Low blur molecular resist
View Patent ↗A molecular resist composition and method of use is disclosed wherein the composition includes no silicon containing material, no polymeric material, and a substituted oligosaccharide, wherein the substituted oligosaccharide is substituted with at least one acid-cleavable —OR group, wherein the substituted oligosaccharide has 2 to 10 monosaccharides, wherein the molecular resist may be initially insoluble in developer, which may be an aqueous alkaline solution or developer consisting essentially of water. In some embodiments, the molecular resist may become soluble in the developer consisting essentially of water upon exposure to radiation having a wavelength of 193 nm or less and a post-exposure bake temperature from about room temperature to about 110° C. The resist material of the present invention may be used to print feature sizes wherein developed images may have a line/spacing not greater than than 120 nm when the developer consists essentially of water or an aqueous alkaline solution.
1. A resist composition comprising:
a substituted oligosaccharide, wherein the substituted oligosaceharide is substituted with at least one acid-cleavable —OR group and the substituted oligosaccharide has 2 to 10 monosaccharides, wherein:
each monosaccharide in the substituted oligosaccharide has at least three carbon atoms;
the monosaccharides are joined by glycosidic linkages; and
at least one remaining hydroxyl group from a monosaccharide of said substituted oligosaccharide has been replaced by a protective group having the acid-cleavable —OR group, wherein said acid-cleavable —OR group is selected from the following structures:
wherein R 1 -R 14 , R 16 -R 17 , and R 19 -R 35 are each independently selected from the group consisting of hydrogen, a linear alkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, a cycloalkyl 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, and a fluorinated cycloalkyl group having 3-17 carbon atoms,
wherein R 15 , R 18 , and R 36 are each independently selected from the group consisting of a linear alkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, a cycloalkyl 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, and a fluorinated cycloalkyl group having 3-17 carbon atoms, and
wherein any two of R 1 -R 36 that are in the same molecule may be linked to form a three- to eight-membered cyclic group.
2. The resist composition of claim 1 , wherein said acid-cleavable -OR group is
3. A method of patterning a substrate, comprising:
forming a resist layer over and in contact with a material layer of the substrate, said resist layer comprising a positive photoresist composition that includes the resist composition of claim 2 and a radiation sensitive acid generator;
selectively exposing a first portion of the resist layer to imaging radiation such that a remaining portion of the resist layer is not exposed to the imaging radiation, resulting in the acid generator facilitating removal of the acid-cleavable -OR group to generate a reaction product in the first portion of the resist layer;
developing away the first portion of the resist layer by contacting the resist layer with a developer solution in which the remaining portion of the resist layer is insoluble, resulting in formation of a pattern of voids in the resist layer;
forming a pattern of voids in the material layer by etching into the material layer through the pattern of voids in the resist layer; and
after said forming the pattern of voids in the material layer, removing the resist layer.
4. The resist compositioin of claim 1 , wherein said acid-cleavable -OR group is
5. A method of patterning a substrate, comprising:
forming a resist layer over and in contact with a material layer of the substrate, said resist layer comprising a positive photoresist composition that includes the resist composition of claim 4 and a radiation sensitive acid generator;
selectively exposing a first portion of the resist layer to imaging radiation such that a remaining portion of the resist layer is not exposed to the imaging radiation, resulting in the acid generator facilitating removal of the acid-cleavable -OR group to generate a reaction product in the first portion of the resist layer;
developing away the first portion of the resist layer by contacting the resist layer with a developer solution in which the remaining portion of the resist layer is insoluble, resulting in formation of a pattern of voids in the resist layer;
forming a pattern of voids in the material layer by etching into the material layer through the pattern of voids in the resist layer; and
after said forming the pattern of voids in the material layer, removing the resist layer.
6. The resist composition of claim 1 , wherein said acid-cleavable -OR group is
7. A method of patterning a substrate, comprising:
forming a resist layer over and in contact with a material layer of the substrate, said resist layer comprising a positive photoresist composition that includes the resist composition of claim 6 and a radiation sensitive acid generator;
selectively exposing a first portion of the resist layer to imaging radiation such that a remaining portion of the resist layer is not exposed to the imaging radiation, resulting in the acid generator facilitating removal of the acid-cleavable -OR group to generate a reaction product in the first portion of the resist layer;
developing away the first portion of the resist layer by contacting the resist layer with a developer solution in which the remaining portion of the resist layer is insoluble, resulting in formation of a pattern of voids in the resist layer;
forming a pattern of voids in the material layer by etching into the material layer through the pattern of voids in the resist layer; and
after said forming the pattern of voids in the material layer, removing the resist layer.
8. The resist composition of claim 1 , wherein said acid-cleavable -OR group is
9. A method of patterning a substrate, comprising:
forming a resist layer over and in contact with a material layer of the substrate, said resist layer comprising a positive photoresist composition that includes the resist composition of claim 8 and a radiation sensitive acid generator;
selectively exposing a first portion of the resist layer to imaging radiation such that a remaining portion of the resist layer is not exposed to the imaging radiation, resulting in the acid generator facilitating removal of the acid-cleavable -OR group to generate a reaction product in the first portion of the resist layer;
developing away the first portion of the resist layer by contacting the resist layer with a developer solution in which the remaining portion of the resist layer is insoluble, resulting in formation of a pattern of voids in the resist layer;
forming a pattern of voids in the material layer by etching into the material layer through the pattern of voids in the resist layer; and
after said forming the pattern of voids in the material layer, removing the resist layer.
10. The resist composition of claim 1 , wherein said acid-cleavable -OR group is
11. A method of patterning a substrate, comprising:
forming a resist layer over and in contact with a material layer of the substrate, said resist layer comprising a positive photoresist composition that includes the resist composition of claim 10 and a radiation sensitive acid generator;
selectively exposing a first portion of the resist layer to imaging radiation such that a remaining portion of the resist layer is not exposed to the imaging radiation, resulting in the acid generator facilitating removal of the acid-cleavable -OR group to generate a reaction product in the first portion of the resist layer;
developing away the first portion of the resist layer by contacting the resist layer with a developer solution in which the remaining portion of the resist layer is insoluble, resulting in formation of a pattern of voids in the resist layer;
forming a pattern of voids in the material layer by etching into the material layer through the pattern of voids in the resist layer; and
after said forming the pattern of voids in the material layer, removing the resist layer.
12. The resist composition of claim 1 , wherein said acid-cleavable -OR group is
13. A method of patterning a substrate, comprising:
forming a resist layer over and in contact with a material layer of the substrate, said resist layer comprising a positive photoresist composition that includes the resist composition of claim 12 and a radiation sensitive acid generator;
selectively exposing a first portion of the resist layer to imaging radiation such that a remaining portion of the resist layer is not exposed to the imaging radiation, resulting in the acid generator facilitating removal of the acid-cleavable -OR group to generate a reaction product in the first portion of the resist layer;
developing away the first portion of the resist layer by contacting the resist layer with a developer solution in which the remaining portion of the resist layer is insoluble, resulting in formation of a pattern of voids in the resist layer;
forming a pattern of voids in the material layer by etching into the material layer through the pattern of voids in the resist layer; and
after said forming the pattern of voids in the material layer, removing the resist layer.
14. A method of patterning a substrate, comprising:
forming a resist layer over and in contact with a material layer of the substrate, said resist layer comprising a positive photoresist composition that includes the resist composition of claim 1 and a radiation sensitive acid generator;
selectively exposing a first portion of the resist layer to imaging radiation such that a remaining portion of the resist layer is not exposed to the imaging radiation, resulting in the acid generator facilitating removal of the acid-cleavable -OR group to generate a reaction product in the first portion of the resist layer;
developing away the first portion of the resist layer by contacting the resist layer with a developer solution in which the remaining portion of the resist layer is insoluble, resulting in formation of a pattern of voids in the resist layer;
forming a pattern of voids in the material layer by etching into the material layer through the pattern of voids in the resist layer; and
after said forming the pattern of voids in the material layer, removing the resist layer.
15. A resist composition comprising:
a substituted oligosaccharide, wherein the substituted oligosaccharide is substituted with at least one acid-cleavable —OR group and the substituted oligosaccharide has 2 to 10 monosaccharides, wherein:
each monosaccharide in the substituted oligosaccharide has at least three carbon atoms;
the monosaccharides are joined by glycosidic linkages; and
at least one remaining hydroxyl group from a monosaccharide of said substituted oligosaccharide has been replaced by a protective group having the acid-cleavable —OR group selected from the group consisting of ester, —OXC(O)OR 37 , ether, —OR 38 , carbonate, —OC(O)OR 39 , cyclic acetal, —O—C(OR 40 )R 41 H, ketal, —O—C(OR 42 )R 43 R 44 , orthoester, —OC(OR 45 )(OR 46 )R 47 , and combinations thereof, wherein X is a linking group consisting of branched alkylene having 2 to 7 carbon atoms, cycloalkylene having 3 to 17 carbon atoms, alkylcycloalkylene having 4 to 20 carbon atoms, a cycloalkylalkylene having 4 to 20 carbon atoms, and combinations thereof, wherein each R 37 -R 39 is selected from the group consisting of hydrocarbyl substituents with a tertiary carbon attachment point, wherein R 39 is not a t-butyl group, and wherein each of R 40 -R 47 , is independently selected from the group of hydrocarbyl substituents with a primary, secondary or tertiary carbon attachment point consisting of a linear alkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, a cycloalkyl 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, and a fluorinated cycloalkyl group having 3-17 carbon atoms, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, bicycloalkyl groups, alkenyl groups, alkalkenyl groups, and alkenylalkyl groups, alkynyl groups, alkalkynyl groups, alkynylalkyl groups, trifluoropropyl groups, cyanopropyl groups, acryloyl groups, arylacryloyl groups, acryloylaryl groups, alkylacyl groups, arylacyl groups alkylenylacyl groups and alkynylacyl groups, wherein R 47 may be a hydrogen atom, and wherein any two of R 40 -R 47 in the same molecule may be linked to form a three- to eight-membered cyclic group, wherein the monosaccharides are each selected from the group consisting of pentoses, hexoses and combinations thereof.
16. A method of patterning a substrate, comprising:
forming a resist layer over and in contact with a material layer of the substrate, said resist layer comprising a positive photoresist composition that includes the resist composition of claim 15 and a radiation sensitive acid generator;
selectively exposing a first portion of the resist layer to imaging radiation such that a remaining portion of the resist layer is not exposed to the imaging radiation, resulting in the acid generator facilitating removal of the acid-cleavable -OR group to generate a reaction product in the first portion of the resist layer;
developing away the first portion of the resist layer by contacting the resist layer with a developer solution in which the remaining portion of the resist layer is insoluble, resulting in formation of a pattern of voids in the resist layer;
forming a pattern of voids in the material layer by etching into the material layer through the pattern of voids in the resist layer; and
after said forming the pattern of voids in the material layer, removing the resist layer.
17. A resist composition comprising:
a substituted oligosaccharide, wherein the substituted oligosaccharide is substituted with at least one acid-cleavable —OR group and the substituted oligosaccharide has 2 to 10 monosaccharides, wherein:
each monosaccharide in the substituted oligosaccharide has at least three carbon atoms;
the monosaccharides are joined by glycosidic linkages; and
at least one remaining hydroxyl group from a monosaccharide of said substituted oligosaccharide has been replaced by a protective group having the acid-cleavable —OR group selected from the group consisting of —OXC(O)OR 37 , ether, carbonate, —OC(O)OR 39 , cyclic acetal, —O—C(OR 40 )R 41 H, ketal, —O—C(OR 42 )R 43 R 44 , orthoester, —OC(OR 45 )(OR 46 )R 47 , and combinations thereof, wherein X is a linking group consisting of branched alkylene having 2 to 7 carbon atoms, cycloalkylene having 3 to 17 carbon atoms, alkylcycloalkylene having 4 to 20 carbon atoms, a cycloalkylalkylene having 4 to 20 carbon atoms, and combinations thereof, wherein R 37 and R 39 are selected from the group consisting of hydrocarbyl sub stituents with a tertiary carbon attachment point, wherein R 39 is not a t-butyl group, and wherein each of R 40 -R 47 is independently selected from the group of hydrocarbyl substituents with a primary, secondary or tertiary carbon attachment point consisting of a linear alkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, a cycloalkyl 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, and a fluorinated cycloalkyl group having 3-17 carbon atoms, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, bicycloalkyl groups, alkenyl groups, alkalkenyl groups, and alkenylalkyl groups, alkynyl groups, alkalkynyl groups, alkynylalkyl groups, trifluoropropyl groups, cyanopropyl groups, acryloyl groups, arylacryloyl groups, acryloylaryl groups, alkylacyl groups, arylacyl groups alkylenylacyl groups and alkynylacyl groups, and furthermore wherein R 47 may be a hydrogen atom, wherein any two of R 40 -R 47 in the same molecule may be linked to form a three- to eight-membered cyclic group, and wherein the substituted oligosaccharide is represented by the following cyclic formula, and wherein n is a positive integer from 2 to 9:
18. The resist composition of claim 17 , wherein n is a positive integer from 5 to 7.
19. A method of patterning a substrate, comprising:
forming a resist layer over and in contact with a material layer of the substrate, said resist layer comprising a positive photoresist composition that includes the resist composition of claim 17 and a radiation sensitive acid generator;
selectively exposing a first portion of the resist layer to imaging radiation such that a remaining portion of the resist layer is not exposed to the imaging radiation, resulting in the acid generator facilitating removal of the acid-cleavable -OR group to generate a reaction product in the first portion of the resist layer;
developing away the first portion of the resist layer by contacting the resist layer with a developer solution in which the remaining portion of the resist layer is insoluble, resulting in formation of a pattern of voids in the resist layer;
forming a pattern of voids in the material layer by etching into the material layer through the pattern of voids in the resist layer; and
after said forming the pattern of voids in the material layer, removing the resist layer.
20. A resist composition comprising:
a substituted oligosaccharide, wherein the substituted oligosaccharide is substituted with at least one acid-cleavable —OR group and the substituted oligosaccharide has 2 to 10 monosaccharides, wherein:
each monosaccharide in the substituted oligosaccharide has at least three carbon atoms;
the monosaccharides are joined by glycosidic linkages; and
at least one remaining hydroxyl group from a monosaccharide of said substituted oligosaccharide has been replaced by a protective group having the acid-cleavable —OR group, wherein said at least one acid-cleavable —OR group includes at least one of the following structures:
21. The resist composition of claim 20 , wherein said at least one acid-cleavable -OR group includes
22. A method of patterning a substrate, comprising:
forming a resist layer over and in contact with a material layer of the substrate, said resist layer comprising a positive photoresist composition that includes the resist composition of claim 21 and a radiation sensitive acid generator;
selectively exposing a first portion of the resist layer to imaging radiation such that a remaining portion of the resist layer is not exposed to the imaging radiation, resulting in the acid generator facilitating removal of the acid-cleavable -OR group to generate a reaction product in the first portion of the resist layer;
developing away the first portion of the resist layer by contacting the resist layer with a developer solution in which the remaining portion of the resist layer is insoluble, resulting in formation of a pattern of voids in the resist layer;
forming a pattern of voids in the material layer by etching into the material layer through the pattern of voids in the resist layer; and
after said forming the pattern of voids in the material layer, removing the resist layer.
23. The resist composition of claim 20 , wherein said at least one acid-cleavable -OR group includes
24. A method of patterning a substrate, comprising:
forming a resist layer over and in contact with a material layer of the substrate, said resist layer comprising a positive photoresist composition that includes the resist composition of claim 23 and a radiation sensitive acid generator;
selectively exposing a first portion of the resist layer to imaging radiation such that a remaining portion of the resist layer is not exposed to the imaging radiation, resulting in the acid generator facilitating removal of the acid-cleavable -OR group to generate a reaction product in the first portion of the resist layer;
developing away the first portion of the resist layer by contacting the resist layer with a developer solution in which the remaining portion of the resist layer is insoluble, resulting in formation of a pattern of voids in the resist layer;
forming a pattern of voids in the material layer by etching into the material layer through the pattern of voids in the resist layer; and
after said forming the pattern of voids in the material layer, removing the resist layer.
25. A method of patterning a substrate, comprising:
forming a resist layer over and in contact with a material layer of the substrate, said resist layer comprising a positive photoresist composition that includes the resist composition of claim 20 and a radiation sensitive acid generator;
selectively exposing a first portion of the resist layer to imaging radiation such that a remaining portion of the resist layer is not exposed to the imaging radiation, resulting in the acid generator facilitating removal of the acid-cleavable -OR group to generate a reaction product in the first portion of the resist layer;
developing away the first portion of the resist layer by contacting the resist layer with a developer solution in which the remaining portion of the resist layer is insoluble, resulting in formation of a pattern of voids in the resist layer;
forming a pattern of voids in the material layer by etching into the material layer through the pattern of voids in the resist layer; and
after said forming the pattern of voids in the material layer, removing the resist layer.