Negative photoresist compositions and processes for preparing thermally stable, negative images using them

Claim 2

A negative photoresist composition, which comprises:- a) acid-hardening resin system; and b) halogenated, organic, photoacid generating compound which: (i) selectively absorbs actinic radiation having a wavelength in the range of about 299 nanometers or less; (ii) is compatible with the acid-hardening resin system; (iii) is developable in an aqueous base solution; (iv) is capable, upon exposure to actinic radiation having a wavelength in the range of about 299 nanometers or less, of generating halogen acid for crosslinking the acid-hardening resin system at elevated temperature to form a thermally stable negative image.

Claim 3

A composition as claimed in claim 1, in which component (b). selectively absorbs actinic radiation having a wavelength in the range of about 210 to about 299 nanometers, and is capable, upon exposure to such actinic radiation, of generating halogen acid for crosslinking the acid-hardening resin system at elevated temperature to form a thermally stable negative images.

Claim 4

A composition as claimed in claim 2 in which component (b) is present in the composition at a concentration of from about 0.1 to 10, preferably from about 0.1 to 5, weight percent when the exposing radiation dosage is at least 10 mJ/cm 2

Claim 5

A composition as claimed in claim 2 or claim 3, in which component (b) comprises halogenated organic compound selected from: 1,1-bis [p-chlorophenyl]-2,2,2-trichloroethane; 1,1-bis [p-methoxyphenyl]-2,2,2-trichloroethane; 1,2,5,6,9,10-hexabromocyclododecane; 1,10-dibromodecane; 1,1-bis[p-chlorophenyl]-2,2-dichtoroethane; 4,4'-dichloro-2-(trichloromethyl) benzhydrol or 1,1-bis(p-chlorophenyl)2,2,2-trichloroethanol; hexachlorodimethyl sulfone; 2-chloro-6-(trichloromethyl) pyridine; 0,0-diethyl-0-(3,5,6-trichloro-2-pyridyl) phosphorothioate; 1,2,3,4,5,6-hexachlorocyclohexane; N(1,1-bis [p-chlorophenyl]-2,2,2-trichloroethyl) acetamide, tris [2,3-dibromopropyl] isocyanurate; 1,1-bis [p-chlorophenyl]-2,2-dichloroethylene; and their isomers, analogs, homologs, and residual compounds.

Claim 6

A composition as claimed in claim 1, in which component (b) selectively absorbs actinic radiation in the x-ray region, and is capable, upon exposure to x-rays, of generating halogen acid for crosslinking the acid-hardening resin system at elevated temperature to form a thermally stable, negative image.

Claim 7

A composition as claimed in claim 5, which comprises at least 10 weight percent of component (b), component (b) being selected from: 1,1-bis[p-chlorophenyl]-2,2,2-trichloroethane; 4,4'-dichloro-2-(trichloromethyl)benzhydrol; 0,0-diethyl-0-(3,5,6,-trichloro-2-pyridyl)phosphorothioate; 1,2,3,4,5,6-hexachlorocyclohexane (B-isomer); N(1,1-bis[p-chlorophenyl]-2,2,2,-trichloroethyl)-acetamide; tris(2,3,-dibromopropyl]isocyanurate; and

Claim 8

tris[2,3-dichloropropyl]phosphate.

Claim 9

tris[2,3-dichloropropyl]phosphate.

Claim 10

A process for preparing a negative, thermally stable image on a substrate surface, which comprises:- (a) depositing a photosensitive solution on a substrate surface, the photosensitive solution comprising: (i) acid-hardening resin system; and (ii) halogenated, organic, photoacid generating compound which selectively absorbs actinic radiation having a wavelength in the range of about 299 nanometers or less, is compatible with the acid-hardening resin system, and is developable in aqueous base solution. (b) heating the deposited photosensitive solution to form a coating; (c) exposing at least one portion of the coating to a source of actinic radiation having a wavelength in the range of about 299 nanometers or less; (d) developing unexposed portion(s) of the coating with an aqueous base developer; and (e) heating the exposed portion(s) of the coating to an elevated temperature to form a negative image that is thermally stable to temperatures in excess of 200°C.

Claim 11

A process for preparing a negative, thermally stable image on a substrate surface, which comprises:- (a) depositing a photosensitive solution on a substrate surface, the photosensitive solution comprising: (i) acid-hardening resin system; and (ii) halogenated, organic, photoacid generating compound which selectively absorbs actinic radiation having a wavelength in the range of about 299 nanometers or less, is compatible with the acid-hardening resin system, and is developable in aqueous base solution. (b) heating the deposited photosensitive solution to form a coating; (c) exposing at least one portion of the coating to a source of actinic radiation having a wavelength in the range of about 299 nanometers or less; (d) developing unexposed portion(s) of the coating with an aqueous base developer; and (e) heating the exposed portion(s) of the coating to an elevated temperature to form a negative image that is thermally stable to temperatures in excess of 200°C.

Claim 12

A process as claimed in claim 7, in which the source of actinic radiation has a wavelength in the range of about 210 to about 299 nanometers.

Claim 13

A process as claimed in claim 8, in which the photoacid generating compound is selected from:- 1,1-bis [p-chlorophenyl]-2,2,2-trichloroethane; 1,1-bis [p-methoxyphenyl]-2,2,2-trichloroethane; 12,5,6,9,10-hexabromocyclododecane; 1,10-dibromodecane; 1,1-bis[p-chlorophenyll-2,2-dichloroethane; 4,4'-dichloro-2-(trichloromethyl) benzhydrol or 1,1-bis(p-chlorophenyl)2,2,2-trichloroethanol; hexachlorodimethyl sulfone; 2-chloro-6-(trichloromethyl) pyridine; O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl) phosphorothioate; 1,2,3,4,5,6-hexachlorocyclohexane; N(1,1-bis [p-chlorophenyl]-2,2,2-trichloroethyl) acetamide, tris [2,3-dibromopropyl] isocyanurate; 1,1-bis [p-chlorophenyl]-2,2-dichloroethylene; and their isomers, analogs, homologs, and residual compounds.

Claim 14

A process as claimed in claim 7, in which the source of actinic radiation is a source of x-radiation and the photosensitive solution contains at least 10 weight percent of the photoacid generating compound.

Claim 15

A process as claimed in claim 10, in which the photoacid generating compound is selected from:- 1,1-bis[p-chlorophenyl]-2,2,2-trichloroethane; 4,4'-dichloro-2-(trichloromethyI)benzhydrol; O,O-diethyl-O-(3,5,6,-trichloro-2-pyridyl)phosphorothioate; 1,2,3,4,5,6-hexachlorocyclohexane (B-isomer); N(1,1-bis[p-chlorophenyl]-2,2,2,-trichloroethyl)acetamide; tris[2,3,-dibromopropyl]isocyanurate; and tris[2,3-dichloropropyl]phosphate.

Claim 16

A process as claimed in claim 10 or claim 11, in which the image produced has a resolution of from about 0.2 to 1 micrometer.

Claim 17

A process as claimed in any of claims 7 to 12, in which in step (b) the deposited photosensitive solution is heated at about 90°C for about 30 minutes.