Photoresist composition for deep UV and process thereof
View Patent ↗The present invention relates to a novel chemically amplified photoresist, which is sensitive to wavelengths between 300 nm and 100 nm, and comprises a) a novel polymer comprising a sulfone group pendant from a polymer backbone that is insoluble in an aqueous alkaline solution and comprises at least one acidic moiety protected with acid labile group, and b) a compound capable of producing an acid upon irradiation. The invention also relates to a process of imaging the novel positive photoresist composition.
1. A photoresist composition comprising a photoacid generator and a polymer comprising at least one unit as described by structure 1,
where, structure 1 is free of fluorination;
A is a nonaromatic polymer backbone;
W is a single bond or a nonaromatic linking group;
m is present and to 10; further,
either, R 5 and R 6 are connected to form a cyclic unit, and R 4 is independently hydrogen, (C 1 -C 18 ) alkyl, SO 2 R 7 , C(O)R 7 , (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , CO 2 (CH 2 ) n CO 2 R 7 , O(CH 2 ) n CO 2 R 7 , (CH 2 ) n CO 2 R 7 , acidic moiety protected with an acid labile group, and where R 7 is selected from hydrogen, (C 1 -C 18 ) linear, branched or cyclic alkyl, further where R 5 and R 6 are independently selected from (C 1 -C 18 ) linear, branched or cyclic alkyl, (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , (CH 2 )nCO 2 R 7 , where R 7 is selected from (C 1 -C 18 ) linear, branched or cyclic alkyl;
or, R 5 and R 6 are connected to form a cyclic unit and R 4 and R 5 are connected to form an alky cyclic structure, or R 4 and R 5 are connected to from an alkyl cyclic structure containing within the cyclic structure suflone, ether, carbonyl, and carboxyl moieties where R 4 , R 5 and R 6 are independently selected from (C 1 -C 18 ) linear, branched or cyclic alkyl, (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , (CH 2 )nCO 2 R 7 , where R 7 is selected from (C 1 —C 18 ) linear, branched or cyclic alkyl; and
n=1-18.
2. The composition according to claim 1 , where A is a cyclic unit selected from an aliphatic multicyclic unit and an aliphatic monocyclic unit.
3. The composition according to claim 1 , where the unit of structure 1 is further described by structure 2
where,
structure 2 is free of fluorination,
R 1 -R 3 are independently selected from hydrogen, cyano, and (C 1 -C 10 ) alkyl,
W is a valence bond or a nonaromatic linking group;
m is present and to 10; further,
either, R 5 and R 6 are connected to form a cyclic unit, and R 4 is independently hydrogen, (C 1 -C 18 ) alkyl, SO 2 R 7 , C(O)R 7 , (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , CO 2 (CH 2 ) n CO 2 R 7 , O(CH 2 ) n CO 2 R 7 , (CH 2 ) n CO 2 R 7 , acidic moiety protected with an acid labile group, and where R 7 is selected from hydrogen, (C 1 -C 18 ) linear, branched or cyclic alkyl, further where R 5 and R 6 are independently selected from (C 1 -C 18 ) linear, branched or cyclic alkyl, (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , (CH 2 )nCO 2 R 7 , where R 7 is selected from (C 1 -C 18 ) linear, branched or cyclic alkyl;
or, R 5 and R 6 are connected to form a cyclic unit and R 4 and R 5 are connected to form an alkyl cyclic structure, or R 4 and R 5 are connected to form an alkyl cyclic structure containing within the cyclic structure suflone, ether, carbonyl, and carboxyl moieties where R 4 , R 5 and R 6 are independently selected from (C 1 -C 18 ) linear, branched or cyclic alkyl, (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , (CH 2 )nCO 2 R 7 , where R 7 is selected from (C 1 -C 18 ) linear, branched or cyclic alkyl; and
n=1-18.
4. The composition according to claim 2 , where the cyclic unit of structure 1 is selected from those derived from the following monomers,
where, in the above structures, R 1 -R 7 are independently H, (C 1 -C 8 ) alkyl, and at least one of R 1 -R 6 forms the structure 3,
where,
structure 3 is free of fluorination,
W is a valence bond or a nonaromatic linking group;
m is present and to 5; further,
either, R 5 and R 6 are connected to form a cyclic unit, and R 4 is independently hydrogen, (C 1 -C 18 ) alkyl, SO 2 R 7 , C(O)R 7 , (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , CO 2 (CH 2 ) n CO 2 R 7 , O(CH 2 ) n CO 2 R 7 , (CH 2 ) n CO 2 R 7 , acidic moiety protected with an acid labile group, and where R 7 is selected from hydrogen, (C 1 -C 18 ) linear, branched or cyclic alkyl, further where R 5 and R 6 are independently selected from (C 1 -C 18 ) linear, branched or cyclic alkyl, (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , (CH 2 )nCO 2 R 7 , where R 7 is selected from (C 1 -C 18 ) linear, branched or cyclic alkyl;
or, R 5 and R 6 are connected to form a cyclic unit and R 4 and R 5 are connected to form an alkyl cyclic structure, or R 4 and R 5 are connected to form an alkyl cyclic structure containing within the cyclic structure suflone, ether, carbonyl, and carboxyl moieties where R 4 , R 5 and R 6 are independently selected from (C 1 -C 18 ) linear, branched or cyclic alkyl, (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , (CH 2 )nCO 2 R 7 , where R 7 is selected from (C 1 -C 18 ) linear, branched or cyclic alkyl; and
n=1-18.
5. The composition according to claim 1 , where W is selected from an aliphatic cyclic alkyl group, aliphatic linear or branched alkyl group, carbonyl (CO), carbonyloxy (C(O)—O), oxycarbonyl (O—C(O)), carbonate (O—C(O)—O), sulfone (SO 2 ), sulfoxide (SO), oxy (O) and sulfide (S), and aliphatic cyclic alkyl group with a pendant group selected from carbonyl (CO), carbonyloxy (C(O)—O), oxycarbonyl (O—C(O)), carbonate (O—C(O)—O), sulfone (SO 2 ), sulfoxide (SO), oxy (O) and sulfide (S)
6. The composition according to claim 1 , where W is selected from a (C 1 -C 8 ) linear alkyl, (C 1 -C 8 ) branched alkyl, substituted monocycloalkyl, unsubstituted monocycloalkyl, substituted multicycloalkyl and unsubstituted multicycloalkyl.
7. The composition according to claim 1 , where the polymer is a homopolymer.
8. The composition according to claim 1 , where the polymer further comprises at least one comonomeric unit.
9. The composition according to claim 8 , where the comonomeric unit is derived from monomers selected from cyclic anhydrides, (meth)acrylate esters, vinyl acetals and cycle olefins.
10. The process of imaging a positive photoresist composition comprising the steps of:
a) coating a substrate with a film of photoresist composition of claim 1 ;
b) baking the substrate to substantially remove the solvent;
c) imagewise irradiating the photoresist film;
d) baking the photoresist film; and,
e) developing the irradiated photoresist film using an alkali developer.
11. The photoresist composition according to claim 10 , further comprising coating an antireflective film on the substrate prior to coating the photoresist.
12. The process of claim 10 , further where the photoresist film is sensitive at 193 nm.
13. The process of claim 10 , wherein the photoresist film is imagewise irradiated using immersion lithography.
14. The process of claim 10 , wherein the photoresist film is imagewise irradiated with light of wavelength in the range of 100 nm to 300 nm.
15. The process of claim 10 , wherein the heating in step d) ranges from a temperature of from about 90° C. to about 150° C. for from about 30 seconds to about 180 seconds on a hot plate.
16. The process of claim 10 , wherein the alkali developer comprises an aqueous solution of tetramethyl ammonium hydroxide.
17. A polymer comprising at least one unit as described by structure 1,
where, the polymer comprises at least one acid labile group and structure 1 is free of fluorination, and where,
A is a nonaromatic polymer backbone;
W is a single bond or a nonaromatic linking group;
m is present and to 10; further,
either, R 5 and R 6 are connected to form a cyclic unit, and R 4 is independently hydrogen, (C 1 -C 18 ) alkyl, SO 2 R 7 , C(O)R 7 , (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , CO 2 (CH 2 ) n CO 2 R 7 , O(CH 2 ) n CO 2 R 7 , (CH 2 ) n CO 2 R 7 , acidic moiety protected with an acid labile group, and where R 7 is selected from hydrogen, (C 1 -C 18 ) linear, branched or cyclic alkyl, further where R 5 and R 6 are independently selected from (C 1 -C 18 ) linear, branched or cyclic alkyl, (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , (CH 2 )nCO 2 R 7 , where R 7 is selected from (C 1 -C 18 ) linear, branched or cyclic alkyl;
or, R 5 and R 6 are connected to form a cyclic unit and R 4 and R 5 are connected to form an alkyl cyclic structure, or R 4 and R 5 are connected to form an alkyl cyclic structure containing within the cyclic structure suflone, ether, carbonyl, and carboxyl moieties where R 4 , R 5 and R 6 are independently selected from (C 1 -C 18 ) linear, branched or cyclic alkyl, (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , (CH 2 )nCO 2 R 7 , where R 7 is selected from (C 1 —C 18 ) linear, branched or cyclic alkyl; and
n=1-18.
18. The polymer according to claim 17 , where A is selected from at least one of an aliphatic multicyclic unit, an aliphatic monocyclic unit, a substituted ethylene unit and an unsubstitued ethylene unit.
19. A photoresist composition comprising a photoacid generator and a polymer, where the polymer comprises at least one unit selected from
20. A photoresist composition comprising a photoacid generator and polymer consisting of a unit as described by structure 1 and at least one comonomeric unit derived from monomers of vinyl acetals, and where structure 1 is,
where,
the structure 1 is free of fluorination,
A is a nonaromatic polymer backbone;
W is a single bond or a nonaromatic linking group;
m=0-10;
R 4 and R 5 are independently hydrogen, (C 1 -C 18 ) alkyl, SO 2 R 7 , C(O)R 7 , (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , CO 2 (CH 2 ) n CO 2 R 7 , O(CH 2 ) n CO 2 R 7 , (CH 2 ) n CO 2 R 7 , acidic moiety protected with an acid labile group, R 4 and R 5 may be connected to form an unsubstituted or substituted alky cyclic structure, R 4 and R 5 may be connected to form an unsubstituted or substituted alkyl cyclic structure containing within the cyclic structure sulfone, ether, carboxyl, and other hetero moieties, where R 7 is selected from (CH 2 ) n CN, hydrogen,(C 1 -C 18 ) linear, branched or cyclic alkyl, and acidic moiety protected with acid labile group;
R 6 is independently (C 1 -C 18 ) linear, branched or cyclic alkyl, (CH 2 ) n SO 2 R 7 , (CH 2 ) n COR 7 , (CH 2 ) n OR 7 , (CH 2 )nCO 2 R 7 where R 7 is selected from (C 1 -C 18 ) linear, branched or cyclic alkyl, and acid labile group; and, optionally,
R 5 and R 6 are connected to form an unsubstituted or substituted cyclic alkyl unit comprising a sulfone group; and,
n=1-18.