1. A chemical amplification resist composition for forming resist patterns which comprises a combination of an alkali-soluble base resin, a photoacid generator and a dissolution inhibitor, in which said dissolution inhibitor is a compound of the following formula (I):
23
wherein
A represents atoms necessary to complete a cyclic or acyclic structure constituting a matrix portion of the molecule of said dissolution inhibitor,
SIG may be the same or different and each represents a dissolution inhibiting group capable of being released from said cyclic or acyclic structure A, to which said dissolution inhibiting group is directly or indirectly bonded, upon the action of an acid which is released from said photoacid generator, and
m represents the number of said dissolution inhibiting groups SIG bonded to said structure A and is an integer of 1 or more, and
said structure a of said compound of the dissolution inhibitor contains at least one lone pair-containing portion which can provide a hydrogen bond sufficient to shift and gather an alkali-soluble moiety of said base resin towards a side of said molecule of the dissolution inhibitor compound, and
said lone pair-containing portion is a member selected from the group consisting of:
(1) a double bonded oxygen atom-containing group of the following formula:
24
(2) an alkoxy or alkoxycarbonyl group of the following formula:
OCH3, OCH2CH3, OOCCH3, OOCCH2CH3, OCCH3, OCCH2CH3, COOCH3 or COOCH2CH3; and
(3) a halogen atom including chlorine, fluorine, iodine and bromine.
2. The chemical amplification resist composition as in claim 1, in which at least two double bonded oxygen-containing groups (1), at least three alkoxy or alkoxycarbonyl groups (2) andor at least three halogen atoms (3) are included in the same molecule of said dissolution inhibitor compound.
3. The chemical amplification resist composition as in claim 1 or 2, in which said structure A of said dissolution inhibitor compound is a cyclic group having no conjugated double bond.
4. The chemical amplification resist composition as in any one of claims 1 to 3, in which said dissolution inhibiting group SIG of said dissolution inhibitor compound is a member selected from the group consisting of:
25
wherein
R1, R2 and R3 may be the same or different and each represents a hydrogen or a methyl, ethyl, phenyl, cyclohexyl or cyclopentyl which may be substituted or unsubstituted, and
R4 represents a substituted or unsubstituted, methylene or ethylene group.
5. The chemical amplification resist composition as in any one of claims 1 to 4, in which said base resin is a member selected from the group consisting of phenol-novolak resin, cresol-novolak resin, phenol-cresol-novolak resin, copolymer of polyhydroxystyrene, polycarboxystyrene andor hydroxystyrene with a monomer containing a carbon-carbon double bond, copolymer of carboxystyrene with a monomer containing a carbon-carbon double bond, copolymer of hydroxystyrene with carboxystyrene, silphenylenesiloxane polymer containing an acetylated benzene ring, siloxane polymer containing an acetylated benzene ring, silphenylenesiolxane polymer containing a silanol group, siloxane polymer containing a silanol group, silphenylenesiloxane polymer containing a carboxyl or acidic hydroxyl group, and siloxane polymer containing a carboxyl or acidic hydroxyl group.
6. A process for the formation of resist patterns which comprises the steps of:
coating a chemical amplification resist composition on a substrate to be fabricated, said resist composition comprising a combination of an alkali-soluble base resin, a photoacid generator and a dissolution inhibitor, in which said dissolution inhibitor is a compound of the following formula (I):
26
wherein
A represents atoms necessary to complete a cyclic or acyclic structure constituting a matrix portion of the molecule of said dissolution inhibitor,
SIG may be the same or different and each represents a dissolution inhibiting group capable of being released from said cyclic or acyclic structure A, to which said dissolution inhibiting group is directly or indirectly bonded, upon the action of an acid which is released from said photoacid generator, and
m represents the number of said dissolution inhibiting groups SIG bonded to said structure A and is an integer of 1 or more, and
said structure A of said compound of the dissolution inhibitor contains at least one lone pair-containing portion which can provide a hydrogen bond sufficient to shift and gather an alkali-soluble moiety of said base resin to and on a side of said molecule of the dissolution inhibitor compound, and
said lone pair-containing portion is a member selected from the group consisting of:
(1) a the double bonded oxygen atom-containing group of the following formula:
27
(2) an alkoxy or alkoxycarbonyl group of the following formula:
OCH3, OCH2CH3, OOCCH3, OOCCH2CH3, OCCH3, OCCH2CH3, COOCH3 or COOCH2CH3; and
(3) a halogen atom including chlorine, fluorine, iodine and bromine, thereby forming a resist coating on said substrate;
selectively exposing said resist coating to a patterning radiation capable of causing a decomposition of said dissolution inhibitor compound; and
developing the exposed resist coating with an aqueous alkaline solution.
7. A chemical amplification resist composition for forming resist patterns which comprises a combination of an alkali-soluble base resin, a photoacid generator and a dissolution inhibitor, in which said dissolution inhibitor is a compound of the following formula (II):
28
wherein
A represents atoms necessary to complete a cyclic or acyclic structure constituting a matrix portion of the molecule of said dissolution inhibitor,
SIG may be the same or different and each represents a dissolution inhibiting group capable of being released from said cyclic or acyclic structure A, to which said dissolution inhibiting group is indirectly bonded through a linkage group L, upon the action of an acid which is released from said photoacid generator, and is concentratedly distributed in the molecule of said dissolution inhibitor,
L is a linkage group connecting the SIG group to said structure A, and may be independently included for each SIG group or may be commonly included for two or more SIG groups with the proviso that the number of atoms contained between the adjacent SIG groups is not more than 4, and
n represents the number of said SIG groups bonded to said structure A and is an integer of 3 or more.
8. The chemical amplification resist composition as in claim 7, in which the structure A of said dissolution inhibitor compound contains at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a halogen atom, a nitrogen atom and a phosphorus atom.
9. The chemical amplification resist composition as in claim 7 or 8, in which the structure A of said dissolution inhibitor compound contains at least one double-bonded oxygen atom-containing group of the following formula:
29
10. The chemical amplification resist composition, as in any one of claims 7 to 9, in which the structure A of said dissolution inhibitor compound is an aromatic group, a saturated cyclic group or a chain group.
11. The chemical amplification resist composition as in claim 10, in which the saturated cyclic group constituting said structure A of the dissolution inhibitor compound is a member selected from the group consisting of cyclooctyl ring, cycloheptyl ring, cyclohexyl ring, cyclopentyl ring, cyclobutyl ring, adamantyl ring, tetrahydrofuranyl ring, tetrahydrothiophenyl ring, dioxanyl ring, cyclooctanonyl ring, cycloheptanonyl ring, cyclohexanonyl ring, cyclopentanonyl ring, cyclobutanonyl ring, butylocactone ring, piperidinyl ring and piperadinyl ring.
12. The chemical amplification resist composition as in any one of claims 7 to 11, in which said dissolution inhibiting group SIG of said dissolution inhibitor compound is a member selected from the group consisting of:
30
wherein
R1, R2 and R3 may be the same or different and each represents a hydrogen or a methyl, ethyl, phenyl, cyclohexyl or cyclopentyl which may be substituted or unsubstituted, and
R4 represents a substituted or unsubstituted, methylene or ethylene group.
13. The chemical amplification resist composition as in any one of claims 7 to 12, in which said base resin is a member selected from the group consisting of phenol-novolak resin, cresol-novolak resin, phenol-cresol-novolak resin, copolymer of polyhydroxystyrene, polycarboxystyrene andor hydroxystyrene with a monomer containing a carbon-carbon double bond, copolymer of carboxystyrene with a monomer containing a carbon-carbon double bond, copolymer of hydroxystyrene with carboxystyrene, silphenylenesiloxane polymer containing an acetylated benzene ring, siloxane polymer containing an acetylated benzene ring, silphenylenesiolxane polymer containing a silanol group, siloxane polymer containing a silanol group, silphenylenesiloxane polymer containing a carboxyl or acidic hydroxyl group, and siloxane polymer containing a carboxyl or acidic hydroxyl group.
14. A process for the formation of resist patterns which comprises the steps of:
coating a chemical amplification resist composition on a substrate to be fabricated, said resist composition comprising a combination of an alkali-soluble base resin, a photoacid generator and a dissolution inhibitor, in which said dissolution inhibitor is a compound of the following formula (II):
31
wherein
A represents atoms necessary to complete a cyclic or acyclic structure constituting a matrix portion of the molecule of said dissolution inhibitor,
SIG may be the same or different and each represents a dissolution inhibiting group capable of being released from said cyclic or acyclic structure A, to which said dissolution inhibiting group is indirectly bonded through a linkage group L, upon the action of an acid which is released from said photoacid generator, and is concentratedly distributed in the molecule of said dissolution inhibitor,
L is a linkage group connecting the SIG group to said structure A, and may be independently included for each SIG group or may be commonly included for two or more SIG groups with the proviso that the number of atoms contained between the adjacent SIG groups is not more than 4, and
n represents the number of said SIG groups bonded to said structure A and is an integer of 3 or more, thereby forming a resist coating on said substrate;
selectively exposing said resist coating to a patterning radiation capable of causing a decomposition of said dissolution inhibitor compound; and
developing the exposed resist coating with an aqueous alkaline solution.
15. A chemical amplification resist composition for forming resist patterns which comprises a combination of an alkali-soluble base resin, a photoacid generator and a dissolution inhibitor, in which said dissolution inhibitor is a compound of the following formula (III):
32
wherein
A represents atoms necessary to complete a cyclic or acyclic structure constituting a matrix portion of the molecule of said dissolution inhibitor,
SIG may be the same or different and each represents a dissolution inhibiting group capable of being released from said cyclic or acyclic structure A, to which said dissolution inhibiting group is directly or indirectly bonded, upon the action of an acid which is released from said photoacid generator, said SIG group being a member selected from the group consisting of:
33
wherein
R5, R6 and R7 may be the same or different and each represents hydrogen or any substituent group with the proviso that at least one of said substituent groups is a halogenated alkyl group of 3 or less carbon atoms, and
n represents the number of said dissolution inhibiting groups SIG bonded to said structure A and is an integer of 3 or more, and
said dissolution inhibitor compound has a molecular weight of 300 to 1500.
16. The chemical amplification resist composition as in claim 15, in which the structure A of said dissolution inhibitor compound is benzophenone, adamantane or cyclohexane.
17. The chemical amplification resist as in claim 15 or 17, in which said base resin is a member selected from the group consisting of phenol-novolak resin, cresol-novolak resin, phenol-cresol-novolak resin, copolymer of polyhydroxystyrene, polycarboxystyrene andor hydroxystyrene with a monomer containing a carbon-carbon double bond, copolymer of carboxystyrene with a monomer containing a carbon-carbon double bond, copolymer of hydroxystyrene with carboxystyrene, silphenylenesiloxane polymer containing an acetylated benzene ring, siloxane polymer containing an acetylated benzene ring, silphenylenesiolxane polymer containing a silanol group, siloxane polymer containing a silanol group, silphenylenesiloxane polymer containing a carboxyl or acidic hydroxyl group, and siloxane polymer containing a carboxyl or acidic hydroxyl group.
18. The chemical amplification resist composition as in any one of claims 15 to 17, in which the photoacid generator is a member selected from the group consisting of a sulfonium salt compound, an iodonium salt compound, a benzyltosylate compound and an organic halogen-containing compound.
19. A process for the formation of resist patterns which comprises the steps of:
coating a chemical amplification resist composition on a substrate to be fabricated, said resist composition comprising a combination of an alkali-soluble base resin, a photoacid generator and a dissolution inhibitor, in which said dissolution inhibitor is a compound of the following formula (III):
34
wherein
A represents atoms necessary to complete a cyclic or acyclic structure constituting a matrix portion of the molecule of said dissolution inhibitor,
SIG may be the same or different and each represents a dissolution inhibiting group capable of being released from said cyclic or acyclic structure A, to which said dissolution inhibiting group is directly or indirectly bonded, upon the action of an acid which is released from said photoacid generator, said SIG group being a member selected from the group consisting of:
35
wherein
R5, R6 and R7 may be the same or different and each represents hydrogen or any substituent group with the proviso that at least one of said substituent groups is a halogenated alkyl group of 3 or less carbon atoms, and
n represents the number of said dissolution inhibiting groups SIG bonded to said structure A and is an integer of 3 or more, and has a molecular weight of 300 to 1500, thereby forming a resist coating on said substrate;
selectively exposing said resist coating to a patterning radiation capable of causing a decomposition of said dissolution inhibitor compound; and
developing the exposed resist coating with an aqueous alkaline solution.
20. A process for the preparation of a chemical amplification resist composition comprising a combination of an alkali-soluble base resin, a photoacid generator and a dissolution inhibitor, which process comprises the steps of:
preparing a dissolution inhibitor compound of the following formula (I):
36
wherein
A represents atoms necessary to complete a cyclic or acyclic structure constituting a matrix portion of the molecule of this compound,
SIG may be the same or different and each represents a dissolution inhibiting group capable of being released from said cyclic or acyclic structure A, to which said dissolution inhibiting group is directly or indirectly bonded, upon the action of an acid which is released from said photoacid generator, and
m represents the number of said dissolution inhibiting groups SIG bonded to said structure A and is an integer of 1 or more, and
said structure A contains at least one lone pair-containing portion which can provide a hydrogen bond sufficient to shift and gather an alkali-soluble moiety of said base resin towards a side of said molecule of the dissolution inhibitor compound, and
said lone pair-containing portion is a member selected from the group consisting of:
(1) a double bonded oxygen atom-containing group of the following formula:
37
(2) an alkoxy or alkoxycarbonyl group of the following formula:
OCH3, OCH2CH3, OOCCH3, OOCCH2CH3, OCCH3, OCCH2CH3, COOCH3 or COOCH2CH3; and
(3) a halogen atom including chlorine, fluorine, iodine and bromine; and
dissolving the resulting dissolution inhibitor compound along with the base resin and the photoacid generator in a resist solvent to make a resist solution.
21. A process for the preparation of a chemical amplification resist composition comprising a combination of an alkali-soluble base resin, a photoacid generator and a dissolution inhibitor, which process comprises the steps of:
preparing a dissolution inhibitor compound of the following formula (II):
38
wherein
A represents atoms necessary to complete a cyclic or acyclic structure constituting a matrix portion of the molecule of this compound.
SIG may be the same or different and each represents a dissolution inhibiting group capable of being released from said cyclic or acyclic structure A, to which said dissolution inhibiting group is indirectly bonded through a linkage group L, upon the action of an acid which is released from said photoacid generator, and is concentratedly distributed in the molecule of said dissolution inhibitor,
L is a linkage group connecting the SIG group to said structure A, and may be independently included for each SIG group or may be commonly included for two or more SIG groups with the proviso that the number of atoms contained between the adjacent SIG groups is not more than 4, and
n represents the number of said SIG groups bonded to said structure A and is an integer of 3 or more; and
dissolving the resulting dissolution inhibitor compound along with the base resin and the photoacid generator in a resist solvent to make a resist solution.
22. A process for the preparation of a chemical amplification resist composition comprising a combination of an alkali-soluble base resin, a photoacid generator and a dissolution inhibitor, which process comprises the steps of: preparing a dissolution inhibitor compound of the following formula (III):
39
wherein
A represents atoms necessary to complete a cyclic or acyclic structure constituting a matrix portion of the molecule of this compound,
SIG may be the same or different and each represents a dissolution inhibiting group capable of being released from said cyclic or acyclic structure A, to which said dissolution inhibiting group is directly or indirectly bonded, upon the action of an acid which is released from said photoacid generator, said SIG group being a member selected from the group consisting of:
40
wherein
R5, R6 and R7 may be the same or different and each represents hydrogen or any substituent group with the proviso that at least one of said substituent groups is a halogenated alkyl group of 3 or less carbon atoms, and
n represents the number of said dissolution inhibiting groups SIG bonded to said structure A and is an integer of 3 or more, and
said dissolution inhibitor compound has a molecular weight of 300 to 1500; and
dissolving the resulting dissolution compound along with the base resin and the photoacid generator in a resist solvent to make a resist solution.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A method for determining sound velocity Cb in a base material of a specimen to be tested, using an ultrasonic probe,
the probe comprising: a transmitting transducer; a receiving transducer; and a precursor body; said precursor body: a) having a coupling surface by which the probe is couplable to the base material, b) carrying the receiving transducer and the transmitting transducer, and c) having a sound velocity Cv; said transmitting transducer and said receiving transducerbeing oriented to be inclined towards each other and each towards the coupling surface so that a main transmission direction of the transmitting transducer and a main receiving direction of the receiving transducer intersect below the coupling surface; said transmitting transducer and receiving transducerbeing spaced apart at a center to center distance K; said transmitting transducer and said receiving transducer being spaced at a center to center distance Dv from the coupling surface;
said method comprising:
generating an ultrasonic pulse by the transmitting transducer which is passed through the precursor body into the base material;
the ultrasonic pulse producing a creeping wave in the base material, the creeping wave being a surface wave, at least a portion of the creeping wave reaching the receiving transducer via the precursor body; and
measuring a shortest sound travel time Ttot of the ultrasonic pulse and the sound velocity Cb in the base material by a path between the transmitting transducer and the receiving transducer that supplies the shortest total travel time Ttot.
2. The method according to claim 1, wherein the path that supplies the shortest total travel time Ttot is determined by summing a travel distance from the transmitting transducer to the base material, a travel distance within the base material and a travel distance from the base material to the receiving transducer and by optimizing said travel distances with regard to the shortest total travel time Ttot.
3. The method according to claim 1, wherein the shortest total travel time Ttot is obtained through
T
tot
=
K
Cb
+
2
\u2062
Dv
\u2061
(
1
Cv
\u2062
\u2062
cos
\u2061
(
arc
\u2062
\u2062
sin
\u2061
(
Cv
Cb
)
)
–
tan
\u2061
(
arc
\u2062
\u2062
sin
\u2061
(
Cv
Cb
)
)
Cb
)
.
4. The method according to claim 1, wherein main beams of the transmitting transducer and the receiving transducer lie in the same plane, the main beams being inclined at the same angle relative to a coupling surface.
5. The method according to claim 1, further including determining sound velocity in a coating material applied as a layer on base material, the method comprising:
placing the probe onto the layer having a thickness Ds;
generating an ultrasound pulse by the transmitting transducer that traverses both the precursor body and the layer at an incline toward the coupling surface;
producing a creeping wave in the base material a portion of which creeping wave again traverses the layer and the precursor body at an incline toward the coupling surface prior to reaching the receiving transducer;
registering and measuring a receive signal with the shortest total travel time Ttot; and
determining the coating thickness Ds of the layer from that path that supplies the shortest total travel time Ttot.
6. The method according to claim 5, wherein the shortest travel time Ttot is obtained from
Ttot
=
K
Cb
+
2
\u2062
(
Dv
\u2062
(
1
Cv
\u2062
\u2062
cos
\u2062
\u2062
arc
\u2062
\u2062
sin
\u2061
(
Cv
Cb
)
–
tan
\u2062
\u2062
arc
\u2062
\u2062
sin
\u2061
(
Cv
Cb
)
Cb
)
+
Ds
\u2061
(
1
Cs
\u2062
\u2062
cos
\u2062
\u2062
arc
\u2062
\u2062
sin
\u2061
(
Cs
Cb
)
–
tan
\u2062
\u2062
arc
\u2062
\u2062
sin
\u2062
\u2062
(
Cs
Cb
)
Cb
)
)
,
wherein Ds=the thickness of the layer.
7. The method according to claim 1, wherein the path that supplies the shortest total travel time Ttot is determined by summing up a travel distance from the transmitting transducer to the base material, a travel distance within the base material and a travel distance from the base material to the receiving transducer and by differentiation after the angle.
8. A device for determining sound velocity Cb in a base material of a specimen to be tested, comprising:
an ultrasonic probe comprising: a transmitting transducer; a receiving transducer; and a precursor body;
said precursor body: a) having a coupling surface by which the probe is couplable to the base material, b) carrying the receiving transducer and the transmitting transducer, and c) having a sound velocity Cv;
said transmitting transducer and said receiving transducer being oriented to be inclined towards each other and each towards the coupling surface so that a main transmission direction of the transmitting transducer and a main receiving direction of the receiving transducer intersect below the coupling surface;
said transmitting transducer and said receiving transducer being spaced apart at a center to center distance K; and
said transmitting transducer and said receiving transducer being spaced at a center to center distance Dv from the coupling surface,
wherein the transmitting transducer is configured to generate an ultrasonic pulse which passes through the precursor body into the base material, wherein the ultrasonic pulse produces a creeping wave in the base material, the creeping wave being a surface wave, a portion of the creeping wave being configured to reach the receiving transducer via the precursor body, and wherein the shortest sound travel time Ttot of the ultrasonic pulse is measurable and the sound velocity Cb in the base material is determinable by the very path between the transmitting transducer and the receiving transducer that supplies the shortest total travel time Ttot.
9. The device of claim 8, wherein main beams of the transmitting transducer and said receiving transducer lie in the same plane, the main beams inclined at the same angle relative to the coupling surface.