BE1010516A4 - Working in positive photosensitive composition. - Google Patents

Abstract

The composition of the invention essentially comprises (a) a resin having an acid-decomposable radical, the solubility of which increases in an alkaline developer upon reaction with an acid, (b) a compound which generates an acid when is irradiated with actinic radiation; and (c) an acid-decomposable, non-polymeric dissolution inhibitor, of molecular weight not greater than 3000, containing an acid-decomposable radical, the solubility of which increases in an alkaline developer upon reaction with an acid. Said acid-decomposable non-polymeric dissolution inhibitor comprises at least three structural units per molecule, each of which has an acid-decomposable radical, substituted on a benzene ring, and there are at least nine bonding atoms (excluding the radicals decomposable by an acid) inserted between two radicals decomposable by an acid located at the greatest distance.

Description

       

    <Desc / Clms Page number 1>
 



  Photosensitive composition working in positive AREA OF THE INVENTION
The present invention relates to a positive working photosensitive composition which can be used in the manufacture of a lithographic printing plate or a semiconductor such as an integrated circuit (IC), or in the manufacture of a circuit board for a liquid crystal, a thermal head or other devices manufactured by photofabrication.



  BASIS OF THE INVENTION
Known positive working photoresist compositions generally include an alkali soluble resin and a naphthoquinone diazide compound as the photosensitive material. Examples of such compositions include the phenol novolak / substituted naphthoquinone diazide compounds disclosed in US Patents 3,666,473, US-4,115,128 and US-4,173,470. Typical examples of such compositions include a formed novolak resin of cresol formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazidesulfonic ester, as disclosed in LF Thompson, "Introduction to Microlithography", ACS, # 219, pages 112-121.



   In a positive working photoresist containing essentially a novolak resin and a quinone diazide compound, the novolak resin provides high resistance to plasma attack, while the naphthoquinone diazide compound serves as a dissolution inhibitor. In addition, when irradiated with light, the naphthoquinone diazide compound produces a carboxylic acid, thereby losing its ability to inhibit dissolution and increase the solubility of the novolak resin in alkalis.



   In view of the above, numerous photoresists working in a positive manner comprising a novolak resin and a photosensitive material of naphthoquinone diazide have to date been developed and implemented.

  <Desc / Clms Page number 2>

 practical use. These positive working photoresists have provided satisfactory results in the fabrication of fine lines having a line width as small as 0.8 µm to 2 µm.



   However, the degree of integration of integrated circuits has gradually increased. In the manufacture of semiconductor supports such as SLSI (Super Large Scale Integration), it is necessary to produce ultra-fine designs composed of lines having a very small width, of less than half a micrometer. To achieve the necessary resolution power, the wavelength of the exposure light used in the exposure apparatus for photolithography has been shifted to the short wavelengths. We are currently studying
 EMI2.1
 the use of far ultraviolet radiation, excimer type lasers (e.g. XeCl, KrF, ArF), x-rays, etc.



   When a conventional resin consisting of a novolak resin and a naphthoquinone diazide compound is used to form a lithographic pattern by using far ultraviolet radiation or excimer laser radiation, the light Difficulty reaching the base of the photoresist, because novolak and naphthoquinone diazide compounds exhibit strong absorption in the far ultraviolet region. This absorption results in a low sensitivity and a drawing which shrinks.



   One way to solve this problem is to use a chemically sensitized photoresist composition, as disclosed in US Patent 4,491,628 and in European Patent EP-249,139. A chemically sensitized photoresist composition is a patterning material which produces an acid in the exposed area when irradiated with radiation such as far ultraviolet radiation. The acid then acts as a catalyst for a reaction which increases the solubility, in a developer, of the area irradiated by radiation.

  <Desc / Clms Page number 3>

 actinic, to form a drawing on a support.



   Examples of such a chemically sensitized photoresist composition include a combination of a compound which undergoes photodecomposition, to produce an acid and an acetal or an O, N-acetal (as disclosed in
 EMI3.1
 JP-A-48-89003 (the term "JP-A" used herein means a "published unexamined Japanese patent application")), a combination of a compound which undergoes photodecomposition, to produce an acid and an orthoester or an amide acetal compound (as disclosed in JP-A-51-120714), a combination of a compound which undergoes photodecomposition to produce an acid and a polymer having an acetal or ketal radical in its main chain (as disclosed in JP-A-53-133429), a combination of a compound which undergoes photodecomposition,

   to produce an acid and an enolether compound (as disclosed in JP-A-55-12995), a combination of a compound which undergoes photodecomposition to produce an acid and an N-acyliminocarboxylic acid compound (as disclosed in JP-A- 55-126236), a combination of a compound which undergoes photodecomposition to produce an acid and a polymer having an orthoester group in its main chain, as disclosed in JP-A-56-17345, a combination of a compound which undergoes photodecomposition to produce an acid and a tertiary alkyl ester compound (as disclosed in JP-A-60-3625), a combination of a compound which undergoes photodecomposition to produce an acid and a silylëTSter compound ( as disclosed in JP-A-60-10247),

   and a combination of a compound which undergoes photodecomposition to produce an acid and a silylether compound (as disclosed in JP-A-60-37549 and JP-A-60-121446). Such a chemically sensitized photoresist composition has a quantum yield in principle greater than 1, and therefore has a high photosensitivity.



   Likewise, examples of systems which remain stable at room temperature but decompose on heating in the presence of an acid, to become soluble in

  <Desc / Clms Page number 4>

 alkalis, include a combination of a compound which produces an acid upon exposure, and an ester of a secondary or tertiary carboxylic acid, or a carboxylic ester compound, as disclosed in JP-A-59-45439, JP-A-60-3625, JP-A-62-229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642, Polym. Eng. Sce., Vol. 23, p. 1012 (1983), ACS. Sym., Vol. 242, page 11 (1984), Semiconductor World 1987, Nov., page 91, Macromolecules, vol. 21, page 1475 (1988), and SPIE, vol. 920, page 42 (1988).

   Compared to a novolak / naphthoquinone diazide resin composition, such a system also has high photosensitivity and has low absorption in the deep ultraviolet region. Thus, the systems described above are effective for light sources having a short wavelength.



   The above composition of chemically sensitized photoresist working in positive can be divided into two main groups, which include a ternary system consisting of an alkali-soluble resin, a compound which produces an acid upon exposure to a radiation, and of a compound having an acid-decomposable radical which inhibits the dissolution of the alkali-soluble resin, and a binary system consisting of a resin having a radical which reacts with an acid to become soluble in alkalis, and a light-sensitive agent for producing an acid (hereinafter referred to as an acid photogenerator). :

  -
The binary system is disadvantageous in that the content in the resin of an acid-decomposable radical is high, which causes the resist film to shrink during baking after exposure.



   On the other hand, the ternary system is disadvantageous in that its ability to inhibit the dissolution of an alkali-soluble resin is insufficient, which causes during development a significant reduction in the thickness of the film, which leads to deterioration

  <Desc / Clms Page number 5>

 notable profile of the resist.



   JP-A-4-158 363 discloses a tertiary pattern-forming material which compensates for the insufficient dissolution inhibiting ability of the acid-decomposable dissolution inhibitor, by protecting some of the soluble radicals in the alkali of an alkali-soluble resin. However, the dissolution inhibition capacity of the acid decomposable dissolution inhibitor, presented by way of example in the patent cited above, leaves much to be desired. The reduction of the developing layer cannot therefore be completely inhibited in such a system.



   In addition, German patent DE-4 214 363 discloses a multifunctional dissolution inhibitor, decomposable by an acid, represented by the structural formula (A) below. However, a ternary pattern-forming material comprising such a compound is disadvantageous in that the pattern obtained has a marked standing wave.
 EMI5.1
 



   The ternary system, however, allows great freedom in the selection of materials, and is therefore a favorable system. However, the development of an acid decomposable compound having excellent dissolution inhibiting ability is desirable for use in this system.



  SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a photosensitive composition working in positive, which exhibits little shrinkage of the layer during baking after exposure, and a small reduction in

  <Desc / Clms Page number 6>

 layer thickness during development, to obtain an excellent profile and a high resolving power without this causing the appearance of a standing wave.



   The above object of the present invention will become more apparent from the detailed description and examples which follow.



   The present inventors have studied in depth the effectiveness of the above resistance systems. The result was that it was discovered that the above object of the present invention can be achieved with a chemically sensitized system, working in positive and containing a resin having a radical decomposable by an acid (labile in an acid) , the solubility of which increases in an alkaline developer upon reaction with an acid, an acid photogenerator and a dissolution inhibitor having an acid decomposable group, the dissolution inhibitor compound being a low molecular weight dissolution inhibitor decomposable by an acid which meets the requirements described below, thereby achieving the present invention.



   The present invention provides a positive-working photosensitive composition comprising: (a) a resin having an acid decomposable radical, the solubility of which increases in an alkaline developer after reaction with an acid (hereinafter referred to as "resin having a decomposable radical with an acid "); -.



   (b) a compound which generates an acid when irradiated with rays or actinic radiation; and (c) an acid-decomposable, non-polymeric dissolution inhibitor having a molecular weight of not more than 3000, containing an acid-decomposable radical, the solubility of which in an alkaline developer increases under the action of an acid, wherein said compound (c) has at least three structural units per molecule, each having a decomposable radical

  <Desc / Clms Page number 7>

 by an acid, substituted on a benzene ring, and with at least nine bond atoms (excluding the radicals decomposable by an acid) inserted between two radicals decomposable by an acid and located at the greatest distance.



  DETAILED DESCRIPTION OF THE INVENTION
The compounds for use in the present invention are described in more detail below.



  (A) Resin having an acid decomposable radical: (compound (a) of the present invention)
The resin having an acid decomposable radical according to the present invention is a resin having an acid decomposable radical in a main chain or in a side chain, or in both. It is preferred to use a resin having in its side chain a radical decomposable by an acid.



   Preferred examples of such a decomposable radical
 EMI7.1
 0 0 by an acid include the groups -COO-A and-0-B Other preferred examples of such an acid decomposable radical include the groups-R-COO-A and
 EMI7.2
 0 -Ar-OB In the general formulas above, A represents a radical-C (R) (R) (R), - Si (R) (R) (R or 04 05 06 0,. 0 0 - C (R) (R) -OR. B represents an A or -CO-OA radical.



  0'02 03 04 05 tA t. d t.



  R, R, R, R and R may be the same or different and each represents a hydrogen atom, an alkyl radical, a cycloalkyl radical, an alkenyl radical
 EMI7.3
 *** * 06 or an aryl radical, and R represents an alkyl radical or an aryl radical, provided that at least two of the radicals R to R03 are radicals other than a hydrogen atom, and that two of the radicals R01 to R and R to R can be linked to each other to form a ring, with particularly preferred examples comprising a tetrahydropyran ring and a tetrahydrofuran. RO represents an aliphatic or aromatic hydrocarbon radical in Cul-12, having a valence of 2 or more, which can be substituted.

   The radical -Ar represents an aromatic radical

  <Desc / Clms Page number 8>

 monocyclic or polycyclic having a valence of 2 or more, which may be substituted.



   A preferred example of the above alkyl radical represented by R01 to R is a C1-4 alkyl radical such as a methyl radical, an ethyl radical, a propyl radical, an n-butyl radical, a sec-butyl radical and a radical t-butyl. A preferred example of the above cycloalkyl radical, represented by R to R, is a C3-10 cycloalkyl radical such as a cyclopropyl radical, a cyclobutyl radical, a cyclohexyl radical, and an adamantyl radical. A preferred example of the above alkenyl radical, represented by R to R, is a C2-4 alkenyl radical such as a vinyl radical, a propenyl radical, an allyl radical and a butenyl radical.

   A preferred example of the above aryl radical represented by R to R06 is a C6-14 aryl radical such as a phenyl radical, a xylyl radical, a toluyl radical, a cumenyl radical, a naphthyl radical, and an anthracenyl radical.



   The alkyl, cycloalkyl, alkenyl and aryl radicals described above can be substituted.



   Examples of substituents for these radicals include a hydroxyl radical, a halogen atom (e.g. fluorine, chlorine, bromine, iodine), a nitro radical, a cyano radical, a C-alkyl radical, an alkoxy radical such as methoxy radical, an ethoxy radical, a hydroethoxy radical, a propoxy radical, a hydroxypropoxy radical, an n-butoxy radical, an isobutoxy radical, a secbutoxy radical and-, a t-butoxy radical, an alkoxycarbonyl radical such as a methoxycarbonyl radical and an ethoxycarbonyl radical, an aralkyl radical such as a benzyl radical, a phenethyl radical, and a cumyl radical, an aralkyloxy radical, an acyl radical such as a formyl radical, an acetyl radical, a butyryl radical, a benzoyl radical, a cyanamyl radical and a valeryl radical, an acyloxy radical such as a butyryloxy radical,

   a C alkenyl radical, an alkenyloxy radical such as a vinyloxy radical, a propenyloxy radical, a radical

  <Desc / Clms Page number 9>

 allyloxy and a butenyloxy radical, a C 1-4 aryl radical, an aryloxy radical such as a phenoxy radical, and an aryloxycarbonyl radical such as a benzoyloxy radical.



   Preferred examples of the radicals decomposable by an acid include a silylether radical, a cumylester radical, an acetal radical, a tetrahydropyranylether radical, an enolether radical, an enolester radical, a tertiary alkylether radical, a tertiary alkylester radical, and a tertiary alkylcarbonate radical. Among these radicals, a tertiary alkylester radical, a tertiary alkylcarbonate radical, a cumylester radical and a tetrahydropyranylether radical are preferred.



   The base resin to which the acid-decomposable radical is linked in the form of a side chain is preferably an alkali-soluble resin having
 EMI9.1
 0 an OH-or COOH radical, and better still an R-COOH radical or an Ar-OH radical in its side chain. Examples of such an alkali-soluble resin include poly (hydroxystyrene), hydrogenated polyhydroxystyrene, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, halogen-substituted poly (hydroxystyrene), the hydroxystyrene-substituted maleimide copolymer, the partially o-acylated poly (hydroxystyrene), the copolymer of styrene and maleic anhydride, the methacrylic resin containing a carboxy radical, and derivatives thereof.

   However, it should not be considered that the present invention is limited to these examples. *
The rate of dissolution in alkalis of such an alkali-soluble resin is preferably not less than 170 Â / sec, and in particular not less than 330 Â / sec, as determined at a temperature of 230C in an aqueous solution 0.261 N tetramethylammonium hydroxide (TMAH).



   The alkali-soluble resin preferably has a high transmittance for radiation in far ultraviolet or laser radiation

  <Desc / Clms Page number 10>

 of the excimer type, and in particular a transmittance at 248 nm of 20 to 80% for a thickness of tumor layer at the exposure wavelength, to obtain a rectangular profile (relative to the angle of the side wall of the resist).



   In this regard, particularly preferred examples of such an alkali-soluble resin include poly (hydroxystyrene), hydrogenated poly (hydroxystyrene), poly (hydroxystyrene) substituted by halogen or alkyl, poly (hydroxystyrene) partially o- acylated and hydrogenated novolak resin.



   The poly (hydroxystyrene) used above is chosen from the group consisting of poly (p-hydroxystyrene), poly (m-hydroxystyrene), poly (o-hydroxystyrene) and copolymers of two or three monomers of p-hydroxystyrene , m-hydroxystyrene and o-hydroxystyrene.



   The resin having an acid-decomposable radical according to the present invention can be prepared by reacting an alkali-soluble resin with a precursor of an acid-decomposable radical, or by copolymerization with different monomers of a soluble resin monomer. in alkalis having, linked to it, an acid-decomposable radical, as disclosed in European patent EP-254,853, JP-A-2-25850, JP-A-3-223860 and JP-A-4-251259 .



   The general formulas (a) to (f) of resin having an acid decomposable radical to be used in the present invention are given below; it should not however be considered that the present invention is limited to these examples.

  <Desc / Clms Page number 11>

 
 EMI11.1
 in which: L: represents -COOA0, -O-B0, - (O) n-R0-COO-A0 or -Ar-O-B0
 EMI11.2
 0 0 0 in which Ar, R, A and B are as defined above); R.: The radicals R1 of the same molecule can be identical or different and each represents a hydrogen atom or an alkyl radical in C. -4;

   R2, R4: the radicals R2 and R4 of the same molecule can be identical or different, and each represents a hydrogen atom or a C'-4 alkyl radical; R: represents a hydrogen atom, a carboxyl radical, a cyano radical or a substituted or unsubstituted C6-20 aryl radical; R:: represents a hydrogen atom, a cyano group or - COOR5; R6: represents a straight or branched chain at C @ -10, or a cyclic alkyl radical; R- to R9: represent a hydrogen atom or a radical

  <Desc / Clms Page number 12>

 C alkyl;

   Ar: represents a C6-20 ′ aromatic radical which may be substituted, or a C6-20 cycloalkyl radical which may be substituted. k, # 1, k1, # 1, m: each independently represent a natural number, with k + Q = 1, kQ + QQ = 1, and 0.01 <kQ0.5; n: represents 0 or 1.



   Particularly preferred examples of Ar include a substituted or unsubstituted phenyl, naphthyl, cyclonaphthyl and adamantyl radical. Preferred examples of substituents for Ar include a C 1-4 alkyl radical, a C 7-11 aralkyl radical, a C1-6 acyl radical, a C1-4 alkoxy radical, a C2-4 alkynyl radical, an alkenyloxy radical in 4, a C6-10 aryl radical,
 EMI12.1
 an aryloxy radical at C610, an aralkyloxy radical at Cy. , a C1-6 acyloxy radical. an alkoxycarbonyl radical in
C2-, a C7-11 aryloxycarbonyl radical, a halogen atom, a nitro radical, a hydroxyl radical, a cyano radical and a carboxyl radical.



   Specific examples of these resins include compounds (i) to (xxiii):

  <Desc / Clms Page number 13>

 
 EMI13.1
 

  <Desc / Clms Page number 14>

 
 EMI14.1
 

  <Desc / Clms Page number 15>

 
 EMI15.1
 

  <Desc / Clms Page number 16>

 
 EMI16.1
 

  <Desc / Clms Page number 17>

 
The content of the acid-decomposable radical is represented by B / (B + S) where B is the number of radicals of the acid-decomposable resin, S being the number of acid-soluble radicals which are not protected by the radical decomposable by an acid. The content of the acid decomposable radical is generally in the range from 0.01 to 0.5, preferably from 0.01 to 0.30, and better still from 0.01 to 0.15.

   A B / (B + S) content exceeding 0.5 causes a shrinkage of the layer after PEB (baking after exposure), a loss of adhesion to the support and flaking (of the drawings on the developed resist). On the contrary, a B / (B + S) content of less than 0.01 can lead to a marked standing wave profile on the side wall of the design developed in the resist.



   The weight average molecular weight (Mw) of the resin having an acid decomposable radical is preferably in the range of 1000 to 100,000. An Mw of less than 1000 causes during development a significant reduction in the layer thickness in the unexposed areas. Furthermore, if the Mw of the resin exceeds 100,000, the alkali-soluble resin itself has a low rate of dissolution in the alkalis and a reduced sensitivity. A particularly preferred range of Mw of the resin is from 2000 to 50,000.



   The weight average molecular weight is determined by chromatography on permeable gel, with standards of THF and of polystyrene.
 EMI17.1
 



  Two or more resins having an acid decomposable radical according to the present invention can be used as a mixture. In addition, the resin having an acid decomposable radical according to the present invention can be used in admixture with an alkali-soluble resin devoid of acid decomposable radicals, to control the solubility of the resin in the alkalis.



   The amount of addition of the resin of the present invention is in the range of 50 to 97% by weight, from

  <Desc / Clms Page number 18>

 preferably 60 to 90% by weight, calculated on the total weight of the photosensitive composition (excluding the solvent).



  (B) non-polymeric inhibitor of dissolution, decomposable by an acid (compound (c) of the present invention)
The acid-decomposable non-polymeric dissolution inhibitor (c) of the present invention comprises at least three structural units per molecule, each of which has a substituted acid-decomposable radical on a benzene ring. In addition, there are at least nine bond atoms, preferably at least ten bond atoms, and better still eleven bond atoms (excluding said radicals decomposable by an acid) interposed between at least two of the radicals decomposable by an acid , in the respective structural units.

   In other words, the compound (c) must have a first radical decomposable by an acid, of a first structural unit, which is separated by a predetermined distance from a second radical decomposable by an acid of a second unit structural.



   The upper limit of the number of bonding atoms is preferably 50, and better still 30.



   In the present invention, if the acid-decomposable dissolution-inhibiting compound has three or more, and preferably four or more, structural units each having on a benzene ring a substituted radical decomposable by an acid, two radicals
 EMI18.1
 decomposable by an acid on respective structural units being. separated by a predetermined distance, its ability to inhibit the dissolution of the alkali-soluble resin is significantly enhanced.



   As used herein, the term "distance between radicals decomposable by an acid" refers to the number of bond atoms interspersed between radicals decomposable by an acid, with the exception of the radicals decomposable by an acid themselves. For example, in the case of compounds (1) and (2) below, the distance between

  <Desc / Clms Page number 19>

 radicals decomposable by an acid is four bond atoms. In the case of compound (3), the greatest distance between the groups decomposable by an acid is 12 bond atoms.
 EMI19.1
 



   Radical decomposable by an acid: -COO-A, -O-B
The molecular weight of the acid-decomposable non-polymeric dissolution inhibitor of the present invention is not more than 3000, is preferably 500 to 3000 and more preferably 1000 to 2500.



   In the present invention, the radical containing an acid decomposable radical is preferably a
 EMI19.2
 0 0 radical-COO-A or-OB, and better still a radical represented by 000 -R -COO-A Du-Ar-OB l f'1 "1'd 00 t 0 In the general formulas above. A, B and R are those defined above for the radical decomposable by an acid of the compound (a) of the invention.



   Preferred examples of the non-polymeric inhibitor of dissolution of the compounds by an acid include protected compounds obtained by partial or complete esterification with the radical-R-COO-AouBB described above, the phenolic OH radicals of a polyhydroxylated compound having at minus three hydroxyl radicals and having a

  <Desc / Clms Page number 20>

 
 EMI20.1
 single hydroxyl radical on each benzene ring in their molecule. Particularly preferred examples of the radical-R-COO-AetBB are radicals decomposable by an acid described above for non-polymeric dissolution inhibitors, decomposable by an acid. The esterification method is for example disclosed by J.



  Frechet et al. in Polymer, 24, August, Page 995 (1983). Polyhydroxy compounds and methods useful for the manufacture of these radicals are described in JP-A-1-289946, JP-A-2-2560, JP-A-3-128959, JP-A-3-158855, JP- A-3-179353, JP-A-3-191351, JP-A-3-200251, JP-A-3-200252, JP-A-3-200253, JP-A-3-200254, JP-A- 3-200255, JP-A-3-259149, JP-A-3-279958, JP-A-4-1650, JP-A-4-1651, JP-A-4-11260, JP-A-4- 12356, JP-A-4-12357, JP-A-4-271349, JP-A-5-158233, JP-A-5-224409, JP-A-5-257275, JP-A-5-297581, JP-A-5-297583, JP-A-5-309197, JP-A-5-303200 and JP-A-5-341510.



  Other preferred examples of the polyhydroxy compounds are described in JP-A-1-289946, JP-A-3-128959, JP-A-3-158855, JP-A-3-179353, JP-A-3-200251 , JP-A-3-200252, JP-A-3-200255, JP-A-3-259149, JP-A-3-279958, JP-A-4-1650, JP-A-4-11260, JP -A-4-12356, JP-A-4-12357, JP-A-5-224409, JP-A-5-297581, JP-A-5-297581, JP-A-5-309197, JP-A -5-303200 and JP-A-5-341510.



  Specific examples of the non-polymeric dissolution inhibitor, decomposable by an acid according to the invention include compounds represented by the general formulas (I) to (XII) below:

  <Desc / Clms Page number 21>

 
 EMI21.1
 

  <Desc / Clms Page number 22>

 in which :

   R: represents a hydroxyl radical, a radical
 EMI22.1
 0 0 0 l of t't '-O-R -COO-A or-O-B, with the proviso that three or more of the radicals R of each molecule are radicals -O-R0COO-A0 or -O-B0;
 EMI22.2
 Ra to R, Ry, Rg to R, R to R-, g, R to R2g: these radicals can be identical or different and each represents a hydrogen atom, a hydroxyl radical, a C1-4 alkyl radical. a C1-4 alkoxy radical. a C1-61 acyl radical, a C1- acyloxy radical, a C6 aryl radical, a C610 aryloxy radical, a C7-11 aralkyl radical, a C7-1 aralkyloxy radical, a halogen atom, a nitro radical, a carboxyl radical, a cyano or -N (Rg) (Rg) radical (where Rs and R6 each represents a hydrogen atom, a C1-4 alkyl radical or a C6-10 aryl radical);

   R8: a single bond, a C1-4 alkylene radical or
 EMI22.3
 (in which R14 and R16 may be the same or different, and each represents a single bond, a C, -O -, - S -, - CO-alkylene radical or a carboxyl radical; and RIS represents a hydrogen atom, an alkyl radical in C, an alkoxy radical in C1-4, a radical
 EMI22.4
 acyl in Cul 6, an acyloxy radical in Cl¯ ,, an aryl radical in Cg. o, m nitro radical, a hydroxyl radical, a cyano radical or a carboxyl radical, with the condition that the hydrogen atom of the hydroxyl radical may be substituted by a radical-R -COO-Ao or a radical -Bo);

   Ro, R: these radicals can be the same or different and each represents a methylene radical, a methylene radical substituted by a lower alkyl, a halomethylene radical or a haloalkyl radical (as used here, the term "lower alkyl radical" denotes a C1-4 alkyl radical);

  <Desc / Clms Page number 23>

 R30, R31: these groups may be the same or different, and each represents a hydrogen atom, a lower alkyl radical, a lower haloalkyl radical or an aryl radical in CS-1O 'R32 to R35:

   these radicals may be the same or different, and each represents a hydrogen atom, a hydroxyl radical, a halogen atom, a nitro radical, a cyano radical, a carbonyl radical, a C1-4 alkyl radical, an alkoxy radical in Cul-4, a radical
 EMI23.1
 C2- alkoxycarbonyl, a C7-11 aralkyl radical, a C711 aralkyloxy radical, a C1-6 acyl radical, a C1- acyloxy radical, a C2 alkenyl radical, a C2-4 alkenyloxy radical, a C610 aryl radical, a cabbage aryloxy radical a C7-11 aryloxycarbonyl radical, with the condition that four substituents represented by the same symbol in a molecule cannot be identical; E: represents a single bond or an oxymethylene radical; Y: represents -CO- or -SO2-;

   A: represents a methylene radical, a methylene radical substituted by a lower alkyl, a halomethylene radical or a C haloalkyl radical; a to g, i to k, p to r: each represents an integer from 0 to 4, with the condition that a to j are each greater than 1, and that the several radicals put in parentheses can be identical or different; h, 1 to o, s, t, v to z: each represents an integer from 0 to 3, with the condition that at least one of v, w, y and z is not less than 1; u: represents an integer from 3 to 8

  <Desc / Clms Page number 24>

 
 EMI24.1
 
 EMI24.2
 R36:

   represents a bivalent organic radical (for example, C alkylene, Cg alkenylene, Cg arylene) or a trivalent organic radical (for example radicals having lost a hydrogen atom in C alkylene, alkenylene in Ces and the arylene in C6-14), united bond
 EMI24.3
 0 it simple, -S -, - SO-ou-SIl 0 o
 EMI24.4
 R37: represents a hydrogen atom, a halogen atom, a hydroxyl radical, a monovalent organic radical (for example, Cri- alkyl, Cl 4 alkoxy, C- acyl, g, Cl-6 acyloxy (C8 aryl, C aryloxy, C1-aralkyl, C1-aryloxy, C1-4 haloalkyl) or
 EMI24.5
 
 EMI24.6
 Rgg to R:

   these radicals can be identical and different and each represents a hydrogen atom, a

  <Desc / Clms Page number 25>

 hydroxyl radical, a halogen atom, an alkyl radical, an alkoxy radical, an alkenyl radical, a radical
 EMI25.1
 0-0 0 0 0 0 -OR -COO-Aw or radical-OB (in which R, AD and B are defined above), with the proviso that at least three of the radicals Rg to R are a radical -OR- COO-A or 0 a radical-0-B and that four to six substituents represented by the same symbol cannot be identical; X: represents a single bond or an organic radical
 EMI25.2
 bivalent (for example, C alkylene, C 8 alkenylene, C @ arylene - @); al: represents 0 or 1
 EMI25.3
 in which :

   R43 to R46: these groups may be the same or different and each represents a hydrogen atom, a hydroxyl radical, a halogen atom, an alkyl radical, an alkoxy radical or an alkenyl radical, with the condition that four to six substituents represented by the same symbol cannot be identical;
 EMI25.4
 R <? / R each represents a hydrogen atom, an alkyl radical or
 EMI25.5
 
R5: at least three of the radicals R5 are a radical
 EMI25.6
 0 0. 0 00 0 -O-R-COO-A or a radical-O-B (in which A, B and R

  <Desc / Clms Page number 26>

 are defined above), and the other radicals R5 are hydroxyl radicals; b1, cl, d1: each represents an integer from 0 to 5
 EMI26.1
 in which :

   R49 to R55: these radicals can be the same or different and each represents a hydrogen atom, a hydroxyl radical, a halogen atom, a Con 4 alkyl radical, a Cl-4 alkoxy radical, a nitro radical, a C 2-4 alkenyl radical a C610 aryl radical, an 11 aralkyl radical, a C2 alkoxycarbonyl radical,
 EMI26.2
 an arylcarbonyl radical at Cy, an acyloxy radical at Cl-6 'an acyl radical at Cl- ,, an aralkyloxy radical at Cy-, or an aryloxy radical at C610, with the proviso that six substituents represented by the same symbol cannot be identical;
R6: at least three of the radicals R6 are a radical -O-R0-COO-A0 or a radical-O-B, the other radicals R6 being hydroxyl radicals.
 EMI26.3
 

  <Desc / Clms Page number 27>

 in which: RS6:

   represents a hydrogen atom, or an alkyl radical
 EMI27.1
 in Cl, with the condition that none of the several radicals in Cl¯, RS6 can represent the same radical (for example, alkyl radicals differing in the number of their carbon atoms); R57 to R60: each represent a hydroxyl radical, a hydrogen atom, a halogen atom, a C1-4 alkyl radical, or a C1-4 alkoxy radical, with the condition that three substituents represented by the same symbol cannot be the same;
 EMI27.2
 7 ... aa (daa R: represents the radical-OR -COO-A (in which A, B and 0 0 R are defined above), or the radical-OB, with the condition that none of the three radicals R7 cannot represent the same radical.



   Specific examples of the preferred skeletons of the compound of the non-polymerized inhibitor of dissolution decomposable by an acid according to the invention are given below:

  <Desc / Clms Page number 28>

 
 EMI28.1
 

  <Desc / Clms Page number 29>

 
 EMI29.1
 

  <Desc / Clms Page number 30>

 
 EMI30.1
 

  <Desc / Clms Page number 31>

 
 EMI31.1
 

  <Desc / Clms Page number 32>

 
 EMI32.1
 

  <Desc / Clms Page number 33>

 
 EMI33.1
 In the general formulas (1) to (43) above, R represents a hydrogen atom, -CH-COO-CHCgHg, -CH- COO-C4H95, -COO-C4H9t or
 EMI33.2
 with the proviso that at least three of the radicals R of each molecule are radicals other than a hydrogen atom, and that the substituents R cannot be identical.



   The content of the radical decomposable by an acid in the non-polymeric inhibitor (c) of dissolution decomposable by acids is represented by Nb / (NB + NS) where NB represents an average number of radicals decomposable by an acid in the inhibitor of dissolution (c) and where Ns represents an average number of the fractions which are not protected by the radical decomposable by an acid. The content of the radical decomposable by an acid is preferably 0.25 <Nal (NB + Ns) <lt and better from 05Ng / (Ng + Ng) j 1.

   It is particularly preferred that not less than 50% by weight of the non-polymeric inhibitor of dissolution decomposable by an acid be constituted by
 EMI33.3
 structural units having a relation of 0.5 g / (Ng + N) JL 1 in which Ni represents the number of radicals decomposable by an acid and N1S represents the number of fractions which can be protected by the radical decomposable by an acid , but is not protected. by the latter, per mole of the non-polymeric inhibitor of dissolution decomposable by an acid.



   The amount of addition of the compound (c) of the present invention is in the range of 3 to 50% by weight, preferably 5 to 35% by weight, calculated on the total weight of the photosensitive composition (excluding solvents).



  (C) Compound which generates an acid when irradiated with actinic radiation: (compound (b) of the present invention)

  <Desc / Clms Page number 34>

 
The compound which generates an acid when irradiated with actinic radiation, to be used in the present invention, is suitably chosen from the group consisting of a photoinitiator of a cationic photopolymerization, of a photoinitiator of a photopolymerization radical, a photodecolorant of a pigment, a photodecolorant, known compounds which generate an acid when irradiated with light, for use in microresists and mixtures thereof.

   As used herein, the term "actinic radiation" includes lights having a wavelength of 150-500 nm, electronic radiation, X-rays, a molecular beam and R rays.



   Examples of such compounds include the diazonium salts described in S. I. Schlesinger, "Photogr. Sci.



    Eng. ", 18,387 (1974), and TS Bal et al," Polymer ", 21, 423 (1980), the ammonium salts described in patents US-4-069 055, US-4-069 056 and US -27,992, and Japanese patent application JP-A-3 140140, the phosphonium salts described in DC Necker et al, "Macromolecules", 17.2468 (1984), CS Wen et al, "Proc. Conf. Rad. Curing ", ASIA, p
 EMI34.1
 478, Tokyo, Oct (1988), US-4,069,055 and US-4,069,056, the iodonium salt described in JV Crivello et al, "Macromolecules", 10 (6), 1307 (1977), chem . & Eng.



  News, Nov. 28, p 31 (1988), European patent EP-104 143, JP-A-2-150 848 and JP-A-2-296 514, the sulfonium salts described in JV Crivello et al, " Polymer ", J. 17.73 (1985), JV Crivello et al," J. Org. Chem ", 43.3055 (1978), WR Watt et al," J. Polymer Sci. ", Polymer Chem.



  Ed., 22.1789 (1984), JV Crivello et al, "Polymer Bull.", 14.279 (1985), JV Crivello et al, "Macromolecules", 14 (5), 1141 (1981), JV Crivello et al, "J. Polymer Sci.", Polymer Chem. Ed. 17.2877 (1979), European patents EP-370,694, EP-3,902,114, EP-233,567, EP-297,443 and EP-297,442, US patents 4,933,377, US-4,760 013, US-4,734,444 and US-2,833,827, German patents DE-2,904,626, DE-3,604,580 and DE-3,604,581, the salts of

  <Desc / Clms Page number 35>

 selenonium described in J. V. Crivello et al, "Macromolecules", 10 (6), 1307 (1977), J. V. Crivello et al, "J. Polymer Si.", Polymer Chem. Ed., 17.1047 (1979), onium salts such as the arsonium salts described in C. S.



  Wen et al, "Teh, Proc. Conf. Rad. Curing", ASIA, p 478, Tokyo, Oct. (1988), the halogenated organic compounds described in patents US-3,905,815 and JP-B-46-4605 (used here, the term "JP-B" refers to a "Japanese patent examined publication"), JP-A-48-36281, JP-A-55-32070, JP-A-60-239 736, JP-A -61-169835, JP-A-62- 58241, JP-A-62-212401, JP-A-63-70243, and JP-A-63-298339, the organic metal / halogen compounds described in K .



  Meier et al, "J. Rad. Curing", 13 (4), 26 (1986), T. P. Gill et al, "Inorg. Chem.", 19.3007 (1980), D. Asruc, "Acc.



  Chem. Res. ", 19 (12), 377 (1896), and JP-A-2-161445, the photogenerators of acids having a protective radical of the O-nitrobenzyl type described in S. Hayase et al," J.



  Polymer Sci. ", 25,753 (1987), E. Reichmanics et al," J.



  Polymer Si. ", Polymer Chem. Ed., 23.1 (1985), Q. Q. Zhu et al," J. Photochem. ", 36.85, 39.317 (1987), B. Amit et al," Tetrahedron Lett. ", (24) 2205 (1973), D. H. R. Barton et al," J. Chem. Soc. ", 3571 (1985), P. M. Collins et al," J.



  Chem. Soc. ", Perkin I, 1695 (1975), M. Rudinstein et al," Tetrahedron Lett. ", (17), 1445 (1975), J. W. Wlaker et al," J. Mr. Chem. Soc. ", 110,7170 (1988), S. C. Busman et al," J.
 EMI35.1
 Imaging Technol. ", 11 (4), 191 (1985), H. M. Houlihan et al," Macromolecules ", 21, 2001 (1988), P. M. Collins et al," J.



  Chem. Soc. ", Chem.'Commun., 532 (1972), S. Hayase et al," Macromolecules "18, 1799 (1985), E. Reichmanics et al," J.



  Electrochem. ", Soc., Solid State Sci. Technol., 130 (6), FM Houlihan et al," Macromolecules ", 21.2001 (1988), European patents EP-0290 750, EP-046 083, EP- 156,535,
 EMI35.2
 EP-271,851, and EP-0 388 343, US Patents 3,901,710 and US-4,181,531, JP-A-60-198538, and JP-A-53-133033, a compound which undergoes photodecomposition for generating sulfonic acid, such as an iminosulfonate described in M. Tunooka et al, "Polymer Preprints", Japan, 35 (8); G. Berner et al,

  <Desc / Clms Page number 36>

 "J. Rad. Curing", 13 (49, W. J. Mijs et al, "Coating Technol.", 55 (697), 45 (1983), Akzo, H.

   Adachi et al, "Polymer Preprints", Japan 37 (39, European patents EP-0199 672, EP-84 515, EP-199 672, EP-044 115 and
 EMI36.1
 EP-0 101 122, patents US-4 618 564, US-4 371 605 and US-4 431 774, and JP-A-64-18143, JP-A-2-245756 and JP-A-3-140109 , and the disulfone compounds described in JP-A-61 166544.



   In addition, one can use a polymer compound having in its main chain or a side chain one or more of these radicals or compounds which generate an acid under irradiation with light. Examples of such polymeric compounds include those described in M. E.



  Woodhouses et al, "J. Am. Chem. Soc.", 104.5586 (1982), S.



  P. Pappas et al, "J. Imaging Sci.", 30 (5), 218 (1986), S.



  Kondo et al, "Macromol. Chem.", Rapid Commun., 9, 625 (1988), Y. Yamada et al, "Macromol. Chem.", 152.153, 163 (1972), JV Crivello et al, "J. Polymer Si. ", Polymer Chem. Ed., 17.3845 (1979), US patent 3,849,137, DE-3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP- A-63-146038, JP-A-63-163452, JP-A-62-153853, and JP-A-63-146029.



   In addition, a compound which generates an acid under light irradiation can be used, as described in
 EMI36.2
 (VNR Pillai, "Synthesis", (1), 1 (1980), A. Abad et al, "Tetragedron Lett.", (47) 4555 (1971), DHR Barton et al, "J. Chem. Soc." , (C), 329 (1970), US Patent 3,779,778, Patent EP126,712.



  Among the above compounds which undergo decomposition by actinic radiation to generate an acid, those which are particularly useful are described below.



   (1) An oxazole derivative substituted by trihalomethyl represented by the general formula below (PAG1) or an S-triazine derivative substituted by trimethyl represented by the general formula below (PAG2):

  <Desc / Clms Page number 37>

 
 EMI37.1
 
 EMI37.2
 in which R1 represents a C610 aryl radical or a C24 alkenyl radical, substituted or unsubstituted; Ra represents a C610 aryl radical, a C24 alkenyl radical, a C1-4 alkyl radical, substituted or unsubstituted, or-CYg; and Y represents a chlorine atom or a bromine atom.



   Specific examples of these compounds are given below, but the present invention should not be considered to be limited thereto.
 EMI37.3
 

  <Desc / Clms Page number 38>

 
 EMI38.1
 

  <Desc / Clms Page number 39>

 (2) An iodonium salt represented by the general formula below (PAG3), or a sulfonium salt represented by the general formula below (PAG4):
 EMI39.1
 
In the above general formulas, Ar1 and Ar2 each independently represent a substituted or unsubstituted C6- @ 0 aryl radical.

   Preferred examples of an aryl radical substituent include a C1-4 alkyl radical, a C1-4 haloalkyl radical, a C10 cycloalkyl radical, a C6-10 aryl radical, a C6 alkoxy radical, a nitro radical, a carboxyl radical, a
 EMI39.2
 C2- alkoxycarbonyl radical, a hydroxyl radical, a mercapto radical, and a halogen atom.



  35R, R and R each independently represent a substituted or unsubstituted alkyl radical or aryl radical, preferably a C 8 aryl radical, a C1-8 alkyl radical or a substituted derivative thereof. Preferred examples of substituents for these radicals include a C1-8 alkoxy radical, a C1-6 alkyl radical, a nitro radical, a carboxyl radical, a hydroxyl radical and a halogen atom, for the aryl radical, and a C1-6 alkoxy radical, a carboxyl radical and a C2-5 alkoxycarbonyl radical, for the alkyl radical.



   Z represents, a paired anion. Examples of such
 EMI39.3
 Paired anion include BF4, AsFg, PFg, SbFg, SiFg, Cl04, a perfluoroalkanesulfonic anion such as CF3SO3-, a pentafluorobenzene sulfonic anion, a condensed polynuclear aromatic sulfonic anion such as naphthalene-1-sulfonic anion, an anthraquinones anion pigment containing a sulfone. However, the present invention should not be considered as being there.
 EMI39.4
 limited.



  . 3 4 5, 2 Two of the radicals R \ R and R or Ar 1 and Ar can

  <Desc / Clms Page number 40>

 be linked to each other by a single bond or by a bivalent substitution group, preferred examples comprising a C alkylene radical, a C alkenylene radical a C 6-14 arylene radical, these radicals being each capable of being substituted by a radical
 EMI40.1
 C'-4f alkyl a Cl¯4 alkyoxy radical, a Cl-61 acyl radical a Cl-61 acyloxy radical a Cgo aryl radical, a C610 aryloxy radical, a C7-11 aralkyl radical, a radical C7-11 aralkyloxy, a C1 haloalkyl radical, a halogen atom, a hydroxyl radical or a cyano radical.



   Specific examples of the iodonium and sulfonium salts are given below, but the present invention should not be considered to be limited thereto.

  <Desc / Clms Page number 41>

 
 EMI41.1
 

  <Desc / Clms Page number 42>

 
 EMI42.1
 

  <Desc / Clms Page number 43>

 
 EMI43.1
 

  <Desc / Clms Page number 44>

 
 EMI44.1
 

  <Desc / Clms Page number 45>

 



  The above onium salts, represented by PAG3 and PAG4 are known and can be synthesized by the methods described for example by J. W. Knapczyk et al. in J. Am.



  Chem. Soc., 91, 145 (1969), A. L. Maycock et al. in J. Org.



  Chem., 35, 2632 (1970), E. Goethas et al. in Bull. Soc.



  Chem. Belg., 73, 546 (1964), H. M. Leicester in J. Am. Chem.



  Soc., 51, 3587 (1929) and J. U. Crivello et al. in J. Polym.



  Chem. ed., 18, 2677 (1980) and described in patents US-2,807,648, US-4,247,473, and JP-A-53-101,331.



  (3) Disulfone derivatives represented by the formula below (PAG5) and iminosulfonate derivatives represented by the formula below (PAG6):
 EMI45.1
 
 EMI45.2
 In the above formulas, Ar and Ar4 each independently represent a substituted or unsubstituted Cg-, o aryl radical; R represents a C 1-10 alkyl or C 6-10 aryl radical, substituted or unsubstituted; and A represents a C 4 alkylene radical. a C1 alkenylene radical or a C8 arylene radical. , substituted or unsubstituted.



   The disulfone derivatives can be prepared by the method described for example by G. C. Denser, Jr. et al. in "Journal of Organic Chemistry", vol. 31, p. 3418-3419 (1966) and by T. P: Hilditch in "Journal of the Chemical Society", vol. 93, p. 1524-1527 (1908).



   Specific examples of these compounds are given below, but the present invention should not be considered to be limited thereto.

  <Desc / Clms Page number 46>

 
 EMI46.1
 

  <Desc / Clms Page number 47>

 
 EMI47.1
 

  <Desc / Clms Page number 48>

 



   The amount of addition of the compound which undergoes decomposition when irradiated with actinic radiation, to generate an acid, is in the range from 0.001 to 40% by weight, preferably from 0.01 to 20% by weight, and better still from 0.1 to 5% by weight, calculated on the total weight of the photosensitive composition (excluding the coating solvent).



   The photosensitive composition according to the present invention may further comprise a dye, a pigment, a plasticizer, a surfactant, a photosensitizer and a compound having two or more phenolic OH radicals, which accelerates solubilization in a developer.



   Preferred examples of the dye include oil soluble dyes and basic dyes.



  Specific examples of these dyes include the dyes Oil Yellow &num; 101, Oil Yellow &num; 193, Oil Pink &num; 312, Oil Green BG, Oil Blue BOS, Oil Blue &num; 603, Oil Black BY, Oil Black BS, Oil Black T-505 (these dyes are available from Orient Chemical Industry) Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B (CI45170B), Malachite Green (CI42000), and Methylene Blue (CI52015).



   In addition, the photosensitive composition of the present invention may include a spectral sensitizer, so as to be sensitized to a range of wavelengths longer than the range of far ultraviolet. The acid photogenerator does not exhibit absorption in this longer wavelength range, so that the photosensitive composition is not sensitive to lines i or g.

   Specific examples of preferred spectral sensitizers include benzophenone, p, p'tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthone, 9-ethoxyanthracene, anthracene pyrene, perylene, phenothiazine , benzyl, acridine orange, benzoflavin, acetoflavin-T, le9, 10-diphenylanthracene,

  <Desc / Clms Page number 49>

 9-fluorenone, acetophenone, phenanthrene, 2nitrofluorene, 5-nltroacenaphthene, benzoquinone, 2-chloro-4-nltroaniline, N-acetyl-p-nitroaniline, pnitroaniline, N-acetyl-4 -ntro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2ter-butylanthraquinone, 1,2-benzanthraquinone, 3methyl-1,3-diaza-1,

   9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3'-carbonyl-bis (5, 7-dimethoxycarbonylcoumarine), and coronene. However, the present invention should not be considered to be limited thereto.



   The photosensitive composition of the present invention thus prepared is then applied to a support, in the form of a solution in a solvent capable of dissolving the above components. Preferred examples of the solvent include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, y-butyrolactone, methyl ethyl ketone, monomethyl ether of ethylene glycol, monoethyl ether of ethylene glycol, l 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, lactate ethyl, methyl methoxyproprionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide,

   dimethyl sulfoxide, N-methylpyrrolidone, and tetrahydrofuran. These solvents can be used alone or as a mixture.



   A surfactant can be added to the solvent. Specific examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, for example polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene ketyl ether and polyoxyethylene oleyl ether, polyoxyethylene alkyl allyl ethers , for example polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether, copolymers

  <Desc / Clms Page number 50>

 polyoxyethylene and polyoxypropylene blocks, aliphatic esters of sorbitan, for example sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate and sorbitan tristearate,

   aliphatic esters of polyoxyethylene sorbitan, for example polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, such as fluoropolymers EF1, fluorosurfactants EF1, fluorinated agents EF303, EF352 available from Shinakita Kasei KK), Megafac FI 71, Fi 73 (available from Dainippon Ink KK), Fluorad FC430, FC341 (available from Sumitomo 3M), and Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (available from Asahi Glass Company, Limited), organosiloxane polymer KP431 (available from The Shin-etsu Chemical Industry Co.



    Ltd. ), and the acrylic or methacrylic (co) polymer Poly flow n 75, or n 95 (available from Kyoeisha Ushi Kagadu Kogyo K. K). The amount of addition of the surfactant is generally in the range of at most 2 parts by weight, preferably at most 1 part by weight, calculated on 100 parts by weight of the solids content of the photosensitive composition of the present invention.



   These surfactants can be used alone or in combination.



   The photosensitive composition thus prepared is applied to a support intended for use in the manufacture of precision integrated circuit elements (for example a support coated with silicon / silicon dioxide), by a suitable coating means such as a device. rotary coating, is exposed to light through a mask, is baked and then developed to obtain an excellent resist pattern.



   The developer for the development of the composition

  <Desc / Clms Page number 51>

 photosensitive of the present invention comprises an alkaline aqueous solution of an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia in aqueous solution , a primary amine such as etylamine and n-propylamine, a secondary amine such as diethylamine and di-nbutylamine, a tertiary amine such as triethylamine and methyldiethylamine, an amino alcohol such as dimethylethanolamine and triethanolamine , a quaternary ammonium salt such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, or a cyclic amine such as pyrrole and piperidine.



   The alkalinity of the aqueous alkaline solution (developer) is in the range from 0.001 to 1 N, preferably from 0.01 to 0.5 N, and in particular from 0.05 to 0.3 N.



   In addition, the alkaline aqueous solution can be used in admixture with an appropriate amount of an alcohol, a surfactant or the like.



   The present invention is described in more detail in the following examples, but the present invention should not be considered to be limited thereto.



  SYNTHESIS EXAMPLE 1 [Synthesis of a resin having an acid decomposable radical: Compound (i)] (1) A catalytically active amount of 2,2'-azobisisobutyronrtrile is added to 17.6 g of p-tert-butoxystyrene . The reaction mixture is then subjected to a polymerization reaction at a temperature of 80 ° C. in toluene, in a nitrogen atmosphere, for 6 hours. The reaction solution is cooled and poured into methanol for crystallization. The crystal obtained is recovered by filtration, washed with methanol, and then dried under reduced pressure, to obtain 15.5 g of poly (p-tert-butoxystyrene) in the form of a white powder. The product has an average molecular weight in

  <Desc / Clms Page number 52>

 weight of 12400.



  (2) Poly (p-tertbutoxystyrene) is dissolved in 1,4-dioxane 15.0 g in the form of a white powder. 10 m are then added to the solution. 8 concentrated hydrochloric acid. The mixture is then heated under reflux for 2.5 hours. The reaction solution is cooled and then poured into water for crystallization. The crystal obtained is recovered by filtration, washed with water and then dried under reduced pressure, to obtain 9 g of a poly (ptert-butoxystyrene-p-hydroxystyrene) in the form of a white powder. Analysis by nuclear magnetic resonance (NMR) on H of the polymer thus obtained confirms that it comprises a p-tert-butoxystyrene unit and a p-hydroxystyrene unit in a proportion of 1: 3. The polymer had a molecular weight weight average of 9800.



  SYNTHESIS EXAMPLE 2 [Synthesis of a resin having an acid decomposable radical: compound (ii)]
 EMI52.1
 9 g of a poly (hydroxystyrene) (weight average molecular weight: 9600) are dissolved in 100 mQ of dimethoxyethane. 2.6 g of 3,4-dihydro-2H-pyrane and 0.5 mQ of sulfuric acid are then added to the solution. The mixture is then kept stirring at a temperature of 30 to 40 C for 15 hours. When the reaction is complete, the reaction solution is concentrated under reduced pressure. The residue is neutralized with sodium carbonate and then poured into water for crystallization. The crystal obtained is recovered by filtration, washed with water, and then dried under reduced pressure, to obtain 11.0 g of a poly (p-tetrahydropyranyloxystyrene-p-hydroxystyrene) in the form of a white powder.

   1 H NMR analysis of the polymer thus obtained confirms that it comprises a p-tetrahydropyranyloxystyrene unit and a phydroxystyrene unit in a ratio of 3: 7 (by number).



  SYNTHESIS EXAMPLE 3 [Synthesis of a resin having an acid decomposable radical: compound (iii)]

  <Desc / Clms Page number 53>

 
22 g of pt-butoxycarbonyloxystyrene obtained by the process described in US Pat. No. 4,491,628 undergo a polymerization reaction in toluene at a temperature of 900 ° C. under a nitrogen atmosphere, in the presence of a catalyst of 2.2 ′. azobis (2,4-dimethylvaleronitrile) for 5 hours.

   The reaction solution is then treated in the same way as in synthetic example 1 (1), to obtain 15 g of poly (p-tert-butoxycarbonyloxystyrene) in the form of a white powder. 7 g of the powder are then subjected to the same reaction and to the same subsequent treatments as in synthetic example 1 (2), to obtain 4 g of a poly (p-tert-butoxycarbonyloxystyrene-phydroxystyrene), in the form of a white powder. NMR analysis on H of the polymer thus obtained confirms that it comprises a p-tert-butoxycarbonyloxystyrene unit and a p-hydroxystyrene unit in a ratio of 1: 9 (by number).



  SYNTHESIS EXAMPLE 4 [Synthesis of a resin having a radical decomposable by an acid: compound (xvi)]
28 g of p-tert-butoxystyrene and 3.1 g of fumaronitrile are subjected to a polymerization reaction in toluene at a temperature of 900 C, under a nitrogen atmosphere, in the presence of 2,2'-azobis (2- methyl methylpropionate) for 2 hours. When the reaction is complete, the reaction solution is then poured into methanol for crystallization.

   The crystal obtained is recovered by filtration, washed and then dried, to obtain 20 g of a poly (p-tert-butoxystyrene-fumaronitrile) in the form of a white powder. 20 g of powder are then subjected to the same reaction and to the same subsequent treatment as in synthetic example 1 (2), to obtain 15 g of a poly (p-tert-butoxystyrene-phydroxystyrene-fumaronitrile) in the form of a white powder. Analysis by H NMR of the polymer thus obtained confirms that it comprises a p-tertbutoxystyrene unit and a p-hydroxystyrene unit in a

  <Desc / Clms Page number 54>

 ratio of 1: 4 in number).



  SYNTHESIS EXAMPLE 5-7 [Synthesis of a resin having an acid decomposable radical: compound (i)]
The polymer obtained in synthesis example 1 (1) was treated in the same way as in synthesis example 1 (2), except that the duration during which it was heated under reflux was modified. and with stirring, to obtain resins comprising a p-tert-butoxystyrene unit and a p-hydroxystyrene unit in a ratio (by number) of 1: 1 (synthetic example 5), of 1: 1.5 (example 6) and 1: 9 (Synthesis 7), respectively.



  SYNTHESIS EXAMPLE 8 [Synthesis of a resin having a radical decomposable by a compound acid (xix)]
5.8 g of N- (p-tert-butoxycarbonyloxyphenyl) -maleimide obtained by the process described in patent EP 254 853 and 2 g of styrene were subjected to a polymerization reaction in dioxane, at a temperature of 80 ° C. under atmosphere nitrogen, in the presence of 2,2'-azobisisobutyronitrile for 6 hours. The reaction solution was then treated in the same manner as in synthetic example 1 (1), to obtain 5 g of a copolymer of styrene and of N- (4-tert-butoxycarbonyloxyphenyl) maleimide.

   Analysis by NMR on H of the polymer thus obtained confirms that it contains a styrene unit and a N- (4-tert-butoxycaronyloxypnenyl) maleimide unit in a ratio of 1: 9 (by number).



  SYNTHESIS EXAMPLE 9 [Synthesis of a resin having an acid decomposable radical: compound (v)]
12 g of a poly (p-hydroxystyrene) (weight average molecular weight: 9600) are dissolved in 120 m. of N, N- dimethylacetamide. 7 g of potassium carbonate and then 9 g of t-butyl bromoacetate are added to the solution. The reaction mixture is then kept for 7 hours at

  <Desc / Clms Page number 55>

 a temperature of 1200 C with stirring. The reaction solution is then treated in the same way as in synthetic example 1 (1), to obtain a resin represented by the general formula (v).

   Analysis by H NMR of the resin confirms that it comprises a unit carrying a radical decomposable by an acid and a unit of p-hydroxystyrene in a 1: 6 ratio (in number).



  SYNTHESIS EXAMPLE 10 [Synthesis of the dissolution inhibitor compound (1)]
20 g of a a, a "-tris (4-hydroxyphenyl) -1, 3,5-triisopropylbenzene are dissolved in 400 mQ of tetrahydrofuran. To this solution is then added 14 g of potassium tert-butoxy under an atmosphere of The solution is then stirred for 10 minutes at room temperature, then 29.2 g of di-tert-butyldicarbonate are added to the solution, the solution is then reacted at room temperature for three hours. The reaction is then poured into ice water, the product obtained is then extracted with ethyl acetate, the ethyl acetate phase obtained is further washed with water and dried, the solvent is then removed by distillation. .

   The solid crystalline material obtained is recrystallized from diethyl ether, and then dried to obtain 25.6 g of an exemplary compound 16 (in which the radicals R are t-BOC radicals).



  SYNTHESIS EXAMPLE 11 [Synthesis of the inhibitor of dissolution (2)] 20 * g of a * a ', a "-tris (4-hydroxyphenyl) -1, 3,5- triisopropylbenz'ene are dissolved in 400 mQ of To this solution is added 31.6 g of 3,4-dihydro-2H-pyrane and hydrochloric acid in a catalytically active amount, under a nitrogen atmosphere. The mixture is then heated under reflux. For 24 hours, when the reaction is complete, add a small amount of sodium hydroxide, the reaction system is then filtered, and the solvent is then separated from the filtrate by distillation.

   The product obtained is refined

  <Desc / Clms Page number 56>

 by column chromatography and then dried, to obtain an exemplary compound 16 (in which the radicals R are THP radicals).



  SYNTHESIS EXAMPLE 12 [Synthesis of a dissolution inhibitor compound (3)]
To a solution of 19.2 g (0.04 mole) of an a, a ', a "tris (4-hydroxyphenyl) -1, 3, 5-triisopropylbenzene in 120mQ of N, N-dimethylacetamide, 21.2 is added g (0.15 mole) of potassium carbonate and additionally 27.1 g (0.14 mole) of t-butyl bromoacetate The mixture is then maintained for 7 hours with stirring at a temperature of 120 C.



  Then, the reaction mixture is poured into 1.5 Q of water and extracted with ethyl acetate. After drying over magnesium sulphate, the extract is concentrated and purified by column chromatography (support: silica gel, developer solvent: ethyl acetate and n-hexane in a volume ratio of 3: 7), to obtain 30 g of a light yellow viscous solid material. NMR analysis confirms that this product is an exemplary compound 16 (where all the radicals R are radicals -CH2COOC4H9t).



  SYNTHESIS EXAMPLE 13 Synthesis of the dissolution inhibitor compound (4)]
42.4 g (0.010 mole) of 1- (a-methyl-a- (4'-hydroxyphenyl) ethyl] -4- [a ', a'-bis (4 "-hydroxyphenyl) ethyl] benzene are dissolved in 300 mQ of N, N-dimethylacetamide.



  Then added to the solution 49.5 g (0.35 mole) of potassium carbonate and 84.8 g (0.33 mole) of bromoacetate of cumyl ester. The mixture is then kept stirring for 7 hours at a temperature of 120 C. The reaction mixture is poured into 2 Q of deionized water, neutralized with acetic acid and then extracted with ethyl acetate. The extract in ethyl acetate is concentrated and purified in the same manner as in synthetic example 3, to obtain 70 g of an exemplary compound 8 (where all the radicals R are CHCOOC radicals (CH ), VS).

  <Desc / Clms Page number 57>

 



  SYNTHESIS EXAMPLE 14 [Synthesis of the dissolution inhibitor compound (5)]
To a solution of 14.3 g (0.020 mole) of a, a, a ', a', a ", a" -hexaskis (4-hydroxyphenyl) -1, 3,5triethylbenzene in 120 mQ of N, N-dimethylacetamide , 21.2 g (0.15 mole) of potassium carbonate are added and in addition 27.1 g (0.14 mole) of t-butyl bromoacetate. The mixture is then kept stirring for 7 hours at a temperature of 120 C. The reaction mixture is then poured into 1.5 Q of water and then extracted with ethyl acetate. After drying over magnesium sulfate, the extract is concentrated and purified by column chromatography (support: silica gel; revealing solvent: ethyl acetate and n-hexane in a volume ratio of 2: 8), to obtain 24 g a light yellow powder.

   NMR analysis confirms that the product is an exemplary compound 40 (where all the radicals R are -CH-COO-CHg radicals).



  SYNTHESIS EXAMPLE 15 [Synthesis of the dissolution inhibitor compound (6)]
To a solution of 14.3 g (0.020 mole) of a, a, a ', a', a ", a" -hexaskis (4-hydroxyphenyl) -1, 3,5triethylbenzene in 120 mQ of N, N-dimethylacetamide , 10.6 g (0.14 mole) of potassium carbonate and additionally 13.6 g (0.07 mole) of t-butyl bromoacetate are added. The mixture is then kept stirring for 7 hours at a temperature of 120 C. The reaction mixture
 EMI57.1
 is then poured into 1.5 Q of water. The product is then -, extracted with ethyl acetate.

   After drying over magnesium sulfate, the extract is concentrated and fractionated by column chromatography (support: silica gel; revealing solvent: ethyl acetate and n-hexane in a volume ratio of 1: 5), to obtain 4 g of an exemplary compound 40 (in which three of the R radicals in the molecule are
 EMI57.2
 t -CH-COO-CH radicals, the other radical R being a hydrogen atom.).



  EXAMPLE 1-22
The compounds according to the present invention such as

  <Desc / Clms Page number 58>

 presented in the synthesis examples above were used to prepare resists presenting the formulations given in Table 1.



  COMPARATIVE EXAMPLES 1,2
A t-butoxycarbonyloxystyrene polymer and a t-butoxycarbonyloxy-a-methylstyrene polymer were synthesized according to the method described in US Pat. No. 4,491,628. These polymers are then used to prepare binary resists working in positive. The formulations of these resists are presented in Table 1.



  COMPARATIVE EXAMPLES 3,4, 5
Di-t-butyl terephthalate and tri-t-butoxyfluoroglycitricarbonate as described in JP-A-4 158 363, and a compound having the general formula below:
 EMI58.1
 as described in patent DE-4 214 363 were used as dissolution inhibitors to prepare ternary resists working in positive and presenting the formulations presented in table 1.



  COMPARATIVE EXAMPLE 6
A poly (p-hydroxystyrene) as an acid-decomposable radical-free resin, and the dissolution inhibitor compound (42) of the present invention were used to prepare a positive working ternary resist. The resist formulations are presented in Table 1.

  <Desc / Clms Page number 59>

 



  Table 1: formulations of a photosensitive composition
 EMI59.1
 
 <tb>
 <tb> Inhibitor <SEP> from <SEP> dissolution <SEP> decomposable <SEP> by <SEP> a
 <tb> acid
 <tb> Ex. <SEP> Resin <SEP> (g) <SEP> Photogenerator <SEP> Compound <SEP> Group <SEP> decomposable
 <tb> No. <SEP> of acid <SEP> (g) <SEP> no <SEP> (g) <SEP> by <SEP> a <SEP> acid
 <tb> 1 <SEP> Ex. <SEP> synth. <SEP> 1 <SEP> 1, <SEP> 1) <SEP> PAG3-3 <SEP> 0.05 <SEP> Compound <SEP> TBOC
 <tb> (1) <SEP> 0.05
 <tb> 2 <SEP> Ex. <SEP> synth. <SEP> 2 <SEP> 1.5 <SEP> PAG4-3 <SEP> 0.05 <SEP> Compound <SEP> TBE
 <tb> (1) <SEP> 0.05
 <tb> 3 <SEP> Ex. <SEP> synth. <SEP> 3 <SEP> r <SEP> 1, <SEP> 5 <SEP> PAG4-5 <SEP> 0.05 <SEP> Compound <SEP> THP
 <tb> (3) <SEP> 0.05
 <tb> 4 <SEP> Ex. <SEP> synth. <SEP> 4 <SEP> 1.5 <SEP> PAG4-7 <SEP> 0.05 <SEP> Compound <SEP> TBE
 <tb> (8) <SEP> 0.05
 <tb> 5 <SEP> Ex. <SEP> synth.

    <SEP> 5 <SEP> 1.5 <SEP> PAG4-3 <SEP> 0.05 <SEP> Compound <SEP> TBE
 <tb> (9) <SEP> 0.05
 <tb> 6 <SEP> Ex. <SEP> synth. <SEP> 6 <SEP> 1.5 <SEP> PAG5-12 <SEP> 0.05 <SEP> Compound <SEP> TBOC
 <tb> (13 <SEP> 0.05
 <tb> 7 <SEP> Ex. <SEP> synth. <SEP> 7 <SEP> 1.5 <SEP> PAG4-3 <SEP> 0.05 <SEP> Compound <SEP> TBOC
 <tb> (16 <SEP> 0.05
 <tb> 8 <SEP> Ex. <SEP> synth. <SEP> 8 <SEP> 1.5 <SEP> PAG4-3 <SEP> 0.05 <SEP> Compound <SEP> TBE
 <tb> (16 <SEP> 0.05
 <tb> 9 <SEP> Ex. <SEP> synth. <SEP> 9 <SEP> 1.5 <SEP> PAG4-5 <SEP> 0.05 <SEP> Compound <SEP> CUE
 <tb> (16) <SEP> 0.05
 <tb> 10 <SEP> Ex. <SEP> synth. <SEP> 1 <SEP> 1.5 <SEP> PAG6-3 <SEP> 0.10 <SEP> Compound <SEP> TBE
 <tb> (20) <SEP> 0.05
 <tb> 1 <SEP> 1 <SEP> Ex. <SEP> synth. <SEP> 2 <SEP> 1.5 <SEP> PAG5-13 <SEP> 0.05 <SEP> Compound <SEP> TBE
 <tb> (22) <SEP> 0.05
 <tb> 12 <SEP> Ex. <SEP> synth.

    <SEP> 3 <SEP> 1.5 <SEP> PAG6-15 <SEP> 0.10 <SEP> Compound <SEP> THP
 <tb> (34) <SEP> 0.05
 <tb> 13 <SEP> Ex. <SEP> synth. <SEP> 4 <SEP> 1.5 <SEP> PAG6-14 <SEP> 0, <SEP> 10 <SEP> Compound <SEP> TBOC
 <tb> (36) <SEP> 0.05
 <tb> 14 <SEP> Ex. <SEP> synth. <SEP> 9 <SEP> 1.5 <SEP> PAG4-3 <SEP> 0.05 <SEP> Compound <SEP> TBE
 <tb> (40) <SEP> 0.05
 <tb>
 

  <Desc / Clms Page number 60>

 Table 1:

   formulations of a photosensitive composition (continued)
 EMI60.1
 
 <tb>
 <tb> Inhibitor <SEP> from <SEP> aissoiution <SEP> decomposable <SEP> by <SEP> a
 <tb> acid
 <tb> Ex. <SEP> Resin <SEP> (g) <SEP> Photogenerator <SEP> Compound <SEP> n <SEP> (g) <SEP> Group <SEP> decomposable
 <tb> No. <SEP> of acid <SEP> (g) <SEP> by <SEP> a <SEP> acid
 <tb> 15 <SEP> Ex. <SEP> synth. <SEP> 5 <SEP> 1.5 <SEP> PAG4-4 <SEP> 0.05 <SEP> Compound <SEP> TBOC
 <tb> (42 <SEP> 0.05
 <tb> 16 <SEP> Ex. <SEP> synth. <SEP> 1 <SEP> 1.5 <SEP> PAG4-3 <SEP> 0.05 <SEP> Ex. <SEP> synth. <SEP> TBE
 <tb> 15 (40) <SEP> 0.05
 <tb> 17 <SEP> Ex. <SEP> synth. <SEP> 2 <SEP> 1.5 <SEP> PAG5-12 <SEP> 0.05 <SEP> Ex. <SEP> synth. <SEP> TBE
 <tb> 15 (40) <SEP> 0.05
 <tb> 18 <SEP> Ex. <SEP> synth. <SEP> 8 <SEP> 1.5 <SEP> PAG4-4 <SEP> 0.05 <SEP> Ex. <SEP> synth. <SEP> TBE
 <tb> 15 (40) <SEP> 0.05
 <tb> 19 <SEP> Ex. <SEP> synth.

    <SEP> 9 <SEP> 1.5 <SEP> PAG4-5 <SEP> 0.05 <SEP> Ex. <SEP> synth. <SEP> TBE
 <tb> 15 <SEP> (40 <SEP> 0.05
 <tb> 20 <SEP> Ex. <SEP> synth. <SEP> 1.5 <SEP> PAG6-3 <SEP> 0.10 <SEP> Compound <SEP> TBE
 <tb> 5 <SEP> PVP <SEP> (16 <SEP> 0.05
 <tb> = 2/1
 <tb> 21 <SEP> Ei. <SEP> synth. <SEP> 1, <SEP> 5 <SEP> PAG4-5 <SEP> 0.05 <SEP> Compound <SEP> TBOC
 <tb> 6 / PVP <SEP> (5) <SEP> 0.05
 <tb> = 1/1
 <tb> 22 <SEP> Ex. <SEP> synth. <SEP> 1.5 <SEP> PAG5-12 <SEP> 0.05 <SEP> Compound <SEP> THP
 <tb> 9 / PVP <SEP> (19) <SEP> 0.05
 <tb> = 3/1
 <tb>
 

  <Desc / Clms Page number 61>

 
 EMI61.1
 '8 il) lolmtllattolls (ì'e compositlosl l) hotosellslble (sulte)
 EMI61.2
 
 <tb>
 <tb> Inhibitor <SEP> from <SEP> dissolution
 <tb> decomposable <SEP> by <SEP> a <SEP> acid
 <tb> Example <SEP> Resin <SEP> (g) <SEP> Photogenerator <SEP> Compound <SEP> n <SEP> (9) <SEP> Group
 <tb> No.

    <SEP> of acid <SEP> (9) <SEP> decomposable <SEP> by
 <tb> a <SEP> acid
 <tb> Ex. <SEP> comp. <SEP> 1 <SEP> TBOCS <SEP> 1, <SEP> 0 <SEP> PAG4-3 <SEP> 0, <SEP> 10 - Ex. <SEP> comp. <SEP> 2 <SEP> TEAMS ', <SEP> 0 <SEP> PAG4-3 <SEP> 0, <SEP> 10 - Ex. <SEP> comp. <SEP> 3 <SEP> Ex. <SEP> synth. <SEP> 1 <SEP> 1, <SEP> 5 <SEP> PAG4-3 <SEP> 0.05 <SEP> DTBTP <SEP> 0, <SEP> 65
 <tb> Ex. <SEP> comp. <SEP> 4 <SEP> Ex <SEP> synth. <SEP> 1 <SEP> 1, <SEP> 5 <SEP> PAG4-3 <SEP> 0.05 <SEP> TBFTC <SEP> 0, <SEP> 65 - Ex. <SEP> comp. <SEP> 5 <SEP> Ex. <SEP> synth. <SEP> 1 <SEP> 1.5 <SEP> PAG4-3 <SEP> 0.05 <SEP> TBE6SI <SEP> 0, <SEP> 50
 <tb> Ex. <SEP> comp. <SEP> 6 <SEP> PVP <SEP> 1, <SEP> 5 <SEP> PAG4-3 <SEP> 0.05 <SEP> Comp. <SEP> (42) <SEP> 0.50 <SEP> TBE
 <tb>
 

  <Desc / Clms Page number 62>

 The abbreviations used in Table 1 are as follows: <resin> TBOCS:

   T-butoxycarbonyloxystyrene polymer (number average molecular weight: 21,600) TBAMS: t-butoxycarbonyloxy-a-methylstyrene polymer (weight average molecular weight: 46,900) PVP: p-hydroxystyrene polymer (weight average molecular weight: 9,600) <Dissolution inhibitor> DTBPT: Di-t-butylterephthalate TBFTC: Tri-t-butoxyfluoroglycitricarbonate TBE6SI:
 EMI62.1
 
R: -CH-COOC <radical decomposable by an acid in the dissolution inhibitor>
 EMI62.2
 [Preparation and evaluation of a photosensitive composition]. The respective materials presented in Table 1 were dissolved in 6 of diglime. The solutions were then passed through a 0.2 µm filter to prepare resist solutions.

   These solutions of resists were applied to a silicon wafer, using a rotary coating device rotating at 3000 rpm, and then dried on a hot plate of the vacuum adsorption type, at 110 ° C. for 60 seconds, to obtain a resist layer having a layer thickness of 1.0 µm.

  <Desc / Clms Page number 63>

 



   This resist layer was exposed using a sequential 248 nm KrF excimer type laser (NA = 0.42). After exposure, the resist layer was heated on the hot plate of the vacuum adsorption type, at a temperature of 100 ° C. for 60 seconds, and then immediately immersed in an aqueous solution at 1.19% by weight of tetramethylammonium hydroxide. (TMAH) for 60 seconds, then rinse with water for 30 seconds and dry. The drawings thus obtained on the silicon wafer were observed with a scanning electron microscope in order to evaluate the profile (angle of the side walls) of the resist. The results are presented in Table 2.



   The sensitivity is defined here as the inverse of an exposure necessary to reproduce a mask drawing of 0.50 μm, and is expressed in relative value compared to that of comparative example 1, defined as being equal to 1.0.



   The layer shrinkage is expressed in terms of the ratio between the layer thickness before and after exposure and curing.



   The resolving power of Table 2 indicates a critical resolving power, which is expressed as the minimum reproduced size of a mask design after the exposure necessary to fully reproduce a mask design with a size of 0.50 µm.



   The amplitude of the standing standing waves in
 EMI63.1
 the resistance profile was evaluated with a mask design of 0.7 u. m, compared to Comparative Example 1 serving as a reference. P indicates a situation less good than the reference, G indicates an identical or better situation than the reference.



   From the results presented in Table 2, it can be seen that the resists according to the present invention are not sensitive to the standing wave effect and exhibit less shrinkage of the layer after exposure, which provides an excellent profile and a resolving power

  <Desc / Clms Page number 64>

 Student.

  <Desc / Clms Page number 65>

 



  Table 2: Results of the evaluation
 EMI65.1
 
 <tb>
 <tb> Example <SEP> Sensitivity <SEP> Withdrawal <SEP> from <SEP> the <SEP> Decrease <SEP> from <SEP> To provide <SEP> from <SEP> Drawings <SEP> from <SEP> resist
 <tb> no. <SEP> relative <SEP> layer <SEP> (%) <SEP> the <SEP> layer <SEP> (%) <SEP> resolution <SEP> (um)
 <tb> Profile <SEP> Waves <SEP> stat.
 <tb>



  1 <SEP> 1.3 <SEP> 1 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 2 <SEP> 1,2 <SEP> 2 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 3 <SEP> 1.5 <SEP> 3 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 4 <SEP> 1, <SEP> 3 <SEP> f <SEP> 2 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 5 <SEP> 1,2 <SEP> 1 <SEP> 2 <SEP> 0.34 <SEP> good <SEP> G
 <tb> 6 <SEP> 1,2 <SEP> 2 <SEP> 1 <SEP> 0.34 <SEP> good <SEP> G
 <tb> 7 <SEP> 1, <SEP> 3 <SEP> 3 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 8 <SEP> 1, <SEP> 3 <SEP> 1 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 9 <SEP> 1.4 <SEP> 1 <SEP> 1 <SEP> 0.30 <SEP> good <SEP> G
 <tb> 10 <SEP> 1.3 <SEP> 1 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 11 <SEP> 1,2 <SEP> 1 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 12 <SEP> 1.3 <SEP> 2 <SEP> 1 <SEP> 0.30 <SEP> good <SEP> G
 <tb> 13 <SEP> 1.3 <SEP> 2 <SEP> 1 <SEP> 0.30 <SEP> good <SEP> G
 <tb> 14 <SEP> 1.4 <SEP> 1 <SEP> 1 <SEP> 0,

  30 <SEP> good <SEP> G
 <tb> 15 <SEP> 1.3 <SEP> 1 <SEP> 2 <SEP> 0.34 <SEP> good <SEP> G
 <tb> 16 <SEP> 1.3 <SEP> 1 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 17 <SEP> 1,2 <SEP> 1 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 18 <SEP> 1.3 <SEP> 1 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 19 <SEP> 1.5 <SEP> 1 <SEP> 1 <SEP> 0.30 <SEP> good <SEP> G
 <tb> 20 <SEP> 1.4 <SEP> 2 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 21 <SEP> 1.4 <SEP> 1 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb> 22 <SEP> 1.4 <SEP> 1 <SEP> 1 <SEP> 0.32 <SEP> good <SEP> G
 <tb>
 

  <Desc / Clms Page number 66>

 Table 2:

   Assessment results (continued)
 EMI66.1
 
 <tb>
 <tb> Example <SEP> Sensitivity <SEP> Withdrawal <SEP> from <SEP> the <SEP> Decrease <SEP> from <SEP> To provide <SEP> from <SEP> Drawings <SEP> from <SEP> resist
 <tb> no <SEP> relative <SEP> layer <SEP> (%) <SEP> the <SEP> layer <SEP> (%) <SEP> resolution <SEP> (um)
 <tb> Profile <SEP> Waves <SEP> stat.
 <tb>



  Ex. <SEP> comp. <SEP> 1 <SEP> 1, <SEP> 0 <SEP> 10 <SEP> 4 <SEP> 0.40 <SEP> tapered <SEP> G
 <tb> Ex. <SEP> comp. <SEP> 2 <SEP> 0.9 <SEP> 11 <SEP> 4 <SEP> 0.40 <SEP> tapered <SEP> G
 <tb> Ex. <SEP> comp. <SEP> 3 <SEP> 1,2 <SEP> 4 <SEP> 5 <SEP> 0.40 <SEP> tapered <SEP> G
 <tb> Ex. <SEP> comp. <SEP> 4 <SEP> 1, <SEP> 2 <SEP> @ <SEP> 3 <SEP> 4 <SEP> 0.40 <SEP> tapered <SEP> G
 <tb> Ex. <SEP> comp. <SEP> 5 <SEP> 1,2 <SEP> 3 <SEP> 2 <SEP> 0.36 <SEP> good <SEP> p
 <tb> Ex. <SEP> comp.

    <SEP> 6 <SEP> 1.5 <SEP> 1 <SEP> 2 <SEP> 0.34 <SEP> good <SEP> p
 <tb>
 

  <Desc / Clms Page number 67>

 
The chemically sensitized and positive-working photosensitive composition according to the present invention exhibits a less shrinkage of the layer by curing after exposure and a lesser reduction of the layer after development (in unexposed areas), and provides an excellent profile and a power of high resolution without the appearance of standing waves.



   Although the invention has been described in detail and with reference to specific embodiments, it will appear to those skilled in the art that various changes and modifications can be made thereto without departing from the scope and from the field which it covers. .


    

Claims (11)

Claims 1. A photosensitive composition working in positive comprising: (a) a resin having a radical decomposable by an acid, the solubility of which increases in an alkaline developer during a reaction with an acid, (b) a compound which generates an acid when it is irradiated with rays or actinic radiation;  and (c) an acid-decomposable non-polymeric dissolution inhibitor, having a molecular weight of not more than 3000, containing an acid-decomposable radical, the solubility of which increases in an alkaline developer upon reaction with an acid, in which said non-polymeric acid-decomposable dissolution inhibitor comprises at least three structural units per molecule, each of which has an acid-decomposable radical, substituted on a benzene ring, and there are at least nine bonding atoms (at the exclusion of radicals decomposable by an acid) inserted between two radicals decomposable by an acid located at the greatest distance.  2. A positive-working photosensitive composition according to claim 1, wherein said resin (a) has a main chain and a side chain, and has an acid decomposable radical in the main chain or in the side chain, or in both. .  3. A photosensitive composition working in a positive manner according to claim 1, in which the resin (a) is a resin obtained by protecting an alkali-soluble radical from an alkali-soluble resin by a radical decomposable by an acid, the rate of dissolution in alkalis of the alkali-soluble resin (a) being not less than 170 Å / sec, when it is determined at 23 ° C. in a 0.261 N aqueous solution of tetramethylammonium hydroxide (TMAH) .  4. A positive-working photosensitive composition according to claim 1, wherein the resin (a)  <Desc / Clms Page number 69>  has a weight average molecular weight in the range of 1000 to 100,000.  5. A photosensitive composition working in positive according to claim 1, in which at least 10 bonding atoms (excluding the atoms of the radicals decomposable by an acid) are interposed between two radicals decomposable by an acid of the inhibitor of dissolution not polymer decomposable by an acid.  6. A positive-working photosensitive composition according to claim 1, in which at least 11 bonding atoms (excluding the atoms of the radicals decomposable by an acid) are interposed between two radicals decomposable by an acid located at the greatest distance, non-polymeric acid decomposable dissolution inhibitor.  7. The photosensitive composition working positively according to claim 1, in which the resin (a) is present at a content of 50 to 97% by weight, calculated on the total weight of the photosensitive composition; the compound (b) is present at a content of 0.001 to 40% by weight calculated on the total weight of the photosensitive composition; and the compound (c) is present at a content of 3 to 50% by weight, calculated on the total weight of the photosensitive composition.  8. A photosensitive positive-working composition according to claim 3, in which the alkali-soluble resin is chosen from the group consisting of poly (hydroxystyrene), hydrogenated poly (hydroxystyrene), halogen-substituted poly (hydroxystyrene), poly (hydroxystyrene) substituted by alkyl, partially o-acylated poly (hydroxystyrene) and hydrogenated novolak resins.  9. A photosensitive composition working in positive according to claim 8, in which the poly (hydroxystyrene) is chosen from the group consisting of poly (p-hydroxystyrene), poly (m-hydroxystyrene), poly (o-hydroxystyrene) and two or three copolymers  <Desc / Clms Page number 70>  monomers of p-hydroxystyrene, m-hydroxystyrene and 0-hydroxystyrene.  10. A photosensitive positive-working composition according to claim 1, in which said compound (c) inhibitor of dissolution decomposable by an acid has a molecular weight of 500 to 3000.  11. A photosensitive positive-working composition according to claim 1, in which said non-polymeric decomposable dissolution inhibitor (c) with an acid has a molecular weight of 1000 to 2500.