetylmethylamide, and acetyloctylamide groups); substituted or unsubstituted ureido groups having 1 to 18 carbon atoms (desirably, 1 to 8 carbon atoms) (such as unsubstituted ureido groups, methylureido groups, ethylureido j^oups, and dimethylureido groups); substituted or unsubstituted carbamoyl groups having 1 to 18 carbon atoms (desirably 1 to 8 carbon atoms) (such as unsubstituted carbamoyl groups, methylcarbamoyl groups, ethylcarbamoyl groups, n-butylcarbamoyl groups, t-butylcarbamoyl groups, dimethylcarbamoyl groups, morpholinocarbamoyl groups, and pyrrolidinocarbamoyl groups); unsubstituted sulfamoyl groups or substituted sulfamoyl groups having 1 to 18 carbon atoms (desirably, 1 to 8 carbon atoms) (such as methylsulfamoyl and phenylsulfamoyl groups); halogen atoms (such as fluorine, chlorine, and bromine atoms); hydroxyl groups; mercapto groups; nitro groups; cyano groups, carboxyl groups; sulfo groups; phosphono groups (such as diethoxyphosphono groups); and heterocyclic groups (such as oxazole rings, benzooxazole rings, thiazole rings, benzothiazole rings, imidazole rings, benzoimidazole rings, indolenine rings, pyridine rings, morpholine rings, piperidine rings, pyrrolidine rings, sulfolane rings, fiiran rings, thiophene rings, pyrazole rings, pynole rings, chroman rings, and coumarin rings). [0097] R and R are desirably alkyl groups having 1 to 18 carbon atoms, and optimally, methyl groups.
If 1 ^ 1'? 'I A
[0098] Each of R , R , R , and R independently denotes a hydrogen atom or a subsliluent. When R", R'^, R'^, or R''* denotes a substituent, the substituent is not specifically limited. Examples of these substituents are the examples given for the substituents denoted by R and R .
[0099] In general formula (IV), each of L , L , and L independently denotes a methine chain. The methine chain may be substituted. Examples of substituents are
19
those given by way of example for tiie substituents denoted by R and R . The absence
of substituents is desirable.
[0100] m' denotes an integer falling within a range of 0 to 2. When m denotes 2,
plural L^s and L'^s present may be identical or different, m' is desirably 0 or 1, and is
optimally 0.
[0101] X^ denotes a counter ion that neutralizes the charge of the compound denoted
by general formula (IV). Whether a given dye is a cation or an anion, and whether or
not it possesses a net ion charge, depends on auxochromes and substituents. When the
substituent comprises a dissociative group, it may dissociate and hold a negative charge.
30

In that case, as well, the overall charge of the molecule is neutralized by X'. Typical cations include inorganic and organic ammonium ions (such as tetraalkylammonium ions and pyridinium ions) and alkali metal ions. On the other hand, anions may be inorganic anions or organic anions, such as halogen anions (such as fluoride ions, chloride ions, bromide ions, and iodide ions), substituted arylsulfonic acid ions (such as p-toluenesulfonic acid ions and p-cMorobenzenesulfonic acid ions), aryldisulfonic acid ions (such as 1,3-benzenedisulfonic acid ions, 1,5-naphthalenedisulfonic acid ions, and 2,6-naphthalenedisulfonic acid ions), alkyl sulfuric acid ions (such as methyl sulfate ions), sulfuric acid ions, thiocyanic acid ions, perchloric acid ions, tetrafluoroboric acid ions, picric acid ions, acetic acid ions, and trifluoromethanesulfonic acid ions.
Charge-equilibrating counter ions in the form of ionic polymers or other dyes having the opposite charge of the dye may be employed. Metal complex ions (such as bisbenzene-l,2-dithiolate nickel (III) and azo dye chelate compounds) may also be possible. [0102] General formula (V)
In general formula (V), Z denotes a group of nonmetal atoms required to form an optionally condensed, five- or six-membered nitrogen-containing hetero ring, r denotes 0 or 1. The details of specific examples of nitrogen-containing hetero rings formed with Z are identical to those of the nitrogen-containing hetero rings formed with Z' and Z^ in general formula (PV). Each of R*^ and R'^ independently denotes a hydrogen atom or a substituent. The substituent is not specifically limited when R'^ or R denotes a substituent, and when Z comprises a substituent. Examples of these substiluenLs are the substituents given by way of example for substituents denoted by R' andRl
[0103] Each of R^, R'', R^, and R^ independently denotes a substituent. The details of specific examples of R to R are the same as those for R and R in general formula (IV).
[0104] n denotes an integer falling within a range of 0 to 4. When n is equal to or greater than 2, plural R^s present may be identical or different, n' is desirably 0. [0105] In general formula (V), each of L'* and L^ independently denotes a methine chain. The methine chain may comprise a substituent. Examples of the substituent are those given by way of example for the substituents denoted by R and R in general formula (IV). The absence of substituents is desirable.
[0106] X denotes a counter ion that neutralizes the charge of the compound denoted by general formula (V). The details of X , such as specific examples, are identical to those of X' in general formula (IV).
31

[0107] Specific examples of the compound for photoresist of the present invention in the form of cyanine dyes and styryl dyes are the cyanine dyes described in Japanese Unexamined Patent Publication (KOKAI) No. 2001-232945 and the styryl dyes described in Japanese Unexamined Patent Publication (KOKAI) No. 2002-74740. Some of these compounds will be given by way of example below. IV-1 to IV-65 are specific examples of cyanine dyes ;and V-1 to V-10 are specific examples of styryl dyes. [0108] [Chem.28]

[0126] From the perspective of sensitivity during pattern exposure by laser, the
thermal decomposition temperatiu-e of the compound for photoresist of the present
invention in the form of a cyanine dye or styryl dye is desirably equal to or higher than
100°C but equal to or lower than (SOO°C, preferably equal to or higher than 120°C but
equal to or lower than 550°C, and optimally equal to or higher than 150°C but equal to
or lower than SOOT.
[0127] The compound for photoresist of the present invention in the form of a cyanine
dye or styryl dye can be synthesized by known methods, and in some cases, commercial
products are available.
[0128] The compound for photoresist of the present invention can also be a compound
comprising a merocyanine dye skeleton. In the present invention, the term
"merocyanine dye skeleton" means a dye skeleton having an electrically neutral methine
chromophore.
[0129] Among compounds comprising a merocyanine dye skeleton, the merocyanine
dyes denoted by general formula (VI) below are examples of merocyanine dyes that are
desirable from the perspective of light absorption characteristics, thermal decomposition
characteristics, and the like.
[0130] [Chem.46]
General formula (VI)

■X
\/, ii_, ^2\—y
-Y11 .Y
H1

[0131] In general formula (VI), Z" denotes a group of atoms forming a five- or
11 19 11 19
six-membered hetero ring with X and X . Each of X and X independently
11 19
denotes a carbon atom or a hetero atom. However, at a mimmum, either X or X denotes a hetero atom. Nitrogen atoms or sulfur atoms are desirable as hetero atoms. [0132] Examples of hetero rings formed by Z'^ X", and X'^ are thiazoline rings, oxazoline rings, dithiol rings, imidazoline rings, benzo-condensed rings thereof, or rings having the structures indicated below. [0133] [Chem.47]


R'-fQp----

[0134] In the above, each of R' to R^ independently denotes a substituent. The substituents are not specifically limited. Examples are the substituents described

further below as substituents that can be present on hetero rings.
[0135] Of the above, desirable hetero rings are thiazoline rings, oxazoline rings, dithiol rings, imidazoline rings, and benzo-condensed rings thereof Optimal hetero rings are benzothiazoline rings, benzooxazoline rings, benzodithiol rings, or benzoimidazoline rings. These can be further condensed with other aromatic rings. [0136] The above hetero ring may comprise substituents other than hydrogen atoms. Examples of desirable substituents iire alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 14 carbon atoms, aralkyl groups having 7 to 15 carbon atoms, heterocyclic groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 14 carbon atoms, alkylsulfenyl groups having 1 to 20 carbon atoms, arylsulfenyl groups having 6 to 14 carbon atoms, alkylsulfonyl groups having 1 to 20 carbon atoms, arylsulfonyl groups having 6 to 14 carbon atoms, acyl groups having 2 to 21 carbon atoms, carbamoyl groups having 1 to 25 carbon atoms, sulfamoyl groups having 0 to 32 cai-bon atoms, alkoxycarbonyl groups having 1 to 20 carbon atoms, aryloxycarbonyl groups having 7 to 15 carbon atoms, acylamino groups having 2 to 21 carbon atoms, sulfonylamino groups having 1 to 20 carbon atoms, amino groups having 0 to 32 carbon atoms, cyano groups, nitro groups, hydroxy groups, carboxy groups, sulfo groups, and halogen atoms. Examples of preferred substituents are alkyl groups having 3 to 16 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 3 to 16 carbon atoms, and aryloxy groups having 6 to 10 carbon atoms.
[0137] In general formula (VI), each of Y' and Y^ independently denotes a substituent. At a minimum, either Y^ or Y"^ denotes a cyano group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, alkylsulfone group, arylsulfone group, alkylsulfonyl group, arylsulfonyl group, or aminosulfonyl group. Additional examples of substituents are those given by way of example as substituents that can be present in hetero rings.
[0138] Each of Y^ and Y^ desirably independently denotes a cyano group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, alkylsulfone group, arylsulfone group, alkylsulfonyl group, arylsulfonyl group, or aminosulfonyl group. Y' and Y^ desirably denote cyano groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, or aminocarbonyl groups. When Y' and Y^ denote alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, alkylsulfone groups, arylsulfone groups, alkylsulfonyl groups, arylsulfonyl groups or aminosulfonyl groups, they may further comprise substituents. Examples of

the substituents are alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 14 carbon atoms, aralkyl groups having 7 to 15 carbon atoms, heterocyclic groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 14 carbon atomis, alkylsulfenyl groups having 1 to 20 carbon atoms, arylsulfenyl groups having 6 to 14 carbon atoms, alkylsulfonyl groups having 1 to 20 carbon atoms, arylsulfonyl groups having 6 to 14 carbon atoms, acyl groups having 2 to 21 carbon atoms, carbamoyl groups having 1 to 25 carbon atoms, sulfamoyl groups having 0 to 32 carbon atoms, alkoxycarbonyl groups having 1 to 20 carbon atoms, aryloxycarbonyl groups having 7 to 15 carbon atoms, acylamino groups having 2 to 21 carbon atoms, sulfonylamino groups having 1 to 20 carbon atoms, amino groups having 0 to 32 carbon atoms, cyano groups, nitro groups, hydroxy groups, carboxy groups, sulfo groups, and halogen atoms. Desirable examples are alkyl groups having 3 to 16 carbon atoms and aryl groups having 6 to 10 carbon atoms.
[0139] Y' and Y^ may be linked together to form a ring. Examples of the ring that is formed are the above exemplified ring structures A-1 to A-64. Desirable rings are A-8, A-9, A-10, A-11, A-12, A-13, A-14, A-16, A-17, A-36, A-39, A-41, A-54, and A-57. Preferred rings are A-2, A-8, A-9, A-10, A-13, A-14, A-16, A-17, and A-57. Optimal rings are A-2 and A-9.
[0140] In general formula (VI), each of L and L independently denotes a methine group. The methine group may be substituted. Examples of the substituent are the above substituents given by way of example of substituents that may be present on the hetero ring.
[0141] In general formula (VI), n denotes an integer falling within a range of 0 to 2. From the perspective of wavelength suitability, 0 or 1 is desirable, and 0 is optimal. [0142] The compounds denoted by general formula (VI) may be bonded at any position to form a polymer; in that case, the various units may be identical or different, and may be bonded to polymer chains such as polystyrene, polymethacrylate, polyvinylalcohol, and cellulose.
[0143] The compound denoted by general formula (VI) may have a charge or may be neutral. Whether the compound denoted by general formula (VI) is a cation or an anion, and whether or not it possesses a net ion charge, depends on auxochromes and substituents. When the substituent comprises a dissociative group, it may dissociate and hold a negative charge. In that case, as well, the overall charge of the molecule is neutralized by a counter ion. Typical counter ions in the form of cations include inorganic and organic ammonium ions (such as tetraalkylammonium ions and pyridinium ions) and alkali metal ions. On the other hand, anions may be inorganic

anions or organic anions, such as halogen anions (such as fluoride ions, chloride ions, bromide ions, and iodide ions), substituted arylsulfonic acid ions (such as p-toluenesulfonic acid ions and p-clilorobenzenesulfonic acid ions), aryldisulfonic acid ions (such as 1,3-benzenedisulfonic acid ions, 1,5-naphthalenedisulfonic acid ions, and 2,6-naphthalenedisulfonic acid ions), alkylsulfuric acid ions (such as methyl sulfate ions), sulfiiric acid ions, thiocyanic acid ions, perchloric acid ions, tetrafluoroboric acid ions, picric acid ions, acetic acid ions, and trifluoromethanesulfonic acid ions.
Charge-equilibrating counter ions in the form of ionic polymers or other dyes having the opposite charge of the dye may be employed. Metal complex ions (such as bisbenzene-l,2-dithiolate nickel (III)) may also be possible.
[0144] Specific desirable examples of the compound denoted by general formula (VI) are given below, but the present invention is not limited thereto. [0145] [Chem.48]

M. Sturmer, Heterocyclic Compounds - Special topics in heterocyclic chemistry, Chapter 18, Section 14, pp. 482-515, John Wiley & Sons, New York and London, published in 1977; Rodd's Chemistry of Carbon Compounds, 2nd Ed., Vol. IV, Part B, published in 1977, Chapter 15, pp. 369-422, published by Elsevier Science Publishing Company, Inc., New York; British Patent No. 1,077,611; and the like, which are expressly incorporated herein by reference in their entirety.
[0154] From the perspective of sensitivity during pattern exposure by laser, the thermal decomposition temperature of the compound for photoresist of the present invention in the form of a compound having a merocyanine dye structure is desirably equal to or higher than lOO^C but equal to or lower than 600°C, preferably equal to or higher than 100°C but equal to or lower than 600°C, more preferably equal to or higher than 120°C but equal to or lower than 550°, and optimally, equal to or higher than 150°C but equal to or lower than 500°C.
[0155] The compound for photoresist of the present invention can be a compound comprising a phthalocyanine dye skeleton. Among compounds comprising a phthalocyanine dye skeleton, from the perspectives of light absorption characteristics, thermal decomposition characteristics, and the like, the phthalocyanine dye denoted by general formula (VII) below is an example of a desirable phthalocyanine dye. [0156] [Chem. 56] General formula (VII)

[0157] In general formula (VII), R denotes a substituent. Examples of the
substituent are those given by way of example as R"' to R"* and R^' to R^^ in general
formula (VIII), described further below.
[0158] n denotes an integer falling within a range of 1 to 8, desirably 1 to 6, and
preferably, 1 to 4. When n^ is an integer of equal to or greater than 2, plural R^'s
present may be identical to or different from each other.
[0159] M denotes two hydrogen atoms, a divalent to tetravalent metal atom, a divalent
to tetravalent oxymetal atom, or a divalent to tetravalent metal atom comprising a ligand.
Specific examples and desirable examples thereof are those set forth further below for
general formula (VIII).

[0160] An example of a desirable embodiment of the phthalocyanine dye denoted by
general formula (VII) is the phthalocyanine dye denoted by general formula (VIII)
below.
[0161] [Chem. 57]
General formula (VIII)
RP1 RP2

RP6 RP5
[0162] In general formula (VIII), each of R"' to R"** and R"^' to R'^** independently denotes a hydrogen atom, halogen atom, cyano group, nitro group, formyl group, carboxyl group, sulfo group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 14 carbon atoms, substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or imsubstituted aryloxy group having 6 to 14 carbon atoms, substituted or unsubstituted acyl group having 2 to 21 carbon atoms, substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, substituted or unsubstituted arylsulfonyl group having 6 to 14 carbon atoms, heterylsulfonyl group having 1 to 10 carbon atoms, substituted or unsubstituted carbamoyl group having 1 to 25 carbon atoms, substituted or unsubstituted sulfamoyl group having 0 to 32 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, substituted or unsubstituted aryloxycarbonyl group having 7 to 15 carbon atoms, substituted or unsubstituted acylamino group having 2 to 21 carbon atoms, substituted or unsubstituted sulfonylamino group having 1 to 20 carbon atoms, or substituted or unsubstituted amino group having 0 to 36 carbon atoms. In this context, the amino groups include anilmo groups. From the perspectives of solvent solubility, absorption characteristics, and thermal decomposition properties, at least 8 from among R"' to R"* and R'^' to R^^ are hydrogen atoms, but without all of R"' to R"^ being hydrogen atoms.

[0163] Each of R"' to R"^ and R"^' to R"^^ desirably independently denotes a hydrogen atom, halogen atom, carboxyl group, sulfo group, substituted or unsubstituted alkyl group having 1 to 16 carbon atoms (such as a methyl, ethyl, n-propyl, or i-propyl group), substituted or unsubstituted aryl group having 6 to 14 carbon atoms (such as a phenyl, p-methoxyphenyl, or p-octadecylphenyl group), substituted or unsubstituted alkoxy group having 1 to 16 carbon atoms (such as a methoxy, ethoxy, or n-octyloxy group), substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms (such as a phenoxy or p-ethoxyphenoxy group), substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms (such as a methanesulfonyl group, n-propylsulfonyl group, or n-octylsulfonyl group), substituted or unsubstituted arylsulfonyl group having 6 to 14 carbon atoms (such as a toluenesulfonyl or benzenesulfonyl group), substituted or unsubstituted sulfamoyl group having 0 to 20 carbon atoms (such as a methylsulfamoyl or n-butylsulfamoyl group), alkoxycarbonyl group having 1 to 17 carbon atoms (such as a methoxycarbonyl or n-butoxycarbonyl group), substituted or xmsubstituted aryloxycarbonyl group having 7 to 15 carbon atoms (such as a phenoxycarbonyl or m-chlorophenylcarbonyl group), substituted or unsubstituted acylamino group having 2 to 21 carbon atoms (such as an acet^-'lamino, pivaloylamino, or n-hexylamino group), or a sulfonylamino group having 1 to 18 carbon atoms (such as a methanesulfonylamino or n-butanesulfonylamino group).
[0164] R"' to R"^ and R"^ to R^^ more preferably denote hydrogen atoms, halogen atoms, carboxyl groups, sulfo groups, substituted or unsubstituted alkyl groups having 1 to 16 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 16 carbon atoms, substituted or unsubstituted alkylsulfonyl groups having 1 to 20 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 14 carbon atoms, substituted or unsubstituted sulfiunoyl groups having 2 to 20 carbon atoms, alkoxycarbonyl groups having 1 to 13 carbon atoms, substituted or unsubstituted acylamino groups having 2 to 21 carbon atoms, or sulfonylammo groups having 1 to 18 carbon atoms.
[0165] More preferably, R"^ to R°^ denote hydrogen atoms, halogen atoms, sulfo groups, substituted or unsubstituted alkoxy groups having 1 to 16 carbon atoms, substituted or unsubstituted alkylsulfonyl groups having 1 to 20 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 14 carbon atoms, substituted or unsubstituted sulfamoyl groups having 2 to 20 carbon atoms, substituted or unsubstituted acylamino groups having 2 to 21 carbon atoms, or sulfonylamino groups having 1 to 18 carbon atoms, and R^' to R''^ denote hydrogen atoms or halogen atoms.

Particularly preferably, R"*^ to R"^ denote hydrogen atoms, sulfo groups, substituted or unsubstituted alkylsulfonyl groups having 1 to 20 carbon atoms, unsubstituted arylsulfonyl groups having 6 to 14 carbon atoms, or unsubstituted sulfamoyl groups having 7 to 20 carbon atoms, and R'^' to R''* denote hydrogen atoms. [0166] In general formula (VIII), from the perspectives of solvent solubility, absorption characteristics, and theimal decomposition properties, either R"' or R*^, either R*^ or R"", either R"^ or R"^ and either R"'' or R"^ -- a total of four -- desirably simultaneously don't denote hydrogen atoms.
[0167] In general formula (VIII), when the above-described groups denoted by R"' to R"^ and R*^' to R^* have substituents, examples of the substituents are as follows:
chain or cyclic substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms (such as methyl, ethyl, isopropyl, cyclohexyl, benzyl, and phenethyl groups), substituted or unsubstituted aryl groups having 6 to 18 carbon atoms (such as phenyl, chlorophenyl, 2,4-di-t-amylphenyl, and 1-naphthyl groups), substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms (such as vinyl and 2-methylvinyl groups), substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms (such as ethynyl, 2-methylethynyl, and 2-phenylethynyl groups), halogen atoms (such as F, CI, Br, and I), cyano groups, hydroxyl jp-oups, carboxyl groups, substituted or unsubstituted acyl groups having 2 to 20 carbon atoms (such as acetyl, benzoyl, salicyloyl, and pivaloyl groups), substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms (such as methoxy, butoxy, and cyclohexyloxy groups), substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms (such as phenoxy, 1 -napthoxy, and p-methoxyphenoxy groups), substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms (such as methyldiio, butylthio, benzylthio, and 3-methoxypropylthio groups), substituted or unsubstituted arylthio groups having 6 to 20 carbon atoms (such as phenylthio and 4-chlorophenylthio groups), substituted or unsubstituted alkylsulfonyl groups having 1 to 20 carbon atoms (such as methanesulfonyl and butanesulfonyl groups), substituted or unsubstituted arylsulfonyl groups having 6 to 20 carbon atoms (such as benzenesulfonyl and paratoluenesulfonyl groups), substituted or unsubstituted carbamoyl groups having 1 to 17 carbon atoms (such as unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, and dimethylcarbamoyl groups), substituted or unsubstituted acylamino groups having 1 to 16 carbon atoms (such as acetylamino and benzoylamino groups), substituted or unsubstituted acyloxy groups having 2 to 10 carbon atoms (such as acetoxy and benzoyloxy groups), substituted or unsubstituted alkoxycarbonyl groups having 2 to 10 carbon atoms (such as methoxycarbonyl and ethoxycarbonyl groups), five- or six-membered substituted or

unsubstituted heterocyclic groups (such as pyridine groups, thienyl groups, furyl groups, thiazolyl groups, imidazolyl groups, pyrazolyl groups, and other aromatic heterocyclic groups; pynolidine rings, piperidine rings, morpholine rings, pyran rings, thiopyran rings, dioxane rings, dithiolane rings, and other nonaromatic heterocyclic groups). [0168] In general formula (VIII), desirable examples of the substituents substituting the groups described above as the groups denoted by R"^ to R*^ and R'^^ to R''* are chain or cyclic substituted or unsubstituted alkyl groups having 1 to 16 carbon atoms, aryl groups having 6 to 14 carbon atoms, alkoxy groups having 1 to 16 carbon atoms, aryloxy groups having 6 to 14 carbon atoms, halogen atoms, alkoxycarbonyl groups having 2 to 17 carbon atoms, carbamoyl groups having 1 to 10 carbon atoms, and acylamino groups having 1 to 10 carbon atoms.
Of these, the following are desirable: chain or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, chlorine atoms, alkoxycarbonyl groups having 2 to 11 carbon atoms, carbamoyl groups having 1 to 7 carbon atoms, and acylamino groups having 1 to 8 carbon atoms.
Of these, the following are preferred: branched chain or cyclic unsubstituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkoxy groups having 1 to 8 carbon atoms, unsubstituted alkoxycarbonyl groups having 3 to 9 carbon atoms, phenyl, and chlorine atoms. The optimal substituents are unsubstituted alkoxy groups having 1 to 6 carbon atoms.
[0169] M denotes two hydrogen atoms, a divalent to tetravalent metal atom, a divalent to tetravalent oxymetal atom, or a divalent to tetravalent metal atom comprising a ligand. M desirably denotes a divalent to tetravalent metal atom. Of these, copper atoms, zinc atoms, magnesium atoms, or palladium atoms are desirable. Copper atoms and zinc atoms are preferred, and copper atoms are optimal.
[0170] The compounds denoted by general formula (VII) or (VIII) may be bonded at any position to form polymers. In that case, the individual units may be identical to or different from each other, and may be bonded to a polymer chain such as polystyrene, polymethacrylate, polyvinylalcohol, or cellulose.
[0171] The compounds denoted by general formula (VII) or (VIII) may be employed singly as specific compounds, or several such compounds of differing structure may be mixed for use. In particular, to prevent crystallization of the resist film, it is desirable to employ a mixture of isomers having substituents at different positions. [0172] Specific examples of phthalocyanine dyes that are desirable as the compound for photoresist of the present invention will be given below. However, the present

[0176] Tlie phlhalocyaninc dye as the compound for photoresist of tlic present invention can be synthesized, for example, by the method described or cited by Shirai and Kobayaslii, published by IPC (Ltd.), "Phthalocyanine Chemistry and Functions" (pp. 1 to 62); C. C. Leznoff and A. B. P. Lever, published by VCH, "Phthalocyanines -Properties and Applications" (pp. 1 to 54), which are expressly incorporated herein by reference in their entirety, or a similar method. It is also available as a commercial product in some cases.
[0177] From the perspective of sensitivity during pattern exposure by laser, the thermal decomposition temperature of the compound for photoresist of the present invention in the form of a compound comprising a phthalocyanine dye skeleton is desirably equal to or higher than lOO^C but equal to or lower than 600°C, preferably equal to or higher than 120°C but equal to or lower than 550°C, and optimally equal to or higher than 150°C but equal to or lower than 500°C.
[0178] The compound for photoresist of the present invention can be an azo compound or a complex compound of an azo compound and a metal ion. In the present invention, the term "azo compound" is a general temi for organic compounds in which two organic groups (R and R') are linked by an azo group (-N=N-). [0179] Various metals capable of forming complexes can be employed as the metal forming a complex with the azo compound. From the perspective of forming an absorption spectrum with good shape, transition metals are desirable and Ni, Co, Cu, Fe, Zn, and Pd are preferred. The complex affords good thin film formation properties in the course of forming a resist film from a resist coating liquid, so the azo compound desirably forms a complex with a metal ion.
[0180] The azo compound denoted by general formula (IX) below is a desirable example of an azo compound from the perspective of light absorption characteristics, thermal decomposition characteristics, and the like. [0181] [Chem.60] General formula (IX)
Q^-N=-N-Q2
[0182] In general formula (IX), Q' denotes an aryl group or a heterocyclic group, with
a hetero ring being desirable.
[0183] When Q' is an aryl group, it is desirably a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms, preferably a substituted or unsubstituted benzene
having 6 to 20 carbon atoms.
[0184] When Q' is a hetero ring, it is desirably a substituted or unsubstituted

jlve-inembered hetero ring or a substituted or unsubstituted six-membered hetero ring. A five-membered hetero ring comprising 1 to 20 cai-bon atoms and 1 or more nitrogen atoms is prefeired. It may fonn a condensed ring with a benzene ring, benzofijran ring, pyridine ring, pyrrole ring, indole ring, thiophene ring, or the like. [0185] Examples of Q* are an oxazole nucleus having 3 to 25 carbon atoms (such as 2-3-methyloxazolyl), a thiazole nucleus having 3 to 25 carbon atoms (such as 2-3-methylthiazolyl), an imidazole nucleus having 3 to 25 carbon atoms (such as 2-1,3-diethylimidazolyl), an indolenine nucleus having 10 to 30 carbon atoms (such as 3,3-dimethylindolenine), a quinoline nucleus having 9 to 25 carbon atoms (such as 2-]-methylquinoIyl), a selenozole nucleus having 3 to 25 carbon atoms (such as 2-3-methylbenzoselenazolyl), a pyridine nucleus having 5 to 25 carbon atoms (such as 2-pyridyI), a thiazoline nucleus, an oxazoline nucleus, a selenazoline nucleus, a tellurazoline nucleus, a tellurazole nucleus, a benzotellurazole nucleus, an imidazoline nucleus, an imidazo[4,5-quinoxaline] nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, a pyrimidine nucleus, a pyrrole nucleus, a pyrazole nucleus, a pyrazolone, a pyridine nucleus, an isooxazole nucleus, a triazole nucleus, barbituric acid, and Meldrum's acid. These may be further substituted.
[0186] In general formula (IX), Q^ denotes an aryl group, heterocyclic group, or CR'*^R''^. In this context, each of R''^ and R''^ independently denotes a substituent. However, the total value of the Hiimmett's Op value of the substituent denoted by R'*' and that of the substituent denoted by R"^^ is equal to or greater than 0.6. When the total value of these Hammett's Op values is equal to or greater than 0.6, the compound for photoresist can achieve suitable absorption characteristics and thennal decomposition properties. Hammett's substituent constant Op values (referred to as "cp values", hereinafter) are described, for example, in Chem. Rev. 91, 165 (1991) and in references cited therein. Those that are not described therein can be calculated by the method described in these references.
[0187] When Q^ is an aryl group, it is desirably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably a substituted or unsubstituted benzene having 6 to 20 carbon atoms.
[0188] When Q^ is a hetero ring, it is desirably a substituted or unsubstituted five-membered hetero ring or a substituted or unsubstituted six-membered hetero ring, and preferably a five-membered hetero ring having 1 to 20 carbon atoms and comprising one or more nitrogen atoms.
[0189] When Q^ is the group denoted by CR^'R''^ the Hammett's Op value of the substituent denoted by R'" and that of the substituent denoted by R"*^ are both desirably

equal to or greater than 0.6. Examples of such R and R" are: cyano groups, nitro groups, acyl groups having 1 to 10 cai-bon atoms (such as acetyl, propionyl, butyryi, pivaloyl, and benzoyl groups), alkoxycarbonyl groups having 2 to 12 carbon atoms (such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, and decyloxycarbonyl groups), aryloxyciirbonyl gi-oups having 7 to 11 carbon atoms (such as phenoxycarbonyl groups), carbamoyl groups having 1 to 10 carbon atoms (such as methylcarbamoyi, ethylcarbamoyl, and phenylcarbamoyi groups), alkylsulfonyl groups having 1 to 10 carbon atoms (such as methanesulfonyl groups), arylsulfonyl groups having 6 to 10 carbon atoms (such as benzenesulfonyl groups), alkoxysulfonyl groups having 1 to 10 carbon atoms (such as methoxysulfonyl groups), sulfamoyl groups having 1 to 10 carbon atoms (such as ethylsulfamoyl and phenylsulfamoyl groups), alkylsulfmyl groups having 1 to 10 carbon atoms (such as methanesulfmyl and ethane sulfinyl groups), arylsulfmyl groups having 6 to 10 carbon atoms (such as benzenesulfmyl groups), alkylsulfenyl groups having 1 to 10 carbon atoms (such as methanesulfenyl and ethanesulfenyl groups), arylsulfenyl groups having 6 to 10 carbon atoms (such as benzenesulfenyl groups), halogen atoms, alkynyl groups having 2 to 10 carbon atoms (such as ethynyl groups), diacylamino groups having 2 to 10 carbon atoms (such as diacetylamino groups), phosphoryl groups, carboxyl groups, and five-membered or six-membered heterocyclic groups (such as 2-ben2;othiazolyl, 2-benzooxazoly], 3-pyridyl, 5-(lH)-tetrazolyl, and 4-pyrimidyI groups). [0190] R'" and R'*^ are desirably cyano groups, acyl groups having 1 to 10 carbon atoms, alkoxycarbonyl groups having 2 to 12 carbon atoms, carbamoyl groups having 1 to 10 carbon atoms, or five- or six-membered heterocyclic groups; preferably acyl groups having 1 to 10 carbon atoms, alkoxycarbonyl groups having 2 to 12 carbon atoms, or carbamoyl groups having 1 to 10 carbon atoms; and optimally, alkoxycarbonyl groups having 2 to 12 carbon atoms or carbamoyl groups having 1 to 10 carbon atoms.
[0191] General formula (IX) comprises multiple tautomers due to differences in notation of resonant structures. In particular, when Q^ is CR R ^ and either R"*^ or R''^ IS -CO-E^ (where E' is a substituent) — for example, when R'' is -CO-E^ — the usual notation is that of general formula (XI) below. Compounds of such notation are included in general formula (IX). [0192] [Chem. 61] General formula (XI)

Q

[Di general formula (XI), Q' is defined in the same manner as in general formula (IX), R'" denotes a substituent of which total value of a Hammetfs Cp value with that of the substitxient denoted by -C(OH)-E^ is equal to or gi-eater than 0.6, and p, denotes a
substituent.] |:::
[0193] The compound denoted by general fomiula (IX) is desirably denoted by general fonnula (X-1) or (X-2) below. [0194] [Chem. 62] General foiinula (X-1)
General fonnula (X-2)
[0195] In general fomiula (X-1), A/ denotes a group of atoms forming a hetero fing
with a carbon atom and nitrogen atom to which tliis is bonded. In general formula
(X-2), A'^ denotes a group of atoms forming a hetero aromatic ring with a carbon atom
and nitrogen atom to which this is bonded.
[0196] The hetero aromatic rings formed by A and A are desirably tliioazole, oxazole,
pyrazole, imidazole, thiadiazole, isoxazole, or triazole rings; preferably oxazole,
pyrazole, thiadiazole, isoxazole, or triazole rings; and optimally, pyrazole, thiadiazole,
or isoxazole rings.
[0197] Q^ and Q'' are defined identically to Q^ in general formula (IX), and the
specific examples and desirable ranges thereof are also identical thereto.
[0198] The above groups may comprise substituents. Examples of the substituents,
when present, are substituted or unsubstituted linear, branched, or cyclic alkyl groups
having 1 to 18 carbon atoms (desirably, 1 to 8 carbon atoms) (such as methyl, ethyl,

propyl, isopropvL n-bulyl, isobut}'!, sec-butyl, t-butyl, cyclohexyl, methoxyethyl,
ethoxycarbonylethyl, cyanoethyl, diethylaminoethyl, hydroxyethyl, chloroethyl,
acetoxyethyl, and trifluoromethyl groups); alkenyl groups having 2 to 18 carbon atoms
(desirably, 2 to 8 carbon atoms) (such as vinyl groups); allcynyl groups having 2 to 18
carbon atoms (desirably, 2 to 8 carbon atoms) (such as ethynyl gi'oups); substituted or
unsubstituted aryl groups having 6 to 18 carbon atoms (desirably, 6 to 10 carbon atoms)
(such as phenyl, 4-methylphenol, 4-methoxyphenyl, 4-carboxyphenyl, and
3,5-dicaTboxyphenyl groups); substituted or unsubstituted aralkyl groups having 7 to 18
carbon atoms (desirably, 7 to 12 carbon atoms) (such as benzyl and carboxybenzyl
groups); substituted or unsubstituted acryl groups having 2 to 18 carbon atoms
(desirably 2 to 8 carbon atoms) (such as acetyl, propionyl, butanoyl, and cliloroacetyl
groups); substituted or unsubstituted alkyl or arylsulfonyl groups having 1 to 18 carbon
atoms (desirably, 1 to 8 carbon atoms) (such as methanesulfonyl and p-toluenesulfonyl
groups); alkylsulflnyl groups having 1 to 18 carbon atoms (desirably, 1 to 8 carbon
atoms) (such as methanesulfmyl, ethanesulfinyl, and octanesulfmyl groups);
alkoxycarbonyl groups having 2 to 18 carbon atoms (desirably, 2 to 8 carbon atoms)
(such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups);
aryloxycarbonyl groups having 7 to 18 carbon atoms (desirably, 7 to 12 carbon atoms)
(such as phenoxycarbonyl, 4-methylphenoxycarbonyl and 4-methoxyphenylcarbonyl
groups); substituted or unsubstituted alkoxy groups having 1 to 18 carbon atoms
(desirably, 1 to 8 carbon atoms) (such as methoxy, ethoxy, n-butoxy, and
methoxyethoxy groups); substituted or unsubstituted aryloxy groups having 6 to 18
cnrhnn atoms (desirably, 6 to 10 carbon atoms) (such as phenoxy and
4-methoxyphenoxy groups); alkylthio groups having 1 to 18 carbon atoms (desirably, 1
to 8 carbon atoms) (such as methyltliio and ethylthio groups); arylthio groups having 6
to 10 carbon atoms (desirably, 1 to 8 carbon atoms) (such as phenylthio groups);
substituted or unsubstituted acyloxy groups having 2 to 18 carbon atoms (desirably, 2 to
8 carbon atoms) (such as acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy,
benzoyloxy, and chloroacetyloxy groups); substituted or unsubstituted sulfonyloxy
groups having 1 to 18 carbon atoms (desirably 1 to 8 carbon atoms) (such as
methanesulfonyloxy groups); substituted or unsubstituted carbamoyloxy groups having
2 to 18 carbon atoms (desirably, 2 to 8 carbon atoms) (such as methylcarbamoyloxy and
diethylcarbamoyloxy groups); unsubstituted amino groups and substituted amino groups
having 1 to 18 carbon atoms (desirably 1 to 8 carbon atoms) (such as methylamino,
dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino,
pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino.

phenoxycarbonylamino, phenylcarbamoylamino, ethyltliiocarbamoylaniino,
methylsulfamoylamino, phenylsiilfamoylamino, ethylcarbonylamino,
ethylthiocarbonylamino, cyclohexylcarbonylamino, benzoylamino, cUoroacetylamino,
methanesulfonylamino, and benzenesulfonylamino groups); amide groups having 1 to
18 carbon atoms (desirably, 1 to 8 carbon atoms) (such as acetamide, acetylmethylamide,
and acetyloctylamide groups); substituted or unsubstituted ureido groups having 1 to 18
carbon atoms (desirably, 1 to 8 carbon atoms) (such as unsubstituted ureido,
methylureido, ethylureido, and dimethylureido groups); substituted or unsubstituted
carbamoyl groups having 1 to 18 carbon atoms (desirably 1 to 8 carbon atoms) (such as
unsubstituted carbamoyl, methylcarbamoyi, ethylcarbamoyi, n-butylcarbamoyi,
t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, and
pyrrolidinocarbamoyl groups); unsubstituted sulfamoyl groups and substituted sulfamoyl groups having 1 to 18 carbon atoms (desirably, 1 to 8 carbon atoms) (such as methylsulfamoyl and phenyl sulfiimoyl groups); halogen atoms (such as fluorine, chlorine, and bromine); hydroxyl groups; mercapto groups; nitro groups; cyano groups; carboxyl groups; sulfo groups; phosphono groups (such as diethoxyphosphono groups); and heterocyclic groups (such as oxazole rings, benzooxazole rings, thiazole rings, benzothiazole rings, imidazole rings, benzoimidazole rings, indolenine rings, pyridine rings, morpholine rings, piperidine rings, pyrrolidine rings, sulfolane rings, furan rings, thiophene rings, pyrazole rings, pyrrole rings, chroman rings, and coumarin rings). [0199] Specific examples of azo compounds that are desirable as the compound for photoresist of the present invention are given below. However, the present invention is not limited thereto. [0200] [Chem. 63]

Example Compound (36)

Cu

Example Compound (37)

Cu

Example Compound (38)

Co

Example Compound (39)

Co

Example Compound (40) N

Examtple Compound (41)Cu

Example Compound (42) Cu

Example Compound (43)

Cu

[0209] The compound for photoresist of the present invention in the form of azo
compounds and azo complex compounds can be synthesized by Icnown methods, and
are in some cases available as commercial products.
[0210] From the perspective of sensitivity during pattern exposure by laser, the
thermal decomposition temperature of the compound for photoresist of the present
invention in the form of azo compounds and azo complex compounds is desirably equal
to or higher than 100°C but equal to or lower than 600°C, preferably equal to or higher
than nO^C but equal to or lower th;an 550°C, and more preferably, equal to or higher
than 150°C but equal to or lower than 500°C.
[0211] The compound for photoresist of the present invention that is optimal for the
wavelength of light employed in pattern exposure can be selected.
For example, as for the maximum absorption wavelength (Xmax), as the general index, when the wavelength of the laser beam employed is Xnm, a compound for photoresist can be selected that has a A,max falling within a range of }i± 150 nm, desirably X± 100 nm, so that the photoresist film will be efficiently decomposed or modified during pattern exposure. For example, when employing a semiconductor laser beam with a wavelength of 650 nm, a compound for photoresist with a maximum absorption wavelength falling within a range of 500 nm to 800 rmi, desirably falling within a range of 550 nm to 750 nm, can be selected. When employing a semiconductor laser beam with a wavelength of 405 nm, a compound for photoresist with a maximum absorption wavelength falling within a range of 255 nm to 555 nm, desirably falling within a range of 305 rmi to 505 nm, can be selected.
For the reasons as described above, the compound for photoresist of the present invention in the form of a compounid comprising a phthalocyanine dye skeleton can be selected that has a maximum absor]3tion wavelength (Xmax) falling within a range of X ± 150 nm, desirably X, ± 100 nm. For example, when employing a semiconductor laser beam with a wavelength of 650 nm, a compound with a maximum absorption

wavelength falling within a range of 500 nm to 800 lun, desirably falling within a range of 550 nm to 750 nm, can be selected. Further, a compound with a maximum absorption wavelength falling within a range of 255 nm to 555 nm, desirably falling within a range of 305 nm to 505 nm, can be selected. Phthalocyanine dyes are known to have intense primary absorption at 600 nm to 900 nm, generally known as Q-band absorption, and secondary absorption at 300 nm to 500 nm, knovra as Soret-band absorption. The above maximum absorption wavelength may refer to either the primary absorption wavelength or the secondary absorption wavelength. "When employing a semiconductor laser beam with a wavelength of 405 nm, the 300 nm to 500 nm Soret-band absorption wavelength desirably falls within the desirable range given above. [0212] [Photoresist liquid]
The photoresist liquid of the present invention comprises the compound for photoresist of the present invention and, desirably, a solvent. The photoresist liquid of the present invention may comprise one or more of the compound for photoresists of the present invention. A solvent that is a good solvent to the compound for photoresist of the present invention is desirably employed. In addition to the above components, the photoresist liquid of the present invention may optionally comprise other components. To form a resist film of good processability, the content of the compound for photoresist in the photoresist liquid of the present invention is desirably equal to or greater than 50 mass percent, preferably equal to or greater than 70 mass percent, more preferably equal to or greater than 90 mass percent, based on the total solid component of the photoresist liquid. By v/ay of example, the upper lim.it is 100 mass percent. [0213] The photoresist liquid of the present invention can be coated on a surface being processed and the solvent can be evaporated off to form a photoresist film. Examples of coating methods are spraying, spin coating, dipping, roll coating, blade coating, doctor roll coating, doctor blade coating, curtain coating, slit coating, and screen printing. The use of spin coating is desirable from the perspectives of good production efficiency and ease of controlling the film thickness. Conventionally known methods can be employed to remove the solvent from the photoresist liquid that has been coated. For example, when coated by the spin coating method, the rotational speed of the spinning can be increased to evaporate off the solvent, hi this process, air can be sprayed through nozzles onto the coated surface to accelerate evaporation of the solvent. In the same manner as in the process of coating conventional photoresist, a spin coated photoresist liquid film can be heated (baked) in what is known as prebaking. One particularly preferred method of removing the solvent is to coat the photoresist liquid by

spin coating and then increase the rotational speed of the spinning to remove the solvent. In that case, it is desirable to further conduct annealing by heating. Ajinealing has the effect of increasing the strength and stability of the photoresist film. The lower limit of the heating temperature is, for example, equal to or higher than 55°C, desirably equal to or higher than 65°C, and preferably, equal to or higher than TS^C. The upper limit of the heating temperature is, for example, equal to or lower than 200°C, desirably equal to or lower than 150°C, and preferably, equal to or lower than 100°C. The lower limit of the time is, for example, equal to or more than 5 minutes, desirably equal to or more than 15 minutes, and preferably, equal to or more than 30 minutes. The upper limit is, for example, equal to or less than 4 hours, desirably equal to or less than 2 hours, and preferably, equal to or less than 1 hour. Conducting armealing under conditions within such ranges can improve the strength and stability as the photoresist film without decreasing production efficiency.
[0214] Taking into account the coating properties (such as keeping the film thickness after coating and removing the solvent within desired ranges, achieving a uniform film thickness over the entire surface being processed, and the formation of a coating of uniform thickness over a number of irregularities on the surface being processed), the concentration of the total solid component in the photoresist liquid of the present invention is desirably equal to or greater than 0.1 mass percent but equal to or less than 10 mass percent, preferably equal to or greater than 0.4 mass percent but equal to or less than 5 mass percent, and more preferably, equal to or greater than 0.7 mass percent but equal to or less than 2 mass percent.
[0215] Among solvents that can be employed in the photoresist liquid of the present invention, taking into account the coating properties in the spin coat method, it is desirable for the solvent to be suitably volatile during coating, and in terms of manufacturing suitability, desirable for the solvent to have physical properties such as the following:
1. A boiling point of equal to or higher than 60°C but equal to or lower than 300°C is desirable, equal to or higher than 70°C but equal to or lower than 250°C is preferred, and equal to or higher than 80°C but equal to or lower than 200°C is optimal.
2. A viscosity of equal to or higher than 0.1 cP but equal to or lower than 100 cP is desirable, equal to or higher than 0.5 cP but equal to or lower than 50 cP is preferred, and equal to or higher than 1 cP but equal to or lower than 10 cP is optimal.
3. A flash point of equal to or higher than 25°C is desirable, equal to or higher than 30°C is preferred, and equal to or higher than 35°C is optimal. [0216] Specific examples of the above solvents are: hydrocarbons (such as

cyclohexane and l,l-dimethylc\'clohexane), alcohols (such as butanol, diacetone alcohol, and tetrafluoropropanol), glycol ethers (such as methyl cellosolve, propylene glycol monom ethyl ether, and propylene glycol monomethylether acetate), esters (such as butyl acetate, methyl lactate, and ethyl lactate), ketones (such as methyl ethyl ketone and methyl isobutyl ketone), nitriles (such as propionitrile and benzonitrile), amides (such as dimethylformamide), sulfones (such as dimethylsulfoxide), carboxylic acids (such as acetic acid), amines (such as triethylamine), halogens (such as trichloromethane and hydrofluorocarbons), and aromatics (such as toluene and xylene). Of these, the particularly preferred solvents in terms of coating properties are: alcohols or glycol ethers. The above solvents may be employed singly or in combinations of two or more.
[0217] It is sufficient for the photoresist liquid of the present invention to comprise at least the compound for photoresist as a solid component. Other components can be incorporated as needed. However, the total of the other components is desirably equal to or lower than 1 parts, relative to the mass of the compound for photoresist.
Examples of other components are binders, antifading agents, oxidation inhibitors, UV-absorbing agents, plasticizers, and lubricants. Examples of binders are natural organic polymeric substances such as gelatms, cellulose derivatives, dextran, rosins, and rubbers; and synthetic organic polymers such as hydrocarbon-based resins such as polyethylene, polypropylene, polystyrene, and polyisobutylene; vinyl-based resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride/polyvinyl acetate copolymers; acrylic resins such as polymethyl acrylate and polymethyl methacrylate; and initial condensates of poI)".'inylalcohol, chlorinated polyeth3der!e, epoxy resin, butyral resin, rubber derivatives, phenol formaldehyde resins, and other thermosetting resins. When adding a binder to the photoresist liquid of the present invention, the quantity of binder added is desirably 0.01 to 1 part, preferably 0.1 to 0.5 part, relative to the mass of the compound for photoresist of the present invention. [0218] The compound for photoresist of the present invention generally does not decompose or denature in a normal indoor illuminated environment. There is thus no need to handle it under safety lamps (such as illumination from which UV radiation or light of shorter wavelengths has been cut), such as is required by conventional photoresists. Various antifading agents can be incorporated to the photoresist liquid to form a resist film affording good light resistance when handled under such common indoor environment illumination.
Generally, singlet oxygen quenchers are employed as antifading agents. Known singlet oxygen quenchers that have been disclosed in the literature, such as in

patent specifications, can be employed. Specific examples are described in each publication such as Japanese Unexamined Patent Publication (KOKAI) Showa Nos. 58-175693, 59-81194, 60-18387, 60-19586, 60-19587, 60-35054, 60-36190, 60-36191, 60-44554, 60-44555, 60-44389, 60-44390, 60-54892, 60-47069, and 63-209995; Japanese Unexamined Patent Publication (KOKAI) Heisei No. 4-25492; Japanese Examined Patent Publication (KOKOKU) Heisei Nos. 1-38680 and 6-26028; German Patent No. 350399; and the Journal of the Chemical Society of Japan, October, 1992, p. 1,141. The quantity of the above singlet oxygen quenchers and other antifading agents that is employed, for example, falls within a range of 0.1 to 50 mass percent, desirably williin a range of 0.5 to 45 mass percent, preferably within a range of 3 to 40 mass percent, and more preferably, within a range of 5 to 25 mass percent, relative to the quantity of the compound for photoresist of the present invention. [0219] As is described further below, the photoresist liquid of the present invention pennits the formation of an etching mask without a developing step. Accordingly, neither the component combination of an o-naphthoquinonediazidosulfonic acid ester and a novolak resin, the component combination of a photoacid generator and a compound decomposing in the presence of an acid, the component combination of a photobase generator and a compound decomposing in the presence of a base, nor the component combination of a photoradical generator and an unsaturated addition-polymerizable compound is an essential component in the photoresist liquid of the present invention, despite the fact that these are contained as essential components in normal photopolymer-type resist liquids requiring a development step. These com.ponents are desirably not incoi-porated in the photoresist liquid of the present invention.
[0220] The photoresist liquid of the present invention can be obtained by mixing the compound for photoresist of the present invention with the above components as needed.
[0221] The photoresist liquid of the present invention can be coated on a surface that is to be processed and the solvent removed to form a photoresist film. The photoresist film can then be exposed to a desired pattern with a laser beam to form a desired resist pattern. The details of coating the photoresist liquid to form a resist film are as set forth above.
[0222] The compound for photoresist of the present invention assumes the function of the photoresist film. Thus, the compound for photoresist is desirably incorporated in a proportion of equal to or more than 50 mass percent, preferably equal to or more than 70 mass percent, and more preferably, equal to or more than 90 mass percent of the total

mass of the photoresist film. The upper limit is, for example, 100 mass percent. The various components that may be contained in the photoresist film are as set forth above for the photoresist composition of the present invention.
[0223] The embodiment of the photoresist liquid of the present invention in which the total solid component thereof is comprised of the compound for photoresist is particularly desirable from the perspective of the ease of recovering and re-using excess photoresist liquid (for example, photoresist liquid that is thrown off the surface being processed during spin coating) after providing it on the surface processed in the spin coating step.
[0224] The photoresist liquid of the present invention can be applied to any application that requires fine processing. For example, it can be employed instead of conventional photoresist liquid in various steps, such as the manufacturing steps of semiconductor devices such as LSIs, LEDs, CCDs, and solar cells; the manufacturing steps of FPDs such as liquid crystals, PDPs, and ELs; and the manufacturing steps of optical parts such as lenses and film. That is, the steps of coating the photoresist liquid of the present invention, removing the solvent, and pattern exposure can be used instead of the steps of coating a conventional photoresist liquid, removing the solvent, pattern exposure, and development.
[0225] The photoresist liquid of the present invention can also be used in the process of fabricating a master for nanoimprinting.
[0226] The photoresist liquid of the present invention can be used to form minute irregularities in surfaces such as the front surface, the rear surface (for example, a sapphire sub.strate and the like), and the lateral surface of an LED chip to enhance the light output efficiency of an LED. Generally, the refractive index of the material constituting the outermost layer (for example, a current diffoision layer or transparent electrode) serving as the light outlet of an LED chip differs from that of the package resin. For example, the refractive index of a current diffusion layer is equal to or greater than 3, while the refractive index of the package resin is about L5. When light is outputted from a portion of such a high refractive index to a portion of low refractive index, the light ends up reflecting at the boundary, reducing light output efficiency. In contrast, providing minute irregularities at the boundary can enhance light output efficiency. Accordingly, after forming the layer serving as the light outlet (for example, a current diffusion layer) of an LED chip, a photoresist film can be formed by coating the photoresist liquid of the present invention and removing a solvent, and exposed to a pattern by irradiation with a laser beam in just portions corresponding to the indentations in a pattern of desired minute irregularities, and subsequently, etching can

be conducted to etch the surface of the outlet corresponding to the portions irradiated with the laser beam to fonn indentations, thereby forming minute irregularities on the outlet. Then, necessary processing (such as forming electrodes on the surface of the current diffusion layer) can be conducted to complete the LED chip. The light outlet of an LED chip obtained in this manner will have minute irregularities on the surface thereof The LED obtained by packaging this LED element will have minute irregularities formed at the boundiary of the package resin and the light outlet, so reflection at the boundary will be reduced, permitting the fabrication of an LED with good light output efficiency. In this manner, when outputting from a portion of high refractive index to a portion of low refractive index, the provision of minute irregularities at the boundary can increase light output efficiency. It suffices for the depth h and the diameter d of indentations formed at the boundary of the light-emitting element to be of a size causing the scattering and diffraction of light generated in the light-emitting element. They are desirably equal to or greater than one-fourth the emission wavelength, and can be designed based on scattering theory. [0227] When forming minute irregularities on the surface being processed in this manner, the photoresist liquid of the present invention can be used to form a photoresist film on the surface, a laser can be used to expose a minute pattern, and it can be employed as a mask to form minute irregularities corresponding to the minute pattem in the surface being processed by RIE or the like. Further, a mask layer can be provided on the surface being processed, the photoresist liquid of the present invention can be used to form a photoresist film thereover, minute processing can be conducted thereon v/ith a laser, minute holes can then be formed in the mask layer by RTF,._ and the surface being processed can be further deeply etched by ICP (inductively coupled plasma) through the mask layer in which the minute holes have been formed. Etching methods employing such a mask layer are advantageous when the surface being processed is hard and difficult to etch, such as sapphire. A mask layer of SiOa, Ti02, SiN, SiON, or some other inorganic oxide film or nitride film is desirable.
[0228] The thickness t of the photoresist film formed with the photoresist liquid of the present invention and the diameter d of the indentations can be established based on the etching step conditions such as the type of the compound for photoresist of the present invention, material of the surface being processed, and selection ratio. They should also be set taking into account the optical characteristics during laser recording. As a desirable range, the upper limit of the thickness t of the resist layer satisfies t < lOOd, with t < lOd being preferable. The lower limit desirably satisfies t > d/100, with t > d/10 being preferable.

[0229] [Method of etching the surface being processed]
The present invention further relates to a method of etching a surface being processed. The etching method of the present invention comprises: forming a photoresist film by coating the photoresist liquid of the present invention on a surface being processed; pattern exposing the photoresist film; and subjecting at least a portion of the surface being processed on which is present the photoresist film following the pattern exposure to etching, to etch at least a portion of the surface being processed in an ai-ea corresponding to the portion that has been exposed in the pattern exposure. [0230] In the photoresist that has been pattern exposed, pits are formed in portions, that have been exposed during pattern exposure, of the photoresist film, or portions are formed in which localized physical changes have occurred, such as low-durability portions, hi etching, the surface being processed corresponding to pits and/or low-durability portions of the photoresist film is preferentially etched, and the underlying surface being processed is also etched, fonning indentations. At least a portion of the surface being processed can be etched in areas corresponding to the portion that has been exposed by pattern exposure to form minute irregularities in the surface being processed. When the surface being processed comprises plural thin films, at least one of the thin films can be removed in the form of a pattern. This can be utilized to fabricate various semiconductor devices.
[0231] Pattern exposure can be conducted by the known method of exposure through a photomask using a stepper. However, it is desirable to pulse modulate the laser beam, narrow the modulated laser beam through a lens, and conduct pattern exposure with the focal point on the photoresist film.. The recording devices used to record information on optical disks are suitable as the pattern exposure device for conducting such light irradiation. However, so long as an adequate amount of light can be converged, a monochromatic beam such as a laser beam is not required.
[0232] As the type of laser beam, any type of laser, such as a gas laser, solid laser, or semiconductor laser, can be employed. However, to simplify the optical system, a solid laser or a semiconductor laser is desirably employed. The laser beam may be a continuous beam or a pulsed beam, but the use of a laser beam with a readily adjustable light-emission interval is desirable. A semiconductor laser is an example of such a laser beam. When the laser carmot be directly on/off modulated, it is desirably modulated with an external modulation element.
[0233] As high a laser power as possible is desirable to increase the processing rate. However, as the laser power increases, the scan rate (the rate at which the laser beam is scanned over the coating film - for example, the rotational speed of the optical disk

drive, described further below) must be increased. Thus, taking into account the upper limit of the scan rate, the upper limit of the laser power is desirably 100 W, preferably 10 W, more preferably 5 W, and optimally, 1 W. The lower limit of the laser pov/der is desirably 0.1 mW, preferably 0.5 mW, and more preferably, 1 mW. [0234] The laser beam desirably has good transmission wavelength breadth and coherence, permitting naiTOwing to a spot size of about the wavelength. Further, the strategies such as those generally employed for optical disks are desirably adopted for the beam pulse irradiation conditions. That is, the conditions such as those employed for optical disks, such as the recording rate, pealc value of the irradiated laser beam, and pulse width, are desirably employed.
[0235] It suffices for the wavelength of the laser beam to permit high laser power. Desirable examples of readily achievable laser wavelengths are 1064 ±30 nm, 800 ± 50 nm, 670 ± 30 nm, 532 ± 30 nm, 405 ± 50 nm, 266 ± 30 nm, and 200 ± 30 nm. Of these, 780 ± 30 nm, 660 ± 20 nm, or 405 ± 20 nm at which high output can be achieved in a semiconductor laser is preferred; 405 ± 10 nm is optimal. It does not matter if Xa < Xw, or Xa > Xw, where la is the mfiximum absorption wavelength of the compound for photoresist employed and A,w is the laser beam wavelength. To uniformly apply light from the front surface to the rear surface of the photoresist film in the direction of thickness and totally apply heat to form holes of regular shape, the level of absorption of the thin film desirably falls witWn a fixed range. When absorption is excessively high, light only reaches the front surface, and when excessively low, the light is not converted to heat and the efficiency deteriorates. The upper limit of extinction coefficient k, which denotes the absorption tendency of a material, is suitably equal to or lower than 2, desirably equal to or lower than 1, and particularly preferably, equal to or lower than 0.5. The lower limit is desirably equal to or higher than 0.0005, equal to or higher than 0.005, or equal to or higher than 0.05. When the above relations are satisfied, the level of light absorption of the compound for photoresist is suitable and it is possible to form good pits or low-durability portions by pattern exposure. [0236] The thickness of the resist film can be suitably set within a range of 1 to 10,000 nm, for example. The lower thickness limit is desirably equal to or higher than 10 nm, preferably equal to or higher than 30 nm. This is because it is difficult to achieve an etching effect when the resist filmi is excessively thin. The upper thickness limit is desirably equal to or lower than 1,000 nm, preferably equal to or lower than 500 nm. This is because when the resist film is excessively thick, great laser power becomes necessary and it becomes difficult to form deep holes, and fiirther, the processing rate decreases.

[0237] For example, pit-fomiing methods publicly loiown in a write-once optical disk, a recordable optical disk and the like can be applied as the light irradiation method. As a specific example, a publicly laiown running OPC technique (for example, see Japanese Patent No. 3,096,239) can be applied, where the intensity of the reflected light of a laser varying with the pit size is detected, the output of the laser is corrected to render the intensity of the reflected light uniform, and uniform pits are formed. In the resist film of the present invention, when portions the physical properties of which have been changed to the point where they are removed by etching when irradiated with light are present in a localized manner, such portions can function as an etching mask by being removed during etching, h is thus unnecessary for pits (openings) that are recognizable to the eye, or the like, to be foraied. The size and processing pitch of pits and portions with changed physical properties can be controlled by adjusting the optical system. Since the light in a laser beam is the most intense near the center, gradually lessening toward the exterior, it is possible to form minute pits, smaller in diameter than the diameter of the laser beam spot, in the coating film. It suffices to linlc laser spots when it is desirable to form pits that are larger than the minimum processing shape of the laser beam.
[0238] Specific embodiments of the optical system used in processing are described below. However, the present invention is not limited to the embodiments indicated below.
The light irradiating device having the same configuration as that of a common optical disk drive can be employed. An optical disk drive configured as described in Japanese Unexamined Patent Publication (KOKAT) No. 2003-7.03348 can be employed. When employing such an optical disk drive and the object being processed, on which the coating film has been formed, is disk-shaped, it is loaded into the disk drive as is. When not of such a shape, the object being processed is adhered to a dummy optical disk or the like and loaded into the disk drive. A laser beam of suitable output is then irradiated onto the coating film. It then suffices to input a pulse signal or continuous signal to the laser beam source to match the pattern being irradiated with the processing pattern. A focusing technique identical to that of an optical disk drive, such as an astigmatizing method, can be employed to readily converge the light onto the surface of the coating film, even when waviness or warping is present on the surface of the coating film. Displacing the optical system toward the radius direction while rotating the object being processed in the same manner as when recording information on an optical recording disk permits periodic irradiation of the entire coating film with light. [0239] As the light irradiating conditions, the lower limit of the numerical aperture NA

of the optical system is desirably equal to or greater than 0.4, preferably equal to or greater than 0.5, and more preferably, equal to or greater than 0.6. The upper limit of the numerical aperture NA is desirably equal to or lower than 2, preferably equal to or lower than 1, and more preferably, equal to or lower than 0.9. When employing a large numerical aperture, employing what is Icnown as the liquid immersion method of positioning a liquid between an object lens and the photoresist film affords the advantage of facilitating focal point adjustment. That is because, when the numerical aperture NA is excessively small, minute processing is precluded, and when excessively large, the margin relative to the angular during light irradiation decreases. The wavelength of the optical system is, for example, 405 ± 30 nm, 532 ± 30 nm, 650 ± 30 nm, or 780 ± 30 nm. That is because these wavelengths readily achieve high output. The shorter the wavelength, the finer the processing that is possible, which is desirable. [0240] The lower limit of the output of the optical system is, for example, equal to or higher than 0.1 mW, desirably equal to or Mgher than 1 mW, preferably equal to or higher than 5 mW, and more preferably, equal to or higher than 20 mW. The upper limit of the output of the optical system is, for example, equal to or lower than 1,000 mW, desirably equal to or lower than 500 mW, and preferably, equal to or lower than 200 mW. This is because processing takes time when the output is excessively low, and the durability of the components making up the optical system decreases when the output is excessively high.
[0241] The lower limit of the linear speed of displacement of the optical system relative to the surface of the coating film is, for example, equal to or greater than 0.1 m/s. desirably equal to or greater than 1 m/s, more preferably equal to or greater than 5 m/s, and still more preferably, equal to or greater than 20 m/s. The upper limit of the linear speed is, for example, equal to or lower than 500 m/s, desirably equal to or lower than 200 m/s, more preferably equal to or lower than 100 m/s, and still more preferably, equal to or lower than 50 m/s. That is because it becomes difficult to increase processing precision when the lineeir speed is excessively high, and time is required for processing as well as it becomes difficult to achieve good shape processing when the linear speed is excessively low. As a specific example of an optical processing device comprising an optical system, a NEO500 made by Pulstec Industrial Co., Ltd. can be employed.
[0242] The photoresist film set forth above can be employed as an etching mask without a developing step following pattern exposure. A post-baking step, during which a heat treatment is conducted, can be inserted after pattern exposure and before the etching step described inrther below. Post baking can firmly bond the photoresist

illm to the surface being processed following pattern exposure, and enhance its function as a mask during subsequent etching. The lower limit of the heating temperature of post baking is, for example, equal to or higher than 55°C, desirably equal to or higher than 65°C, and preferably, equal to or higher than 75°C. The upper limit of the temperature is, for example, equal to or lower than 200°C, desirably equal to or lower than 150°C, and preferably, equal to or lower than 100°C. Conducting a heat treatment with such a range can enhance the above-described effect without diminishing production efficiency.
[0243] Various examples of etching methods can be given, such as wet etcliing and dry etching; it suffices to employ a method corresponding to the physical properties of the surface being etched. To conduct minute processing it is desirable to employ RIE (reactive ion etching), which permits fine patterning with high direct etching gas propagation. RIE is conducted by placing the object being processed within a gas-tight processing chamber, generating a prescribed reduced pressure atmosphere within the processing chamber by introducing a prescribed processing gas and drawing a vacuum, then applying liigh-frequency power to electrodes formed within the processing chamber, for example, to excite a plasma, and using the etchant ions in the plasma to conduct etching to the object being processed. The etching gas of RIE can be selected based on the substance being etched.
The photoresist film formed of the photoresist liquid of the present invention is normally removed following etching but can be allowed to remain, depending on the application. The photoresist film can be removed by a wet removal method employing a stripping solution (such as ethanol), for example.
[0244] The embodiment in which the photoresist liquid of the present invention is employed in etching has been described above. However, the photoresist liquid of the present invention can also be used to deposit a desired substance in a desired area on a surface being processed.
For example, an electrode such as AuZn or AuGe is provided on a portion of the surface of the light outlet (for example, the current diifusion layer) of an LED chip. In that case, the photoresist liquid of the present invention is coated on the surface of the light outlet (such as the surface of the current diffusion layer), the solvent is removed to form a photoresist film, and a laser beam is then irradiated onto an area where an electrode is to be formed to remove the photoresist film. In this case, the amount of the laser beam irradiated onto the photoresist film may be that sufficient to form low-durability portions. In that case, etching can subsequently be conducted to remove the photoresist film from low-durability portions, thereby removing the

photoresist film in the area in which an electrode is being fomied. Subsequently, the substance serving as the electrode (such as AuZn or AuGe) is deposited under vacuum and the photoresist film is then removed to form an electrode in a desired area on the surface of the light outlet.
[0245] As set forth above, the compound for photoresist of the present invention can be used to form minute irregularities and to fabricate semiconductor devices. Specific examples are semiconductor elements, magnetic bubble memories, integrated circuits, and various other electronic components, LED and fluorescent lamps, organic EL elements, plasma displays, and other light-emitting, but is not limited thereto. [0246] EXAMPLES
The present invention will be described below based on Examples. However, the present invention is not limited to the embodiments shown in Examples. [0247] [Example 1] Formation of photoresist film
A 2 g quantity of oxonol dye (Example Compound (II)-5, film ^max: 378 nm; thennal decomposifion temperature: 216°C) was dissolved in 100 mL of tetrafluoropropanol (TFP), and spin coated on a disk-shaped silicon substrate (0.6 mm in thickness, 120 mm in outer diameter, 15 mm in inner diameter) to form a coating film. The spin coating was conducted by dispensing a coating liquid on the inner circum¬ferential portion of the substrate at a coafing starting rotational speed of 500 rpm and a coating ending rotational speed of 100 rpm. The rotational speed was gradually increased to 2,200 rpm to dry the coating film. The coating film that was formed was 100 nm in thickness.
The silicon substrate on which the coating film had been formed was placed in a NEO500 made by Pulstec Industrial Co., Ltd. (wavelength: 405 nm, NA: 0.65), and a laser beam was directed onto the surface of the coating film. The laser beam irradiation conditions were as set forth below. Pits were formed on the coating film at a pitch of 0.5 micrometer.
Laser output: 2 mW
Linear speed: 5 m/s
Recording signal: 5 MHz rectangular wave [0248] [Example 2] Formation of irregularities
The silicon substrate processed in Example 1 was subjected to RIE etching under the following conditions from the surface side on which the coating film had been formed, after which the coating film was removed with ethanol as stripping solution.

The fonnation of minute irregulaiilics on the siuface of the silicon substrate from which the coating fihn had been removed was visually confirmed. From this result, it can be understood that the coating film processed in Example 1 had functioned as an etcliing mask.
Etching gas: SFe+ CHF3 (1:1)
Etching depth: 50 mn
[0249] [Examples 3 to 14] '">
With the exception that Example Compounds given in Table ^ below were employed as oxonol dyes, pits were fomied on the coatmg film at a 0.5 micrometer pitch in the same manner as in Example 1 by irradiation of the coating fihn surface with a laser beam in the same mamier as in Example 1. [0250] [Tables]
Example Compound Xmax of film (nra) Thermal decomposition temperature (°C)
Example 3 (II-l) 380 188
Example 4 (11-2) 393 245
Example 5 (II-3) 385 183
Example 6 (11-4) 378 200
Example 7 (11-16) 382 228
Example 8 (11-17) 393 265
Example 9 (11-18) 385 166
Example 10 (11-19) 378 220
Example 11 (11-20) 378 200
Example 12 (11-21) 377 145
Example 13 (11-22) 462 188
Example 14 (11-23) 572 237
[0251] r[&i^s44^-26]-- ' t''^'^' ^u 'j ^S C.v;f fU^- "^
Silicon substrates having the coating films on which pits had been formed that were obtained in Examples 3 to 14 were subjected to RLE etching in the same manner as in Example 2 and the coating films were removed with a stripping solution in the form of ethanol. The formation of minute irregularities was visually confirmed on the surface of each of the silicon substrates in the same manner as in Example 2. Based on this result, it can be understood that, in the oxonol dyes employed in Examples 3 to 14, the coatmg films thereof had fiinctioned as etcliing masks. Better shape of pits was

aciiie\'ed in tlie Examples in which d)'es having a ?.max witlnn the laser beam wavelength (405 nm) ± 150 nni range were employed than in the Examples in \N'hich dyes having a X,max outside the above range were employed. [0252] [Example 15] Formation of photoresist film
A 2 g quantity of cyanine dye (Example Compound rV-57, film Xmax: 448 nm, thennal decomposition temperature: 275°C) was dissolved in 100 mL of tetrafluoropropanol (TFP), and spin coated on a disk-shaped silicon substrate (0.6 mm in tliiclaiess, 120 mm in outer diameter, 15 mm in imier diameter) to fonn a coating fihn. The spin coating was conducted by dispensing a coating liquid on the inner circum¬ferential portion of the substrate at a coating stalling rotational speed of 500 rpm and a coating ending rotational speed of 100 q3m. The rotational speed was gradually increased to 2,200 rpm to dry the coating film. The coating film that was formed was 100 rnn in thiclaiess.
The silicon substrate on which the coating film had been formed was placed in a NEO500 made by Pulstec Industrial Co., Ltd. (wavelength: 405 nm, NA: 0.65), and a laser beam was directed onto the suiTace of the coating film. The laser beam irradiation conditions were as set forth below. Pits were formed on the coating film at a pitch of 0.5 micrometer.
Laser output: 2 mW
Linear speed: 5 m/s
Recording signal: 5 MHz rectangular wave [0253] [Example 16]
With the exception that the dye employed was changed from a cyanine dye to a styryl dye (Example Compound V-1, film Ajnax: 543 nm, thermal decomposition temperatxure: 280°C), a photoresist film was formed on a silicon substrate by the same method as in Example 15. The resist film was irradiated with a laser beam in the same manner as in Example 1 to form pits at a pitch of 0.5 micrometer in the resist film. [0254] [Examples 17 and 18] Formation of irregularities
The silicon substrates processed in Examples 15 and 16 were subjected to RIE etcliing under the conditions set forth below from the surface side on which the coating film had been formed, after which the coating films were removed with ethanol as stripping solution. The formation of minute in'egularities on the surfaces of the silicon substrates from which the coating films had been removed was visually confirmed From this result, it can be understood that the coating films processed in Examples.-r

and 2 had functioned as etching masks.
Etching gas: SF6 + CHF3 (1:1)
Etching depth: 50 nm
[0255] [Examples 19 to 26] 1
With the exception that tlie cyanine dyes or styryl dyes listed in Table/3 below
were employed as the dye, resist film surfaces were irradiated with laser beams in the
same manner as in Example 15 to fomi pits at a pitch of 0.5 micrometer in resist films
in the same manner as in Example T. /.'i__
[0256] [Table 4] ' ^7

Example Compound Maximum absorption wavelength (nm) Thermal decomposition temperature (°C)
Example 19 IV-61 441 249
Example 20 IV-62 360 310
Example 21 lV-63 379 308
Example 22 IV-64 612 270
Example 23 IV-65 695 268
Example 24 V-2 542 280
Example 25 V-3 524 300
Example 26 V-4 526 305
[0257] [Examples 27 to 34]
Silicon substrates having the resist films on which pits had been formed obtained in Examples 19 to 26 were subjected to RIE etching in the same manner as in Example 17, the coating films were removed with ethanol as stripping solution, and the formation of minute irregularities on the surface of each of the substrates was visually confinned in the same manner as in Example 17. From this result, it can be understood that, also in the cyanine dyes and the styryl dyes employed in Examples 19 to 26, the resist films thereof had functioned as etching masks. Better shape of pits was achieved in the Examples in which dyes having a X,max within the laser beam wavelength (405 nm) ±150 nm range were employed than in the Examples ui which dyes having a ?anax outside the above range were employed. [0258] [Example 35] (1) Formation of photoresist film
A 2 g quantity of merocyanine dye (Example Compound (S-39), thermal

cLv\impositioji temperature: 263''C} was dissolved in 100 mL of tetrafluoropropaiiol (TFP), and spin coated on a disk-shaped silicon substrate (0.6 mm in tlnclcness, 120 mm in outer diameter, 15 nmi in imier diameter) to fonn a coating film. The spin coating was conducted by dispensing a coating liquid on the inner circumferential portion of the substrate at a coating starting roteitional speed of 500 rpm and a coating ending rotational speed of 100 rpm. The rotational speed was gradually increased to 2,200 ipm to dry the coating film. The coating film that was foiTned was 100 nm in thickness with X,max of 379 nm.
The silicon substrate on wliich the coating film had been formed was placed in aNEO500 made by Pulstec Industrial Co., Ltd. (wavelength: 405 nm, NA: 0.65), and a laser beam was directed onto the surface of the coating film. The laser beam irradiation conditions were as set forth below. Pits were formed on the coating fihn at a pitch of 0.5 micrometer.
Laser output: 2 mW
Linear speed: 5 m/s
Recording signal: 5 MHz rectangular wave [0259] (2) Formation of in-egularities
The silicon substrate processed in (1) above was subjected to RIE etching under the conditions set forth below fi-om the surface side on which the coating film had been formed, after which the coating film was removed with ethaiiol as stripping solution. The formation of minute irregularities on the surface of the silicon substrate fi:om which the coathig film had been removed was visually confirmed. From this result, it can be undersluud thcit tlic coating film processed in (1) above functioned as an etcliing mask.
Etching gas: SFe + CHF3 (1:1)
Etching depth: 50 nm
[0260] [Examples 36 to 47] , b
With the exception that the merocyanine dyi (Example Compound S-39) was replaced with Example Compounds listed in Table/4- below, processing identical to that in Example 35 yielded the same results as in Example 35.

[0261] [Tables]

Example Compound Maximum absorption wavelength(nm)
Example 35 (S-39) 379
Example 36 (S-31) 381
Example 37 (S-32) 401
Example 38 (S-33) 416
Example 39 (S-34) 385
Example 40 (S-35) 370
Example 41 (S-36) 376
Example 42 (S-37) 388
Example 43 (S-38) 413
Example 44 (S-40) 344
Example 45 (S-41) 392
Example 46 (S-42) 402
Example 47 (S-43) 368
[0262] [Example 48]
(1) Formation of photoresist film
A 2 g quantity of phthalocyanine dye (Example Compoimd (VII-9), thermal decomposition temperature: 325°C, maximum absorption wavelength Imax: 346 nm) was dissolved in 100 mL of tetrafluoropropanol (TFP), and spin coated on a disk-shaped silicon substrate (0.6 mm in thictoess, 120 mm in outer diameter, 15 mm in inner diameter) to form a coating film. The spin coating was conducted by dispensing a coating liquid on the inner circumferential portion of the substrate at a coating starting rotational speed of 500 rpm and a coating ending rotational speed of 100 rpm. The rotational speed was gradually increased to 2,200 rpm to dry the coating film. The coating film that was formed was 100 nm in thickness.
The silicon substrate on which the coating film had been formed was placed in aNEO500 made by Pulstec Industrial Co., Ltd. (wavelength: 405 nm, NA: 0.65), and a laser beam was directed onto the surface of the coating film. The laser beam irradiation conditions were as set forth below. Pits were formed on the coating film at a pitch of 0.5 micrometer.
Laser output: 2 mW
Linear speed: 5 m/s
Recording signal: 5 MHz rectangular wave
95

[('263] (2) Fonnation of iiTCgularities
The silicon substrate processed in (1) above was subjected to RIE etching under the conditions set forth below fi-om the surface side on which the coating film had been fonned, after wliich the coating film was removed with ethaiiol as stripping solution. The fonnation of minute iixegularities on the surface of the silicon substrate from wMch the coating fihn had been removed was visually confirmed. From this result, it can be understood that the coating film processed in (1) above functioned as an etching mask.
Etchijig gas: SFe + CHF3 (1:1)
Etching depth: 50 nm
[0264] [Examples 49 to 59] ''
With the exception that phtliaiocyanine resin (VII-9) was replaced with
Example Compounds listed in Table,/5 below, processing identical to that in Example,!
yielded results identical to those in Example 48. /ii-V.
[0265] [Table 6]

Example Compound Maximum absorption wavelength (nm) Thermal decomposition temperature (°C)
Example 48 (VII-9) 346 325
Example 49 (VII-10) 343 333
Example 50 (VII-11) 342 367
Example 51 (VII-12) 349 364
Example 52 (Vll-13) 345 253
Example 53 (VII-14) 352 278
Example 54 (VII-15) 350 294
Example 55 (VII-16) 377 415
Example 56 (VII-29) 341 308
Example 57 (VII-41) 322 358
Example 58 (VII-42) 342 363
Example 59 (VII-43) 357 355
[0266] [Example 60] Formation of photoresist film
A 2 g quantity of azo dye (Example Compound (75), film maximum absorption wavelength >.max: 441 nm, thermal decomposition temperature: 270°C) was dissolved in 100 mL of tetrafluoropropanol (TFP), and spin coated on a disk-shaped silicon
96

i-ub_-trale (0.6 mm in ihiclcness, 120 mm in outer diameter, 15 iimi in inner diameter) to fomi a coating film. The spin coating was conducted by dispensing a coating liquid on the inner circumferential portion of the substrate at a coating starting rotational speed of 500 rpm and a coating ending rotational speed of 100 rpm. The rotational speed was gradually increased to 2,200 ipm to diy the coating film. The coating fihn that was fornied was 100 nm in thiclcness.
The silicon substrate on wlaich the coating film had been formed was placed in a NEO500 made by Pulstec Mdustrial Co., Ltd. (wavelength: 405 nm, NA: 0.65), and a laser beam was directed onto the surface of the coating film. The laser beam in-adiation conditions were as set forth below. Pits were formed on the coating film at a pitch of 0.5 micrometer.
Laser output: 2 mW
Linear speed: 5 m/s
Recording signal: 5 MHz rectangular wave [0267] [Example 61] Formation of iiTegulaiities
The silicon substrate having a photoresist film in wliich pits were formed that had been processed in Example 60 was subjected to RIE etcliing under the conditions set forth below from the surface side on which the coating film had been formed, after wliich the coating film was removed with ethanol as stripping solution. The formation of mhiute iixegularities on the surface of the silicon substrate from which the coating film had been removed was visually confmned. From this result, it can be understood dial Llie pholorcsist film obtained in E:\ampic 60 in Vvhich pits had been fonricd fiinctioned as an etching mask.
Etcliing gas: SFe + CHF3 (1:1)
Etching depth: 50 nm
[0268] [Examples 62 to 69] ]J
With the exception that Example Compounds listed in Table J^ below were 'c:^ employed as an azo dye, a laser beam was irradiated onto the photoresist film surface in the same manner as in Example 60, forming pits in the photoresist film at a pitch of 0.5 micrometer in the same manner as in Example 60.
97

^0269] [Table' ■]
f
i 1 ! Example Compound Maximum absorption wavelength (nm) Themial decomposition temperature (°C)
Example 62 (81) 460 254
Example 63 (82) 482 331
Example 64 (85) 439 275
Example 65 (86) 377 322
Example 66 (87) 457 321
Example 67 (44) 455 321
Example 68 (46) 598 340
Example 69 (47) 603 320
[0270] [Examples 70 to 77]
With the silicon substrates having photoresist films in wliich pits were formed that had been obtained in Examples 62 to 69, RIE etcliing was conducted in the same manner as in Example 61, the coating films were removed with ethanol as stripping solution, and the formation of minute in-egulaiities on the surface of each of the silicon substrates was visually confirmed in the same manner as in Example^ Based on this result, it can be understood that, also in the azo dyes employed in Examples 62 to 69, the photoresist films thereof had functioned as etching masks. Better shape of pits was acliieved in the Examples in which dyes having a X,max within the laser beam wavelength (405 mn) ± 15U mn range were employed than in tlie Examples in which dyes having a Xmax outside the above range were employed.
[0271] Minute surface processing can be readily conducted according to the present invention.

[1] A compound for photo resist, selected from the group consisting of a compound
comprising an axonal dye skeleton, a cyanine dye, a story dye, a compound comprising a merocyanine dye skeleton, a compound comprising a phthalocyanine dye skeleton, an azoth compound, and a complex compound of an azoth compound and a metal ion. [2] A compound for photo resist according to claim 1, which is a compound denoted by the following general formula (I): [Chem. 1] General formula (I)

wherein, in general formula (I), each of A, B, C, and D independently denotes an electron-withdrawing group, with a total of a Hammett's Op value of the electron-withdrawing group denoted by A and that of the electron-withdrawing group denoted by B being equal to or greater than 0.6 and a total of a Hammett's Op value of the electron-withdrawing group denoted by C and that of the electron-withdrawing group denoted by D being equal to or greater than 0.6, A and B may be linked together to form a ring, C and D may be linked together to form a ring, R denotes a subsistent on a methane carbon, m denotes an integer of equal to or greater than 0 but equal to or less than 3, n denotes an integer of equal to or greater than 0 but equal to or less than (2m+l), plural Rest present may be respectively identical or different and may be linked together to form a ring when n denotes an integer of equal to or greater than 2, and X denotes a counter ion that neutralizes a charge of the compound denoted by general formula (I).
[3] The compound for photoresist according to claim 2, which has a thermal
decomposition temperature of equal to or higher than 100 °C but equal to or lower than 500 °C.
[4] The compound for photoresist according to claim 1, which is a compound
denoted by the following general formula (IV): [Chem. 2]


wherein, in general formula (IV), each of l) and T} independently denotes a group of nonmetal atoms required to form an optionally condensed, five- or six-membered trogons-containing hetero ring, each of L , L , and L independently denotes a methane chain, m denotes an integer ranging from 0 to 2, each of R and R independently denotes a substituent, plural L s and L s present may be identical or different when m
11 l'^ I*] 1yl
denotes 2; each of p and q independently denotes 0 or 1, each of R , R , R , and R
independently denotes a hydrogen atom or a substituent; and X denotes a counter ion
neutralizing a charge of the compound denoted by general formula (IV).
[5] The compound for photoresist according to claim 1, which is a compound
denoted by the following general fondle (V):
[Chem. 3]

wherein, in general formula (V), Z denotes a group of nonmetal atoms required to form an optionally condensed, five- or six-membered nitrogen-containing hetero ring, each of \} and L^ independently denotes a methane chain, each of R , R , R, and R independently denotes a substituent, n' denotes an integer ranging from 0 to 4, plural Ross present may be identical or diflPsrent when n' is equal to or greater than 2; r denotes 0 or 1, each of R^^ and R'^ independently denotes a hydrogen atom or a substituent; and X^ denotes a counter ion neutralizing a charge of the compound denoted by general formula (V).
[6] The compound for photoresist according to claim 4 or 5, which has a thermal
decomposition temperature of equal to or higher than 100 °C but equal to or lower than

600 =C.
[7] The compound for photoresist according to claim 1, which is a compound
denoted by the following general fondle (VI):
[Chem. 4]

wherein, in general formula (VI), Z^' denotes a group of atoms forming a five- or six-membered hetero ring with X" and X'^, each of X" and X independently denotes a carbon atom or a hetero atom, with at least either of X or X denoting a hetero atom, each of Y' and Y independently denotes a substituent, with at least either of Y' and Y denoting a cyano group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, alkylsulfone group, arylsulfone group, alkylsulfonyl group, arylsulfonyl group, or aminosulfonyl group, Y and Y may be linked together to form a ring, each of L and L independently denotes a methine group, and n denotes an integer rangmg from 0 to 2.
[8] The compound for photoresist according to claim 7, which has a thermal
decomposition temperature of equal to or higher than 150 °C but equal to or lower than 500 °C.
[9] The compound for photoresist according to claim 1, which is a compound
denoted by the following general formula (VII): [Chem. 5]
wherein, in general formula (VII), R'denotes a substituentdenotes an integer ranging from 1 to 8, plural R^'s present may be identical to or different from each other when n^ is an integer of equal to or greater than 2, and M denotes two hydrogen atoms, a divalent to tetravalent metal atom, a divalent to tetravalent oxymetal atom, or a divalent to tetravalent metal atom comprising a ligand. [10] The compound for photoresist according to claim 9, wherein the compound

in general formula (VIII), each of Ra' to Ra" and Rp' to Rp* independently denotes a hydrogen atom, halogen atom, cyano group, nitro group, formyl group, carboxyl group, sulfo group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 14 carbon atoms, substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 14 carbon atoms, substituted or imsubstituted acyl group having 2 to 21 carbon atoms, substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atom’s, substituted or unsubstituted group having 6 to H carbon atoms, heterylsulfonyl group having 1 to 10 carbon atoms, substituted or unsubstituted carbamoyl group having 1 to 25 carbon atoms, substituted or unsubstituted sulfamoyl group having 0 to 32 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, substituted or unsubstituted aryloxycarbonyl group having 7 to 15 carbon atoms, substituted or unsubstituted acylamino group having 2 to 21 carbon atoms, substituted or unsubstituted sulfonylamino group having 1 to 20 carbon atoms, or substituted or unsubstituted amino group having 0 to 36 carbon atoms, with at least 8 from among Ra to Ra and Rp to RP being hydrogen atoms, but without all of Rato Ra^ being hydrogen atoms; and M is defined in the same manner as in general formula (VII).
[11] The compound for photoresist according to claim 10, wherein, in general formula (VIII), either
o
Ra are not a hydrogen atom.

p. 2 J The compound for photoresist according to any of claims 9 to 11, which has a
thermal decomposition temperature of equal to or higher than 150 °C but equal to or
lower than 500 T.
[13] The compound for photoresist according to claim 1, which is a compound
denoted by the following general formula (IX) or a complex compound of the
compound and a metal ion:
[Chem. 7]
General formula (IX)
Q^-N==N-Q2
wherein, in general formula (IX), Q' denotes an aryl group or a heterocyclic group, denotes an aryl group, heterocyclic group, or CR R , each of R and R'independently denotes a substituent with a total value of a Hammett's asp value of the substituent denoted by R"" and that of the substituent denoted by R being equal to or greater than 0.6.
[14] The compound for photoresist according to claim 13, wherein the compound denoted by general formula (IX) is a compound denoted by the following general formula (X-l): [Chem. 8]
General formula (X-l)
wherein, in general formula (X-l), A' denotes a group of atoms forming a hetero
aromatic ring with a carbon atom and nitrogen atom to which this is bonded, and Q is
defined in the same manner as Q in general formula (IX).
[15] The compound for photoresist according to claim 13, wherein the compound
denoted by general formula (IX) is a compound denoted by the following general
formula (X-2):
[Chem. 9]
General formula (X-2)

gherkin. in general formula (X-2), A^ denotes a group of atoms forming a hetero
aromatic ring with a carbon atom and nitrogen atom to which tiles is bonded, and Q'* is
defined in the same manner as Q" in general formula (IX).
[16] The compound for photoresist according to any of claims 13 to 15, which has a
thermal decomposition temperate of equal to or higher than 150 °C but equal to or
lower than 500 °C.
[17] A photoresist liquid, comprising at least one of the compound for photoresist
according to any of claims 1 to 16.
[18] The photoresist liquid according to claim 17, which comprises the compound
for photoresist in a quantity of equal to or greater than 50 mass percent based on total
solid component comprised in the photoresist liquid.
[19] A method of etching a surface being processed, comprising:
forming a photoresist film by coating the photoresist liquid according to claim 17 or 18 on a surface being processed;
pattern exposing the photoresist film; and
subjecting at least a portion of the surface being processed on which is present the photoresist film following the pattern exposure to etching, to etch at least a portion of the surface being processed in an area corresponding to the portion that has been exposed in the pattern exposure.
[20] The method of etching a surface being processed according to claim 19, wherein
a light employed for the pattern exposure is a laser beam having a wavelength, Xing
the compound for photoresist comprised in the photoresist film is a compound selected from the group consisting of a compound comprising an axonal dye skeleton, a cyanine dye, a story dye, a compound comprising a merocyanine dye skeleton, an azo compound, and a complex compound of an azo compound and a metal ion, and has a maximum wavelength within a range of X;tl50 run.
[21] The method of etching a surface being processed according to claim 19, wherein
a light employed for the pattern exposure is a laser beam having a wavelength, Ink,
the compound for photoresist comprised in the photoresist film is a compound comprising a phthalocyanine dye skeleton, and has a maximum absorption within a range of Ail50 nm.