# Patent

## Title
Low activation energy dissolution modification agents for photoresist applications

## Abstract

A photoresist composition including a polymer, a photoacid generator and a dissolution modification agent, a method of forming an image using the photoresist composition and the dissolution modification agent composition. The dissolution modification agent is insoluble in aqueous alkaline developer and inhibits dissolution of the polymer in the developer until acid is generated by the photoacid generator being exposed to actinic radiation, whereupon the dissolution modifying agent, at a suitable temperature, becomes soluble in the developer and allows the polymer to dissolve in the developer. The DMAs are glucosides, cholates, citrates and adamantanedicarboxylates protected with acid-labile ethoxyethyl, tetrahydrofuranyl, and angelicalactonyl groups.

## Background
FIELD OF THE INVENTION
This invention relates generally to the field of photolithography. More specifically, the invention relates to chemically amplified photoresist system compositions containing dissolution modification agents, methods of using chemically amplified photoresist system compositions containing dissolution modification agents and dissolution modification agents for chemically amplified resist systems.
BACKGROUND OF THE INVENTION
The patterning of radiation sensitive polymeric films with actinic radiation such as ultraviolet light at wavelengths of 436, 365, 257, 248, 193 or 157 nanometers (nm) is the principle means of defining high resolution circuitry found in semiconductor devices. The radiation sensitive films, often referred to as photoresists, generally consist of multi-component formulations that are coated onto a desired substrate. The radiation is exposed patternwise and induces a chemical transformation that renders the solubility of the exposed regions of the films different from that of the unexposed areas when the films are treated with an appropriate developer.
Chemically amplified photoresists are based on a catalytic mechanism that allows a relatively large number of chemical events such as, for example, de-protection reactions in the case of positive photoresists or cross-linking reactions in the case of negative tone photoresists, to be brought about by the application of a relatively low dose of radiation that induces formation of a catalyst, often a strong acid. However, chemically amplified photoresists, particularly in the sub-50 nm regime, experience diminished image resolution or contrast, often referred to as “image blur.”
Therefore, there is an ongoing need for new photoresist compositions having improved image resolution capability as well as improved methods of patterning substrates.
SUMMARY OF THE INVENTION
A first aspect of the present invention is a photoresist composition, comprising:
a polymer that is soluble in an aqueous alkaline developer; a photoacid generator; and a dissolution modification agent, the dissolution modification agent represented by at least one of the following structures:




wherein W and X are independently selected from the group consisting of an alkylene group having 1 to 12 carbon atoms, and a fluorinated alkylene group having 1 to 12 carbon atoms;
wherein each P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14 and P15 is independently selected from the group consisting of a structure V, a structure VI and a structure VII:




wherein each R1, R2, R3, R4, R5, R6 and R7 is independently selected from the group consisting of a hydrogen atom, a hydrocarbyl group having 4 to 12 carbon atoms, a substituted hydrocarbyl group having 4 to 12 carbon atoms, a heterohydrocarbyl group having 4 to 12 carbon atoms, and a substituted heterohydrocarbyl group having 4 to 12 carbon atoms; and
wherein any two R1, R2, R3 or any two R4, R5, R6 may be linked to form a three to eight-membered cyclic group.
A second aspect of the present invention is the dissolution modification agent represented by the structure:




A third aspect of the present invention is the dissolution modification agent represented by the structure:




A fourth aspect of the present invention is the dissolution modification agent represented by the structure:




A fifth aspect of the present invention is the dissolution modification agent represented by the structure:




A sixth aspect of the present invention is the photoresist composition further including a casting solvent selected from the group consisting of cyclohexanone, ethyl lactate, propylene glycol methyl ether acetate, gamma-butyrolactone and combinations thereof.
A seventh aspect of the present invention is the photoresist composition not soluble in basic developer prior to exposure to ultraviolet radiation.
An eight aspect of the present invention is the photoacid generator generates a free acid upon exposure to ultraviolet radiation having a wavelength of less than about 250 nm.
A ninth aspect of the present invention is, after exposure of the photoresist composition to ultraviolet radiation, the dissolution modifying agent becomes soluble in the aqueous alkaline developer.
A tenth aspect of the present invention is, after exposure of the photoresist composition to ultraviolet radiation followed by heating to about 100° C. or less, the dissolution modifying agent becomes soluble in the aqueous alkaline developer.
An eleventh second aspect of the present invention is the photoresist composition, further including a casting solvent and wherein the photoresist composition comprises about 8% by weight to about 15% by weight of the polymer, about 1% by weight to about 3% by weight of the photoacid generator and about 10% by weight to about 20% by weight of the dissolution modifying agent.
A twelfth aspect of the present invention is the photoresist composition, wherein the polymer comprises repeating units of one or more monomers represented by the following structures:

M1-R8  (VIIIi)

M2-R9  (VIIIii)

M3-R10  (VIIIiii)

where M1, M2 and M3 are independently selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
where R8 has a structure —R11—CR12R13—OH, in which:

    
    
        R11 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
        R12 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, a substituted alkyl group having 1 to 22 carbon atoms, and a fluorinated alkyl group having 1 to 24 carbon atoms;
        R13 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, and a fluorinated alkyl group having 1 to 24 carbon atoms; and
        wherein R12 and R13 may be linked to form a 3 to 8 carbon atom cyclic ring;
    
    


wherein R9 has a structure —R14—NH—SO2R15, in which:

    
    
        R14 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 2 to 12 carbon atoms; and
        R15 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, a fluorinated alkyl group having 1 to 24 carbon atoms, a substituted alkyl group having 1 to 24 carbon atoms, and a fluorinated alkyl group having 1 to 24 carbon atoms; and
    
    


wherein R10 has a structure —R16—COOH, in which:

    
    
        R16 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms.
    
    


A thirteenth aspect of the present invention is the photoresist composition, wherein the polymer comprises repeating units of one or more monomers represented by the following structures:




    
    
        wherein each R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46 and R47 (R18-R47) is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl substituent with a primary, secondary or tertiary carbon attachment point, the hydrocarbyl substituent selected from the group consisting of a linear alkyl or an alkoxy group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms , an alkoxy group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a bicycloalkyl group having 3-17 carbon atoms, a cycloalkoxy having 3-17 carbon atoms, a bicycloalkoxy group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, an alkenyl group having 2-12 carbon atoms, a cycloalkenyl group having 2-12 carbon atoms, a dihydropyranyl group, a dihydrofuranyl group, an alkalkenyl group having 2-12 carbon atoms, an alkenylalkyl group having 2-12 carbon atoms, an alkynyl group having 2-12 carbon atoms, an alkalkynyl group having 2-12 carbon atoms, an alkynylalkyl group having 2-12 carbon atoms, a trifluoromethyl group, a trifluoroethyl group, a trifluoropropyl group, and a cyanopropyl group; and
    
    


wherein any two of R18-R20, R21-R30, R31-R39 and R40-R47 in the same molecule may be linked to form a 3 to 8 carbon atom cyclic ring.
A fourteenth aspect of the present invention is the photoresist composition of claim 1, wherein the polymer comprises repeating units of one or more monomers represented by the following structures:







A fifteenth aspect of the present invention is the photoresist composition, wherein the polymer comprises repeating units of one or more monomers represented by the following structures:




A sixteenth aspect of the present invention is the photoresist composition, wherein the polymer comprises repeating units of one or more monomers represented by the following structures:




A seventeenth aspect of the present invention is the photoresist composition, wherein the polymer comprises repeating units of one or more monomers represented by the following structure:




wherein M is a polymerizable backbone moiety;
wherein each Ym at each occurrence is independently selected from the group consisting of —C(O)O—, —C(O)—, —OC(O)—, —O—C(O)— and —C(O)—O—;
wherein each Zn at each occurrence is independently selected from the group consisting of an alkylene group having 1 to 12 carbon atoms, a fluorinated alkylene group having 1 to 12 carbon atoms, a heteroalkylene group having 1 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
wherein (a) m and n are both 1, (b) m is 1 and n is 0 or (c) m is 0 and n is 1; and
wherein each occurrence of R48 is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a hydroxy substituted alkylene having 1 to 12 carbon atoms, a hydroxy substituted fluoroalkylene having 1 to 12 carbon atoms, a bis-trifluoromethylmethanol group, and an alkylsulfonamide group having 1 to 12 carbon atoms.
An eighteenth aspect of the present invention is the photoresist composition, wherein the photoacid generator is selected from the group consisting of sulfonium salts, triphenylsulfonium perfluoromethanesulfonate(triphenylsulfonium triflate), triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluoropentanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium iodide, 2,4,6-trimethylphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium benzenesulfonate, tris(t-butylphenyl)sulfonium salts, diphenylethylsulfonium chloride, phenacyldimethylsulfonium chloride, halonium salts, diphenyliodonium perfluoromethanesulfonate(diphenyliodonium triflate), diphenyliodonium perfluorobutanesulfonate, diphenyliodonium perfluoropentanesulfonate, diphenyliodonium salts, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis-(t-butylphenyl)iodonium triflate, bis-(t-butylphenyl)-iodonium camphorsulfonate, α, α′-bis-sulfonyl-diazomethanes, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-(1,1dimethylethylsulfonyl) diazomethane, bis(cyclohexylsulfonyl)diazomethane, trifluoromethanesulfonate esters of imides and hydroxyimides, (trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (MDT), nitrobenzyl sulfonate esters, 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate; sulfonyloxynaphthalimides, N-camphorsulfonyloxynaphthalimide, N-pentafluorophenylsulfonyloxynaphthalimide; pyrogallol derivatives (e.g., trimesylate of pyrogallol), naphthoquinone-4-diazides, alkyl disulfones, s-triazine derivatives; sulfonic acid generators, N-hydroxynaphthalimide dodecane sulfonate (DDSN) and benzoin tosylate.
A nineteenth aspect of the present invention is a method of forming a pattern, comprising: applying a photoresist layer of the photoresist composition of the first aspect of the present invention over a substrate, the photoresist composition, comprising: a polymer that is soluble in an aqueous alkaline developer; a photoacid generator; and a dissolution modification agent, the dissolution modification agent represented by at least one of the following structures:




    
    
        wherein W and X are independently selected from the group consisting of an alkylene group having 1 to 12 carbon atoms, and a fluorinated alkylene group having 1 to 12 carbon atoms;
        wherein each P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14 and P15 is independently selected from the group consisting of a structure V, a structure VI and a structure VII:
    
    






    
    
        wherein each R1, R2, R3, R4, R5, R6 and R7 is independently selected from the group consisting of a hydrogen atom, a hydrocarbyl group having 4 to 12 carbon atoms, a substituted hydrocarbyl group having 4 to 12 carbon atoms, a heterohydrocarbyl group having 4 to 12 carbon atoms, and a substituted heterohydrocarbyl group having 4 to 12 carbon atoms; and
        wherein any two R1, R2, R3 or any two R4, R5, R6 may be linked to form a three to eight-membered cyclic group; and
    
    


selectively exposing a first region of the photoresist layer to actinic radiation while not exposing a second region of the photoresist layer to the actinic radiation to form an exposed photoresist layer; heating the exposed photoresist layer; and removing the first region of the photoresist layer in the aqueous alkaline developer.
A twentieth aspect of the present invention is the method, wherein the heating of the exposed photoresist layer is at a temperature of about 100° C. or less before the removing the first region of the photoresist layer in the aqueous alkaline developer.
A twenty-first aspect of the present invention is the method, wherein the actinic radiation has a wavelength of about 250 nm or less.
A twenty-second aspect of the present invention is the method, wherein the photoresist resist layer has a thickness of between about 0.02 μm and about 5.0 μm.
A twenty-third aspect of the present invention is the method, wherein the substrate is selected from the group consisting of a metal substrate, a ceramic substrate, an organic substrate, a bulk silicon substrate, a silicon-on-insulator substrate and other semiconductor substrates.
A twenty-fourth aspect of the present invention is the method, wherein a conductive, semi-conductive or insulating layer is formed on a top surface of the substrate, and wherein the photoresist layer is formed on a top surface of the conductive, semi-conductive or insulating layer.
A twenty-fifth aspect of the present invention is the method, further including forming an anti-reflective coating over the substrate prior to the applying the photoresist layer over the substrate.
A twenty-sixth aspect of the present invention is the method, wherein the photoresist composition includes a casting solvent selected from the group consisting of cyclohexanone, ethyl lactate, propylene glycol methyl ether acetate, gamma-butyrolactone and combinations thereof.
A twenty-seventh aspect of the present invention is the method, wherein the photoresist composition includes a casting solvent, and wherein the photoresist composition comprises about 8% by weight to about 15% by weight of the polymer, about 1% by weight to about 3% by weight of the photoacid generator and about 10% by weight to about 15% by weight of the dissolution modifying agent.
A twenty-eighth aspect of the present invention is the method, wherein the method further comprises forming the polymer by polymerization of one or more monomers represented by the following structures:

M1-R8  (VIIIi)

M2-R9  (VIIIii)

M3-R10  (VIIIiii)

where M1, M2 and M3 are independently selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
where R8 has a structure —R11—CR12R13—OH, in which:

    
    
        R11 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
        R12 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, and a substituted alkyl group having 1 to 22 carbon atoms;
        R13 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, and a fluorinated alkyl group having 1 to 24 carbon atoms; and
        wherein R12 and R13 may be linked to form a 3 to 8 carbon atom cyclic ring;
    
    


wherein R9 has a structure —R14—NH—SO2R15, in which:

    
    
        R14 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 2 to 12 carbon atoms; and
        R15 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, a fluorinated alkyl group having 1 to 24 carbon atoms, a substituted alkyl group having 1 to 24 carbon atoms, and a fluorinated alkyl group having 1 to 24 carbon atoms; and
    
    


wherein R10 has a structure —R16—COOH, in which:

    
    
        R16 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms.
    
    


A twenty-ninth aspect of the present invention is the method, wherein the method further comprises forming the polymer by polymerization of one or more monomers represented by the following structures:




wherein each R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46 and R47 (R18-R47) is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl substituent with a primary, secondary or tertiary carbon attachment point, the hydrocarbyl substituent selected from the group consisting of a linear alkyl or an alkoxy group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, an alkoxy group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a bicycloalkyl group having 3-17 carbon atoms, a cycloalkoxy having 3-17 carbon atoms, a bicycloalkoxy group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, an alkenyl group having 2-12 carbon atoms, a cycloalkenyl group having 2-12 carbon atoms, a dihydropyranyl group, a dihydrofuranyl group, an alkalkenyl group having 2-12 carbon atoms, an alkenylalkyl group having 2-12 carbon atoms, an alkynyl group having 2-12 carbon atoms, an alkalkynyl group having 2-12 carbon atoms, an alkynylalkyl group having 2-12 carbon atoms, a trifluoromethyl group, a trifluoroethyl group, a trifluoropropyl group, and a cyanopropyl group; and
wherein any two of R18-R20, R21-R30, R31-R39 and R40-R47 in the same molecule may be linked to form a 3 to 8 carbon atom cyclic ring.
A thirtieth aspect of the present invention is the method, wherein the method further comprises forming the polymer by polymerization of one or more monomers represented by the following structures:







A thirty-first aspect of the present invention is the method, wherein the method further comprises forming the polymer by polymerization of one or more monomers represented by the following structures:




A thirty-second aspect of the present invention is the method further comprising forming the polymer by polymerization of one or more monomers represented by the following structures:




A thirty-third aspect of the present invention is the method, wherein the method further comprises forming the polymer by polymerization of one or more monomers represented by the following structures:




wherein M is a polymerizable backbone moiety;
wherein each Ym at each occurrence is independently selected from the group consisting of —C(O)O—, —C(O)—, —OC(O)—, —O—C(O)— and —C(O)—O—;
wherein each Zn at each occurrence is independently selected from the group consisting of an alkylene group having 1 to 12 carbon atoms, a fluorinated alkylene group having 1 to 12 carbon atoms, a heteroalkylene group having 1 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
wherein (a) m and n are both 1, (b) m is 1 and n is 0 or (c) m is 0 and n is 1; and wherein each occurrence of R48 is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a hydroxy substituted alkylene having 1 to 12 carbon atoms, a hydroxy substituted fluoroalkylene having 1 to 12 carbon atoms, a bis-trifluoromethylmethanol group, and an alkylsulfonamide group having 1 to 12 carbon atoms.
A thirty-fourth aspect of the present invention is the method, wherein the photoacid generator is selected from the group consisting of sulfonium salts, triphenylsulfonium perfluoromethanesulfonate(triphenylsulfonium triflate), triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluoropentanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium iodide, 2,4,6-trimethylphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium benzenesulfonate, tris(t-butylphenyl)sulfonium salts, diphenylethylsulfonium chloride, phenacyldimethylsulfonium chloride, halonium salts, diphenyliodonium perfluoromethanesulfonate(diphenyliodonium triflate), diphenyliodonium perfluorobutanesulfonate, diphenyliodonium perfluoropentanesulfonate, diphenyliodonium salts, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis-(t-butylphenyl)iodonium triflate, bis-(t-butylphenyl)-iodonium camphorsulfonate, α, α′-bis-sulfonyl-diazomethanes, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-(1,1dimethylethylsulfonyl) diazomethane, bis(cyclohexylsulfonyl)diazomethane, trifluoromethanesulfonate esters of imides and hydroxyimides, (trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (MDT), nitrobenzyl sulfonate esters, 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate; sulfonyloxynaphthalimides, N-camphorsulfonyloxynaphthalimide and N-pentafluorophenylsulfonyloxynaphthalimide; pyrogallol derivatives (e.g., trimesylate of pyrogallol), naphthoquinone-4-diazides, alkyl disulfones, s-triazine derivatives; sulfonic acid generators, N-hydroxynaphthalimide dodecane sulfonate (DDSN) and benzoin tosylate.



BRIEF DESCRIPTION OF DRAWINGS
The features of the invention are set forth in the appended claims. The invention itself, however, will be best understood by reference to the following detailed description of an illustrative embodiment when read in conjunction with the accompanying drawings, wherein:
FIGS. 1A through 1G are cross-sectional views of an exemplary photoresist patterning method according to the various embodiments of the present invention;
FIG. 2A is plot of photoresist thickness versus post exposure bake temperature for a control photoresist formulation;
FIG. 2B is plot of photoresist thickness versus post exposure bake temperature for an experimental photoresist formulation according to an embodiment of the present invention; and
FIG. 3 is plot of photoresist thickness versus actinic radiation dose as a function of post exposure bake temperature for an experimental photoresist formulation according to an embodiment of the present invention.



DETAILED DESCRIPTION OF THE INVENTION
Chemically amplified (CA) positive photoresists described by the various embodiments of the present invention are intended to be developed in an aqueous developer and include a polymer that is soluble in an aqueous alkaline solution, a dissolution modification agent (DMA), and a photoacid generator (PAG), all usually dissolved in a casting solvent. The PAG generates acid upon exposure to actinic radiation.
Image blur in such a photoresist system is generally thought to result from two contributing factors: gradient-driven diffusion of acid from exposed into non-exposed regions and reaction propagation. Acid diffusion is thought to depend upon such factors as the type of PAG and acid moiety mobility in the photoresist polymer. Acid mobility in a photoresist layer is dependent on a variety of factors, including the chemical functionality of the polymer and the temperature of the photoresist layer. Reaction propagation is thought to depend upon such factors as the activation energy (enthalpy) and the volatility of reaction products (entropy). Both acid diffusion and acid mobility increase with increasing temperature with resultant increasing image blur.
DMAs according to various embodiments of the present invention are hydrophobic and insoluble in aqueous alkaline developer, thus inhibiting polymer dissolution in the unexposed regions of photoresist layers. In some examples, the polymer itself may be soluble in aqueous alkaline developer, but is inhibited from dissolving in the developer by the strong hydrophobic nature of the DMA. At the same time, DMAs according to various embodiments of the present invention, when activated, become hydrophilic and soluble in aqueous alkaline developer and thus enhance polymer dissolution in the exposed regions of photoresist layers. When activated, the DMA become soluble and hydrophilic and no longer inhibits solution of the polymers in the exposed regions of the photoresist layer. DMAs are activated by the acid released by the PAG at temperatures dependent upon the activation energy of protected acid-labile moieties of the DMAs.
Since it is advantageous to minimize the temperature to which exposed photoresist layers are subjected (to minimize image blur), the various embodiments of the present invention utilize DMAs that are relatively small molecules containing polar and/or base-soluble moieties which are protected by low activation (e.g. low temperature) acid-labile functionalities.
FIGS. 1A through 1G are cross-sectional views of an exemplary photoresist patterning method according to the various embodiments of the present invention.
In FIG. 1A, formed on a top surface 100 of a substrate 105 is an optional insulating layer 110. In one example, substrate 100 is selected from the group consisting of a metal substrate, a ceramic substrate, an organic substrate, a bulk silicon substrate, a silicon-on-insulator substrate and other semiconductor substrates. In one example, layer 110 comprises silicon dioxide, silicon nitride, silicon oxynitride and combinations thereof. Layer 110 may include other insulating materials as is known in the art of integrated circuit manufacture. Alternatively, layer 110 may be replaced by a conductive layer or a semi-conductive layer as is known in the art of integrated circuit manufacture.
Formed on a top surface 115 of layer 110 is an optional anti-reflective coating (ARC). In one example, ARC 115 comprises a diazonaphthoquinone (DNQ)/novolak resist material. ARC 115 may be formed on top surface 105 of substrate 100 if there is no layer 110.
Formed on a top surface 125 of ARC 120 is a photoresist layer 130. Photoresist layer 130 may be formed by spin or spray coating, or doctor blading a layer of a photoresist composition on ARC 120, or on layer 110 if there is no ARC 120 or on substrate 105 if there is no ARC 120 or layer 110. The composition of photoresist layer 130, includes a one or more polymers (at least one not soluble in aqueous alkaline developer), a PAG, a DMA and an optional casting solvent.
In one example, the DMA comprises a material represented by at least one of one of the following (I, II, II, IV) structures:




wherein W and X are independently selected from the group consisting of an alkylene group having 1 to 12 carbon atoms, and a fluorinated alkylene group having 1 to 12 carbon atoms;
wherein each P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14 and P15 is independently selected from the group consisting of a structure V, a structure VI and a structure VII:




wherein each R1, R2, R3, R4, R5, R6 and R7 is independently selected from the group consisting of a hydrogen atom, a hydrocarbyl group having 4 to 12 carbon atoms, a substituted hydrocarbyl group having 4 to 12 carbon atoms, a heterohydrocarbyl group having 4 to 12 carbon atoms, and a substituted heterohydrocarbyl group having 4 to 12 carbon atoms; and

    
    
        wherein any two R1, R2, R3 or any two R4, R5, R6 may be linked to form a three to eight-membered cyclic group.
    
    


Structure I is a glucoside, structure II is a citrate, structure III is a cholate and structure IV is an adamantanedicarboxylate. The protecting group of structure V is an ethoxyethyl group, the protecting group of structure VI is a tetrahydrofuranyl group, and the protecting group of structure VII is an angelicalactone.
In a first example, the polymer comprises repeating units of one or more monomers represented by the following structures:

M1-R8  (VIIIi)

M2-R9  (VIIIii)

M3-R10  (VIIIiii)

where M1, M2 and M3 are independently selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
where R8 has a structure —R11—CR12R13—OH, in which:

    
    
        R11 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
        R12 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, a substituted alkyl group having 1 to 22 carbon atoms, and a fluorinated alkyl group having 1 to 24 carbon atoms;
        R13 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, and a fluorinated alkyl group having 1 to 24 carbon atoms; and
        wherein R12 and R13 may be linked to form a 3 to 8 carbon atom cyclic ring;
    
    


wherein R9 has a structure —R14—NH—SO2R15, in which:

    
    
        R14 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 2 to 12 carbon atoms; and
        R15 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, a fluorinated alkyl group having 1 to 24 carbon atoms, a substituted alkyl group having 1 to 24 carbon atoms, and a fluorinated alkyl group having 1 to 24 carbon atoms; and
    
    


wherein R10 has a structure —R16—COOH, in which:

    
    
        R16 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms.
    
    


In a second example, the polymer comprises repeating units of one or more monomers represented by the following structures:




wherein each R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46 and R47 (R18-R47) is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl substituent with a primary, secondary or tertiary carbon attachment point, said hydrocarbyl substituent selected from the group consisting of a linear alkyl or an alkoxy group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, an alkoxy group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a bicycloalkyl group having 3-17 carbon atoms, a cycloalkoxy having 3-17 carbon atoms, a bicycloalkoxy group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, an alkenyl group having 2-12 carbon atoms, a cycloalkenyl group having 2-12 carbon atoms, a dihydropyranyl group, a dihydrofuranyl group, an alkalkenyl group having 2-12 carbon atoms, an alkenylalkyl group having 2-12 carbon atoms, an alkynyl group having 2-12 carbon atoms, an alkalkynyl group having 2-12 carbon atoms, an alkynylalkyl group having 2-12 carbon atoms, a trifluoromethyl group, a trifluoroethyl group, a trifluoropropyl group, and a cyanopropyl group; and
wherein any two of R18—R20, R21—R30, R31—R39 and R40—R47 in the same molecule may be linked to form a 3 to 8 carbon atom cyclic ring.
In a third example, the polymer comprises repeating units of one or more monomers represented by the following structures:







In a fourth example, the polymer comprises repeating units of one or more monomers represented by the following structures:




In a fifth example, the polymer comprises repeating units of one or more monomers represented by the following structures:




In a sixth example, the polymer comprises repeating units of one or more monomers represented by the following structures:




wherein M is a polymerizable backbone moiety;
wherein each Ym at each occurrence is independently selected from the group consisting of —C(O)O—, —C(O)—, —OC(O)—, —O—C(O)— and —C(O)—O—;
wherein each Zn at each occurrence is independently selected from the group consisting of an alkylene group having 1 to 12 carbon atoms, a fluorinated alkylene group having 1 to 12 carbon atoms, a heteroalkylene group having 1 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
wherein (a) m and n are both 1, (b) m is 1 and n is 0 or (c) m is 0 and n is 1; and
wherein each occurrence of R48 is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a hydroxy substituted alkylene having 1 to 12 carbon atoms, a hydroxy substituted fluoroalkylene having 1 to 12 carbon atoms, a bis-trifluoromethylmethanol group, and an alkylsulfonamide group having 1 to 12 carbon atoms.
In a first example the PAG comprises a sulfonium salt.
In a second example, the PAG is selected from is selected from the group consisting of sulfonium salts, triphenylsulfonium perfluoromethanesulfonate(triphenylsulfonium triflate), triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluoropentanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium iodide, 2,4,6-trimethylphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium benzenesulfonate, tris(t-butylphenyl)sulfonium salts, diphenylethylsulfonium chloride, phenacyldimethylsulfonium chloride, halonium salts, diphenyliodonium perfluoromethanesulfonate(diphenyliodonium triflate), diphenyliodonium perfluorobutanesulfonate, diphenyliodonium perfluoropentanesulfonate, diphenyliodonium salts, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis-(t-butylphenyl)iodonium triflate, bis-(t-butylphenyl)-iodonium camphorsulfonate, α, α′-bis-sulfonyl-diazomethanes, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-(1,1dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, trifluoromethanesulfonate esters of imides and hydroxyimides, (trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (MDT), nitrobenzyl sulfonate esters, 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate; sulfonyloxynaphthalimides, N-camphorsulfonyloxynaphthalimide and N-pentafluorophenylsulfonyloxynaphthalimide; pyrogallol derivatives (e.g., trimesylate of pyrogallol), naphthoquinone-4-diazides, alkyl disulfones, s-triazine derivatives; sulfonic acid generators, N-hydroxynaphthalimide dodecane sulfonate (DDSN) and benzoin tosylate.
In one example the casting solvent is selected from the group consisting of cyclohexanone, ethyl lactate, propylene glycol methyl ether acetate, gamma-butyrolactone and combinations thereof.
In one example, the photoresist composition comprises about 8% by weight to about 15% by weight of polymer, about 1% by weight to about 3% by weight of PAG and about 10% by weight to about 15% by weight of DMA.
Preferably, before photoresist layer 130 is exposed to actinic radiation, the photoresist layer is heated to drive out casting solvent (pre-exposure baked or pre-baked) to a temperature of about 90° C. to about 110° C. for about 1 minute. In one example, photoresist layer 130 has a thickness of about 0.02 micron to about 5.0 microns, preferably about 0.05 micron to about 2.5 microns and most preferably about 0.10 micron to about 1.0 microns.
In FIG. 1B, photoresist layer 130 is exposed to actinic radiation 135 through an exemplary mask 140. Mask 140 includes a transparent substrate 145 and opaque islands 150. Other types of masks such as phase contrast masks may be used as well. Portions 135A of actinic radiation 135 pass through transparent region 145 and strike photoresist layer 130 while other portions of the actinic radiation are blocked by opaque islands 150. In regions of photoresist layer 130 struck by portions 135A of actinic radiation 135, the PAG in those regions generates an acid. Actinic radiation 135 may be ultraviolet, electron beam or x-ray. Ultraviolet radiation is preferred, particularly deep ultraviolet radiation having a wavelength of less than about 250 nm and preferably about 193 nm or less.
In FIG. 1C, upon heating photoresist layer 130 (see FIG. 1B) to a temperature of between about 26° C. and about 100° C., preferably below 80° C., more preferably below 50° C. and most preferably to just above room temperature (about 26° C.), the acid generated by the PAG causes cleavage of the acid-labile groups of the DMAs. This causes formation of latent images 155 in photoresist layer 130. However, the acid-labile groups of the DMAs in non-exposed regions of photoresist layer 130 are not activated since no acid was generated by the PAG.
In FIG. 1D, photoresist layer 130 (see FIG. 1C) is developed in an aqueous alkaline solution of a strong base such as tetramethylammonium hydroxide or choline to form photoresist islands 160. Any ARC 120 (see FIG. 1C) not protected by photoresist islands 160 is also removed forming ARC islands 165 exposing top surface 115 of layer 110.
In FIG. 1E, layer 110 is etched, in one example, using a reactive ion etch (RIE) process to form islands 170 of layer 110 (see FIG. 1D) and exposing top surface 100 of substrate 105 where the substrate is not covered by the islands.
In FIG. 1F, photoresist islands 160 and ARC islands 165 are removed.
The operation illustrated in FIG. 1G is optional. In FIG. 1G, trenches 175 are formed in substrate 105, in one example, using a RIE process, islands 170 acting as a “hard” etch mask.
Alternatively, if there is no layer 110 (see FIG. 1A), trenches 175 are formed in substrate 105, in one example, using a RIE process, photoresist islands 160 (see FIG. 1D) acting as a “soft” etch mask.
General DMA Synthesis
The protected DMA glucosides (I), citrates (II), cholates (III) and adamantanedicarboxylates (IV) where the protecting group is represented by an ethoxyethyl group (V) were prepared by treatment of the glucoside, cholate, citrate or adamantanedicarboxylate with the acetal-forming reagent ethyl vinyl ether in the presence of pyridinium p-toluenesulfonate in ether or tetrahydrofuran (THF) solvent.
The protected DMA glucosides (I), citrates (II), cholates (III) and adamantanedicarboxylates (IV) where the protecting group is represented by a tetrahydrofuranyl group (VI) were prepared by treatment of the glucoside, cholate, citrate or adamantanedicarboxylate with the acetal-forming reagent dihydrofuran in the presence of pyridinium p-toluenesulfonate in ether or THF solvent.
The products were purified by silica gel column chromatography and characterized by H-NMR and TLC
Preparation of Tetrahydrofuranyl 3,7,12-tris-(2-oxytetrahydrofuran)cholanoate (Cholic-THF)
To a 250-milliliter 3-necked round-bottomed flask, equipped with a 50-milliliter pressure-equalizing addition funnel, nitrogen inlet, thermowell with digital temperature readout and a magnetic stirbar, was added 10.0 gram (0.0245 moles) of cholic acid, 2.46 gram (0.0098 moles) of pyridinium p-toluenesulfonate and 80 milliliter of anhydrous THF. The addition funnel was charged with 14.8 milliliter (0.196 moles) of 2,3-dihydrofuran and 20 milliliter of anhydrous THF. The dihydrofuran solution was added over 45 minutes with no external cooling to the cholic acid suspension. A slight exotherm was observed. The resulting suspension was stirred overnight at room temperature by which time it had become a solution. The solution was diluted with 200 milliliter of diethylether and washed, in turn, with water, saturated sodium bicarbonate solution, water and brine. The resulting organic layer was stirred with anhydrous magnesium sulfate for 1 hour, filtered, and evaporated to a yellow oil. The oil was re-dissolved in 50 milliliter of ether and passed through a short column of sequential layers of silica gel, sodium carbonate, activated charcoal and Celite. The material was eluted with 300 milliliter of ether and the eluant evaporated on a rotary evaporator to yield 14.9 grams of the title compound as a clear colorless oil. TLC (75% ether/25% pentane) showed one spot (iodine) at Rf 0.65.
Preparation of 1,3-Adamantanediacetic acid substituted with α-angelicalactone:
1,3-Adamantanediacetic acid (5.05 gram, 0.02 mole), α-angelicalactone (7.85 gram, 0.08 mole), and 10 milliliter anhydrous THF were placed in a 100 milliliter round bottom flask equipped with a magnetic stirbar. To this mixture was added 100 milligram of p-toluenesulfonic acid monohydrate and the mixture was heated to mild reflux under nitrogen with stirring. After 17 hours, the solution was cooled to room temperature and quenched with 0.2 milliliter of concentrated ammonium hydroxide. This solution was added dropwise into a mixture of 400 milliliter of de-ionized water and 8 milliliter of concentrated ammonium hydroxide solution. The precipitated material was re-dissolved in 50 milliliter dichloromethane. This solution was washed with 50 milliliter saturated sodium bicarbonate solution followed by 50 milliliter of saturated sodium chloride solution and dried over anhydrous magnesium sulfate for 30 minutes. The solvent was removed on a rotary evaporator and the residue was dried under vacuum to give 3.50 grams of the title compound as a clear, colorless oil.
Control Positive Photoresist Formulation
A control positive CA photoresist was formulated containing 12% by weight of (3-(5-Bicyclo-[2,2,1]heptene-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanol) (NBHFA) homopolymer, 2% by weight Iodonium perfluorooctanesulfonate (I-PFOS) and 3% (MD-PFBUS) as the PAG, and 0.2% by weight tetrabutyl ammonium hydroxide (TBAH) in propylene glycol methyl ether acetate (PGMEA) solvent.
Experimental Positive Photoresist Formulation
An experimental positive CA photoresist was formulated containing 15% by weight of the DMA tetrahydrofuranyl 3,7,12-tris-(2-oxytetrahydrofuran)cholanoate (preparation described supra), 12% by weight of (3-(5-Bicyclo-[2,2,1]heptene-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanol) (NBHFA) homopolymer, 2% by weight Iodonium perfluorooctanesulfonate (I-PFOS) and 3% (MD-PFBUS) as the PAG, and 0.2% by weight tetrabutyl ammonium hydroxide (TBAH) in propylene glycol methyl ether acetate (PGMEA) solvent.
Experimental Positive Photoresist Evaluation
A silicon substrate was coated with 3000 Å of the experimental positive photoresist described supra. The coating was baked at between about 90° C.-110° C. for 1 minute to drive off the solvent. The coating was then exposed at 193 nm (at doses ranging from about 15 mJ/cm2 to about 100 mJ/cm2) and post exposure baked at temperatures ranging from about 26° C. to about 90° C. for 1 minute. In all cases the photoresist coating was developed with 0.263 N tetramethyl ammonium hydroxide. After development, 130 nm line/130 nm space photoresist patterns showing sharp contrast were obtained.
FIG. 2A is plot of photoresist thickness versus post exposure bake temperature for a control photoresist formulation. In FIG. 2A, the control photoresist (NBHFA) described supra was coated on a substrate and baked after exposure at the temperatures indicated. Curve 200 gives the photoresist thickness as a function of temperature before development and curve 205 gives the photoresist thickness as a function of temperature after development. Curve 205 is greater than zero because the style tool used to make the measurement could not register below about 100 Å. FIG. 2A shows that the exposed polymer of the control photoresist was soluble in aqueous developer over the entire post exposure bake temperature range.
FIG. 2B is plot of photoresist thickness versus post exposure bake temperature for an experimental photoresist formulation according to an embodiment of the present invention. In FIG. 2B, the experimental photoresist (NBHFA+Cholic-THF) described supra was coated on a substrate and baked after exposure at the temperatures indicated. Curve 210 gives the photoresist thickness as a function of temperature before development and curve 215 gives the photoresist thickness as a function of temperature after development. Curve 215 is greater than zero because the Alpha Step tool used to make the measurement could not register below about 100 Å. FIG. 2B indicates that the exposed polymer of the experimental photoresist was prevented from dissolving (average thinning rate over the temperature range 70° C. to 144° C. was less than about 0.6 Å/second) in aqueous developer by the added DMA until a temperature of about 144° C., which is the thermal breakdown temperature of the protecting groups of cholic-THF. The inhibition strength [dissolution rate without DMA(DRo)/dissolution rate with DMA (DRA)] was 63,333.
FIG. 3 is plot of photoresist thickness versus actinic radiation dose as a function of post exposure bake temperature for an experimental photoresist formulation according to an embodiment of the present invention. The curves of FIG. 3 are also known as dose response curves or contrast curves. In FIG. 3, a sample of the experimental photoresist (NBHFA+Chloic-THF) described supra, was coated on a silicon substrate, pre exposure baked at 90° C., exposed at 193 nm at the doses indicated, post exposure baked at 26° C. for curve 220, 50° C. for curve 225, 65° C. for curve 230 and 105° C. for curve 235 using a thermal gradient plate (TGP) and developed in 0.263 N tetramethyl ammonium hydroxide for 60 seconds. The curves of FIG. 3 show that the photoresist compositions using DMAs of the embodiments of the present invention are relatively high contrast photoresists and operate over a wide range of post exposure bake temperatures.
Thus, the embodiments of the present invention provide new photoresist compositions having improved image resolution capability, improved methods of patterning substrates and improved DMA materials.
The description of the embodiments of the present invention is given above for the understanding of the present invention. It will be understood that the invention is not limited to the particular embodiments described herein, but is capable of various modifications, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore it is intended that the following claims cover all such modifications and changes as fall within the true spirit and scope of the invention.

## Claims

1. A photoresist composition, comprising:
a polymer that is soluble in an aqueous alkaline developer;
a photoacid generator;
a dissolution modification agent characterized by the property of preventing dissolution of said polymer in said aqueous alkaline developer, said dissolution modification agent insoluble in said aqueous alkaline developer, said dissolution modification agent represented by at least one of the following structures:





wherein each P1, P2, P3, P4, P5, P6, P7, P8 and P15 is independently selected from the group consisting of a structure V, a structure VI and a structure VII:






wherein each R1, R2, R3, R4, R5, R6 and R7 is independently selected from the group consisting of a hydrogen atom, a hydrocarbyl group having 4 to 12 carbon atoms, a substituted hydrocarbyl group having 4 to 12 carbon atoms, a heterohydrocarbyl group having 4 to 12 carbon atoms, and a substituted heterohydrocarbyl group having 4 to 12 carbon atoms; and
wherein any two R1, R2, R3 or any two R4, R5, R6 may be linked to form a three to eight-membered cyclic group; and
wherein said photoresist composition acts as a chemically amplified positive photoresist when exposed to radiation at a wavelength of 193 nm or less.

2. The photoresist composition of claim 1, further including a casting solvent selected from the group consisting of cyclohexanone, ethyl lactate, propylene glycol methyl ether acetate, gamma-butyrolactone and combinations thereof.

3. The photoresist composition of claim 1, wherein said photoresist composition is not soluble in basic developer prior to exposure to ultraviolet radiation.

4. The photoresist composition of claim 1, wherein said photoacid generator generates a free acid upon exposure to ultraviolet radiation having a wavelength of less than about 250 nm.

5. The photoresist composition of claim 1, wherein, after exposure of said photoresist composition to ultraviolet radiation, said dissolution modifying agent becomes soluble in said aqueous alkaline developer.

6. The photoresist composition of claim 1, wherein, after exposure of said photoresist composition to ultraviolet radiation followed by heating to about 100° C. or less, said dissolution modifying agent becomes soluble in said aqueous alkaline developer.

7. The photoresist composition of claim 1, further including a casting solvent and wherein said photoresist composition comprises about 8% by weight to about 15% by weight of said polymer, about 1% by weight to about 3% by weight of said photoacid generator and about 10% by weight to about 20% by weight of said dissolution modifying agent.

8. The photoresist composition of claim 1, wherein said polymer comprises repeating units of one or more monomers represented by the following structures:


M1-R8  (VIIIi)



M2-R9  (VIIIii)



M3-R10  (VIIIiii)

where M1, M2 and M3 are independently selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
where R8 has a structure —R11—CR12R13—OH, in which:
R11 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
R12 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, a substituted alkyl group having 1 to 22 carbon atoms and a fluorinated alkyl group having 1 to 24 carbon atoms;
R13 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, and a fluorinated alkyl group having 1 to 24 carbon atoms; and
wherein R12 and R13 may be linked to form a 3 to 8 carbon atom cyclic ring;

wherein R9 has a structure —R14—NH—SO2R15, in which:
R14 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 2 to 12 carbon atoms; and
R15 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, a fluorinated alkyl group having 1 to 24 carbon atoms, a substituted alkyl group having 1 to 24 carbon atoms, and a fluorinated alkyl group having 1 to 24 carbon atoms; and

wherein R10 has a structure —R16—COOH, in which:
R16 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms.

9. The photoresist composition of claim 1, wherein said polymer comprises repeating units of one or more monomers represented by the following structures:



wherein each R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46 and R47 (R18—R47) is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl substituent with a primary, secondary or tertiary carbon attachment point, said hydrocarbyl substituent selected from the group consisting of a linear alkyl or an alkoxy group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, an alkoxy group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a bicycloalkyl group having 3-17 carbon atoms, a cycloalkoxy having 3-17 carbon atoms, a bicycloalkoxy group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, an alkenyl group having 2-12 carbon atoms, a cycloalkenyl group having 2-12 carbon atoms, a dihydropyranyl group, a dihydrofuranyl group, an alkalkenyl group having 2-12 carbon atoms, an alkenylalkyl group having 2-12 carbon atoms, an alkynyl group having 2-12 carbon atoms, an alkalkynyl group having 2-12 carbon atoms, an alkynylalkyl group having 2-12 carbon atoms, a trifluoromethyl group, a trifluoro ethyl group, a trifluoropropyl group, and a cyanopropyl group; and
wherein any two of R18—R20, R21—R30, R31—R39 and R40—R47 in the same molecule may be linked to form a 3 to 8 carbon atom cyclic ring.

10. The photoresist composition of claim 1, wherein said polymer comprises repeating units of one or more monomers represented by the following structures:

11. The photoresist composition of claim 1, wherein said polymer comprises repeating units of one or more monomers represented by the following structures:

12. The photoresist composition of claim 1, wherein said polymer comprises repeating units of one or more monomers represented by the following structures:

13. The photoresist composition of claim 1, wherein said polymer comprises repeating units of one or more monomers represented by the following structure:



wherein M is a polymerizable backbone moiety;
wherein each Ym at each occurrence is independently selected from the group consisting of —C(O)O—, —C(O)— and —OC(O)—;
wherein each Zn at each occurrence is independently selected from the group consisting of an alkylene group having 1 to 12 carbon atoms, a fluorinated alkylene group having 1 to 12 carbon atoms, a heteroalkylene group having 1 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
wherein (a) m and n are both 1, (b) m is 1 and n is 0 or (c) m is 0 and n is 1; and
wherein each occurrence of R48 is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a hydroxy substituted alkylene having 1 to 12 carbon atoms, a hydroxy substituted fluoroalkylene having 1 to 12 carbon atoms, a bis-trifluoromethylmethanol group, and an alkylsulfonamide group having 1 to 12 carbon atoms.

14. The photoresist composition of claim 1, wherein said photoacid generator is selected from the group consisting of sulfonium salts, triphenylsulfonium perfluoromethanesulfonate (triphenylsulfonium triflate), triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluoropentanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium iodide, 2,4,6-trimethylphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium benzenesulfonate, tris(t-butylphenyl)sulfonium salts, diphenylethylsulfonium chloride, phenacyldimethylsulfonium chloride, halonium salts, diphenyliodonium perfluoromethanesulfonate (diphenyliodonium triflate), diphenyliodonium perfluorobutanesulfonate, diphenyliodonium perfluoropentanesulfonate, diphenyliodonium salts, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis-(t-butylphenyl)iodonium triflate, bis-(t-butylphenyl)-iodonium camphorsulfonate, α, α′-bis-sulfonyl-diazomethanes, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-( 1,1dimethylethylsulfonyl) diazomethane, bis(cyclohexylsulfonyl)diazomethane, trifluoromethanesulfonate esters of imides and hydroxyimides, (trifluoromethylsulfonyloxy)-bicyclo [2.2.1]hept-5-ene-2,3-dicarboximide (MDT), nitrobenzyl sulfonate esters, 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate; sulfonyloxynaphthalimides, N-camphorsulfonyloxynaphthalimide and N-pentafluorophenylsulfonyloxynaphthalimide; pyrogallol derivatives (e.g., trimesylate of pyrogallol), naphthoquinone-4-diazides, alkyl disulfones, s-triazine derivatives; sulfonic acid generators, N-hydroxynaphthalimide dodecane sulfonate (DDSN) and benzoin tosylate.

15. A method of forming a pattern, comprising:
applying a photoresist layer of a photoresist composition over a substrate, said photoresist composition acting as a chemically amplified positive photoresist when exposed to actinic radiation at a wavelength of 193 nm or less, said photoresist composition, comprising:
a polymer that is soluble in an aqueous alkaline developer;
a photo acid generator; and
a dissolution modification agent characterized by the property of preventing dissolution of said polymer in said aqueous alkaline developer, said dissolution modification agent insoluble in said aqueous alkaline developer, said dissolution modification agent represented by one of the following structures:





wherein each P1, P2, P3, P4, P5, P6, P7, P8 and P15 is independently selected from the group consisting of a structure V, a structure VI and a structure VII:






wherein each R1, R2, R3, R4, R5, R6 and R7 is independently selected from the group consisting of a hydrogen atom, a hydrocarbyl group having 4 to 12 carbon atoms, a substituted hydrocarbyl group having 4 to 12 carbon atoms, a heterohydrocarbyl group having 4 to 12 carbon atoms, and a substituted heterohydrocarbyl group having 4 to 12 carbon atoms; and
wherein any two R1, R2, R3 or any two R4, R5, R6 may be linked to form a three to eight-membered cyclic group; and

selectively exposing a first region of said photoresist layer to said actinic radiation at said wavelength of 193 nm or less while not exposing a second region of said photoresist layer to said actinic radiation at said wavelength of 193 nm or less to form an exposed photoresist layer;
after said selectively exposing, heating said photoresist layer to a temperature above 26° C. but no greater than about 100° C., said heating of said photoresist layer causing said dissolution modification agent in said first region to become soluble in said aqueous alkaline developer; and
removing said first region of said photoresist layer in said aqueous alkaline developer.

16. The method of claim 15, wherein said heating of said exposed photoresist layer is at a temperature of about 100° C. or less before said removing said first region of said photoresist layer in said aqueous alkaline developer.

17. The method of claim 15, wherein said actinic radiation has a wavelength of about 250 nm or less.

18. The method of claim 15, wherein said photoresist resist layer has a thickness of between about 0.02 μm and about 5.0 μm.

19. The method of claim 15, wherein said substrate is selected from the group consisting of a metal substrate, a ceramic substrate, an organic substrate, a bulk silicon substrate, a silicon-on-insulator substrate and other semiconductor substrates.

20. The method of claim 15, wherein a conductive, semi-conductive or insulating layer is formed on a top surface of said substrate, and wherein said photoresist layer is formed on a top surface of said conductive, semi-conductive or insulating layer.

21. The method of claim 15, further including forming an anti-reflective coating over said substrate prior to said applying said photoresist layer over said substrate.

22. The method of claim 15, wherein said photoresist composition includes a casting solvent selected from the group consisting of cyclohexanone, ethyl lactate, propylene glycol methyl ether acetate, gamma-butyrolactone and combinations thereof.

23. The method of claim 15, wherein said photoresist composition includes a casting solvent, and wherein said photoresist composition comprises about 8% by weight to about 15% by weight of said polymer, about 1% by weight to about 3% by weight of said photoacid generator and about 10% by weight to about 15% by weight of said dissolution modifying agent.

24. The method of claim 15, wherein the method further comprises forming said polymer by polymerization of one or more monomers represented by the following structures:


M1-R8  (VIIIi)



M2-R9  (VIIIii)



M3-R10  (VIIIiii)

where M1, M2 and M3 are independently selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
where R8 has a structure —R11—CR12R13—OH, in which:
R11 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
R12 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, a substituted alkyl group having 1 to 22 carbon atoms and a fluorinated alkyl group having 1 to 24 carbon atoms;
R13 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, and a fluorinated alkyl group having 1 to 24 carbon atoms; and
wherein R12 and R13 may be linked to form a 3 to 8 carbon atom cyclic ring;

wherein R9 has a structure —R14—NH—SO2R15, in which:
R14 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 2 to 12 carbon atoms; and
R15 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, a fluorinated alkyl group having 1 to 24 carbon atoms, a substituted alkyl group having 1 to 24 carbon atoms, and a fluorinated alkyl group having 1 to 24 carbon atoms; and

wherein R10 has a structure —R16—COOH, in which:
R16 is selected from the group consisting of an alkylene group having 2 to 12 carbon atoms, a substituted alkylene group having 2 to 12 carbon atoms, a heteroalkylene group having 2 to 12 carbon atoms, a substituted heteroalkylene group having 2 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms.

25. The method of claim 15, wherein the method further comprises forming said polymer by polymerization of one or more monomers represented by the following structures:



wherein each R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46 and R47 (R18—R47) is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl substituent with a primary, secondary or tertiary carbon attachment point, said hydrocarbyl substituent selected from the group consisting of a linear alkyl or an alkoxy group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, an alkoxy group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a bicycloalkyl group having 3-17 carbon atoms, a cycloalkoxy having 3-17 carbon atoms, a bicycloalkoxy group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, an alkenyl group having 2-12 carbon atoms, a cycloalkenyl group having 2-12 carbon atoms, a dihydropyranyl group, a dihydrofuranyl group, an alkalkenyl group having 2-12 carbon atoms, an alkenylalkyl group having 2-12 carbon atoms, an alkynyl group having 2-12 carbon atoms, an alkalkynyl group having 2-12 carbon atoms, an alkynylalkyl group having 2-12 carbon atoms, a trifluoromethyl group, a trifluoro ethyl group, a trifluoropropyl group, and a cyanopropyl group; and
wherein any two of R18—R20, R21—R30, R31—R39 and R40—R47 in the same molecule may be linked to form a 3 to 8 carbon atom cyclic ring.

26. The method of claim 15, wherein the method further comprises forming said polymer by polymerization of one or more monomers represented by the following structures:

27. The method of claim 15, wherein the method further comprises forming said polymer by polymerization of one or more monomers represented by the following structures:

28. The method of claim 15, wherein the method further comprises forming said polymer by polymerization of one or more monomers represented by the following structures:

29. The method of claim 15, wherein the method further comprises forming said polymer by polymerization of one or more monomers represented by the following structures:



wherein M is a polymerizable backbone moiety;
wherein each Ym at each occurrence is independently selected from the group consisting of —C(O)O—, —C(O)— and —OC(O)—;
wherein each Zn at each occurrence is independently selected from the group consisting of an alkylene group having 1 to 12 carbon atoms, a fluorinated alkylene group having 1 to 12 carbon atoms, a heteroalkylene group having 1 to 12 carbon atoms, an alicyclic group having 3 to 15 carbon atoms, and a fluoroalicyclic group having 3 to 15 carbon atoms;
wherein (a) m and n are both 1, (b) m is 1 and n is 0 or (c) m is 0 and n is 1; and

wherein each occurrence of R48 is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a hydroxy substituted alkylene having 1 to 12 carbon atoms, a hydroxy substituted fluoroalkylene having 1 to 12 carbon atoms, a bis-trifluoromethylmethanol group, and an alkylsulfonamide group having 1 to 12 carbon atoms.

30. The method of claim 15, wherein said photoacid generator is selected from the group consisting of sulfonium salts, triphenylsulfonium perfluoromethanesulfonate (triphenylsulfonium triflate), triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluoropentanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium iodide, 2,4,6-trimethylphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium benzenesulfonate, tris(t-butylphenyl)sulfonium salts, diphenylethylsulfonium chloride, phenacyldimethylsulfonium chloride, halonium salts, diphenyliodonium perfluoromethanesulfonate (diphenyliodonium triflate), diphenyliodonium perfluorobutanesulfonate, diphenyliodonium perfluoropentanesulfonate, diphenyliodonium salts, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis-(t-butylphenyl)iodonium triflate, bis-(t-butylphenyl)-iodonium camphorsulfonate, α, α-bis-sulfonyl-diazomethanes, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-(1,1dimethylethylsulfonyl) diazomethane, bis(cyclohexylsulfonyl)diazomethane, trifluoromethanesulfonate esters of imides and hydroxyimides, (trifluoromethylsulfonyloxy)-bicyclo [2.2.1]hept-5-ene-2,3-dicarboximide (MDT), nitrobenzyl sulfonate esters, 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate; sulfonyloxynaphthalimides, N-camphorsulfonyloxynaphthalimide and N-pentafluorophenylsulfonyloxynaphthalimide; pyrogallol derivatives (e.g., trimesylate of pyrogallol), naphthoquinone-4-diazides, alkyl disulfones, s-triazine derivatives; sulfonic acid generators, N-hydroxynaphthalimide dodecane sulfonate (DDSN) and benzoin tosylate.

31. A method of forming a pattern, comprising:
applying a photoresist layer of a photoresist composition over a substrate, said photoresist composition acting as a chemically amplified positive photoresist when exposed to actinic radiation at a wavelength of 193 nm or less, said photoresist composition, comprising:
a polymer that is soluble in an aqueous alkaline developer;
a photoacid generator; and
a hydrophobic dissolution modification agent characterized by the property of preventing dissolution of said polymer in said aqueous alkaline developer, said dissolution modification agent represented by one of the following structures:





wherein each P1, P2, P3, P4, P5, P6, P7, P8 and P15 is independently selected from the group consisting of a structure V, a structure VI and a structure VII:






wherein each R1, R2, R3, R4, R5, R6 and R7 is independently selected from the group consisting of a hydrogen atom, a hydrocarbyl group having 4 to 12 carbon atoms, a substituted hydrocarbyl group having 4 to 12 carbon atoms, a heterohydrocarbyl group having 4 to 12 carbon atoms, and a substituted heterohydrocarbyl group having 4 to 12 carbon atoms; and
wherein any two R1, R2, R3 or any two R4, R5, R6 may be linked to form a three to eight-membered cyclic group; and

selectively exposing a first region of said photoresist layer to said actinic radiation at said wavelength of 193 nm or less while not exposing a second region of said photoresist layer to said actinic radiation at said wavelength of 193 nm or less to form an exposed photoresist layer;
after said selectively exposing, heating said photoresist layer to a temperature above 26° C. but no greater than about 100° C., said heating of said photoresist layer causing said dissolution modification agent in said first region to become hydrophilic; and
removing said first region of said photoresist layer in said aqueous alkaline developer.