1. A norbornene-ester based addition polymer having a molecular weight (Mn) larger than 20,000 and comprising a norbornene-ester based monomer as a repeating unit, which comprises more than 50 mol % of exo norbornene-ester.
2. The norbornene-ester based addition polymer according to claim 1, wherein the norbornene-ester monomer is a compound represented by the following Chemical Formula 1:
wherein
m is an integer of 0 to 4;
at least one of R1, R2, R3, and R4 is a radical having an ester group;
each of the other R1, R2, R3, and R4 is hydrogen; C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted by hydrocarbon or unsubstituted; C6 to C40 aryl substituted by hydrocarbon or unsubstituted; C7 to C15 aralkyl substituted by hydrocarbon or unsubstituted; C3 to C20 alkynyl; or halogen; and
if R1, R2, R3, and R4 are not radicals having an ester group, a hydrogen, or a halogen, R1 and R2, or R3 and R4 may be connected to form a C1 to C10 alkylidene group, or R1 or R2 may be connected with R3 or R4 to form a C4 to C12 saturated or unsaturated cyclic group or a C6 to C17 aromatic group.
3. The norbornene-ester based addition polymer according to claim 1, wherein the norbornene-ester based addition polymer is a homopolymer of a norbornene-ester monomer.
4. The norbornene-ester based addition polymer according to claim 1, wherein the norbornene-ester based addition polymer is a copolymer of different norbornene-ester monomers.
5. The norbornene-ester based addition polymer according to claim 1, wherein the norbornene-ester based addition polymer is a copolymer of a norbornene-ester monomer and a norbornene based monomer not having an ester group.
6. The norbornene-ester based addition polymer according to claim 5, wherein the norbornene based monomer not having an ester group is a compound represented by the following Chemical Formula 2:
wherein
m is an integer of 0 to 4;
each of R1, R2, R3, and R4 is selected from a group consisting of: hydrogen; halogen; C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted by hydrocarbon or unsubstituted; C6 to C40 aryl substituted by hydrocarbon or unsubstituted; C7 to C15 aralkyl substituted by hydrocarbon or unsubstituted; C3 to C20 alkynyl; C1 to C20 linear or branched haloalkyl, haloalkenyl, or halovinyl; C5 to C12 halocycloalkyl substituted by hydrocarbon or unsubstituted; C6 to C40 haloaryl substituted by hydrocarbon or unsubstituted; C7 to C15 haloaralkyl substituted by hydrocarbon or unsubstituted; C3 to C20 haloalkynyl; and a non-hydrocarbonaceous polar group having at least one oxygen, nitrogen, phosphorus, sulfur, silicon, or boron atom, independently or simultaneously; and
if R1, R2, R3, and R4 are not hydrogen, halogen, or a polar group, R1 and R2, or R3 and R4 may be connected to form a C1 to C10 alkylidene group, or R1 or R2 may be connected with R3 or R4 to form a C4 to C12 saturated or unsaturated cyclic group, or a C6 to C24 aromatic group.
7. The norbornene-ester based addition polymer according to claim 6, wherein the non-hydrocarbonaceous polar group in Chemical Formula 2 is a functional group selected from a group consisting of: \u2014OR6, \u2014OC(O)OR6, \u2014R5OC(O)OR6, \u2014C(O)R6, \u2014R5C(O)R6, \u2014OC(O)R6, \u2014R5OC(O)R6, \u2014(R5O)p\u2014OR6, \u2014(OR5)p\u2014OR6, \u2014C(O)\u2014O\u2014C(O)R6, \u2014R5C(O)\u2014O\u2014C(O)R6, \u2014SR6, \u2014R5SR6, \u2014SSR6, \u2014R5SSR6, \u2014S(\u2550O)R6, \u2014R5S(\u2550O)R6, \u2014R5C(\u2550S)R6, \u2014R5C(\u2550S)SR6, \u2014R5SO3R6, \u2014SO3R6,\u2014R5N\u2550C\u2550S, \u2014NCO, R5\u2014NCO, \u2014CN, \u2014R5CN, \u2014NNC(\u2550S)R6, \u2014R5NNC(\u2550S)R6, \u2014NO2, \u2014R5NO2,
wherein
R5 is C1 to C20 linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl, vinyl, or halovinyl; C4 to C12 cycloalkyl or halocycloalkyl substituted by hydrocarbon or unsubstituted; C6 to C40 aryl or haloaryl substituted by hydrocarbon or unsubstituted; C7 to C15 aralkyl or haloaralkyl substituted by hydrocarbon or unsubstituted; or C3 to C20 alkynyl or haloalkynyl;
each of R6, R7, and R8 is hydrogen; halogen; C1 to C20 linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl, vinyl, halovinyl, alkoxy, haloalkoxy, carbonyloxy, or halocarbonyloxy; C4 to C12 cycloalkyl or halocycloalkyl substituted by hydrocarbon or unsubstituted; C6 to C40 aryl, haloaryl, aryloxy, or haloaryloxy substituted by hydrocarbon or unsubstituted; C7 to C15 aralkyl or haloaralkyl substituted by hydrocarbon or unsubstituted; or C3 to C20 alkynyl or haloalkynyl;
and p is an integer of 1 to 10.
8. A method for preparing an exo-rich norbornene-ester based monomer, which comprises a step of carrying out a Diels-Alder reaction of dicyclopentadiene and ester compound at 180 to 260\xb0 C. for a duration of time in which the reaction quotient defined by the following Equation 1 ranges from 82,000 to 155,000:
Reaction quotient=reaction temperature (\xb0 C.)2\xd7log reaction time (min).\u2003\u2003Equation 1
9. The method for preparing an exo-rich norbornene-ester based monomer according to claim 8, wherein the norbornene-ester based monomer is a compound represented by the following Chemical Formula 1:
wherein
m is an integer of 0 to 4;
at least one of R1, R2, R3, and R4 is a radical having an ester group;
each of the other R1, R2, R3, and R4 is hydrogen; C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted by hydrocarbon or unsubstituted; C6 to C40 aryl substituted by hydrocarbon or unsubstituted; C7 to C15 aralkyl substituted by hydrocarbon or unsubstituted; C3 to C20 alkynyl; or halogen; and
if R1, R2, R3, and R4 are not radicals having an ester group, a hydrogen, or a halogen, R1 and R2, or R3 and R4 may be connected to form a C1 to C10 alkylidene group, or R1 or R2 may be connected with R3 or R4 to form a C4 to C12 saturated or unsaturated cyclic group or a C6 to C17 aromatic group.
10. A method for preparing a norbornene-ester based addition polymer, which comprises:
a) a step of preparing a norbornene-ester based monomer comprising more than 50 mol % of exo norbornene-ester monomer; and
b) a step of preparing a norbornene-ester based addition polymer having a molecular weight (Mn) larger than 20,000, and comprising more than 50 mol % of exo norbornene-ester monomer as a repeating unit, by polymerizing a monomer comprising the norbornene-ester based monomer of step a) in solution phase in the presence of a catalyst system, which comprises a Group X transition metal compound with an anionic ligand offering \u03c3- and \u03c0-bonds.
11. The method for preparing a norbornene-ester based addition polymer according to claim 10, wherein the step a) is proceeded by carrying out a Diels-Alder reaction of dicyclopentadiene and ester compound at 180 to 260\xb0 C. for a duration of time in which the reaction quotient defined by the following Equation 1 ranges from 82,000 to 155,000:
Reaction quotient=reaction temperature (\xb0 C.)2\xd7log reaction time (min).\u2003\u2003Equation 1
12. The method for preparing a norbornene-ester based addition polymer according to claim 10, wherein the norbornene-ester monomer of the step a) is a compound represented by the following Chemical Formula 1:
wherein
m is an integer of 0 to 4;
at least one of R1, R2, R3, and R4 is a radical having an ester group;
each of the other R1, R2, R3, and R4 is hydrogen; C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted by hydrocarbon or unsubstituted; C6 to C40 aryl substituted by hydrocarbon or unsubstituted; C7 to C15 aralkyl substituted by hydrocarbon or unsubstituted; C3 to C20 alkynyl; or halogen; and
if R1, R2, R3, and R4 are not radicals having an ester group, a hydrogen, or a halogen, R1 and R2, or R3 and R4 may be connected to form a C1 to C10 alkylidene group, or R1 or R2 may be connected with R3 or R4 to form a C4 to C12 saturated or unsaturated cyclic group or a C6 to C17 aromatic group.
13. The method for preparing a norbornene-ester based addition polymer according to claim 10, wherein the norbornene-ester based addition polymer of the step b) is:
i) an addition homopolymer of a norbornene-ester monomer prepared from the same norbornene-ester monomer;
ii) an addition copolymer of two norbornene-ester monomers prepared from different norbornene-ester monomers; or
iii) an addition copolymer of a norbornene-ester monomer and a norbornene-ester monomer prepared from a norbornene based monomer not having an ester group.
14. The method for preparing a norbornene-ester based addition polymer according to claim 13, wherein the iii) norbornene based monomer not having an ester group is a compound represented by the following Chemical Formula 2:
wherein
m is an integer of 0 to 4;
each of R1, R2, R3, and R4 is selected from a group consisting of: hydrogen; halogen; C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted by hydrocarbon or unsubstituted; C6 to C40 aryl substituted by hydrocarbon or unsubstituted; C7 to C15 aralkyl substituted by hydrocarbon or unsubstituted; C3 to C20 alkynyl; C1 to C20 linear or branched haloalkyl, haloalkenyl, or halovinyl; C5 to C12 halocycloalkyl substituted by hydrocarbon or unsubstituted; C6 to C40 haloaryl substituted by hydrocarbon or unsubstituted; C7 to C15 haloaralkyl substituted by hydrocarbon or unsubstituted; C3 to C20 haloalkynyl; and a non-hydrocarbonaceous polar group having at least one oxygen, nitrogen, phosphorus, sulfur, silicon, or boron atom, independently or simultaneously; and
if R1, R2, R3, and R4 are not hydrogen, halogen, or a polar group, R1 and R2, or R3 and R4 may be connected to form a C1 to C10 alkylidene group, or R1 or R2 may be connected with R3 or R4 to form a C4 to C12 saturated or unsaturated cyclic group, or a C6 to C24 aromatic group.
15. The method for preparing a norbornene-ester based addition polymer according to claim 14, wherein the non-hydrocarbonaceous polar group in Chemical Formula 2 is a functional group selected from a group consisting of: \u2014OR6, \u2014OC(O)OR6, \u2014R5OC(O)OR6, \u2014C(O)R6, \u2014R5C(O)R6, \u2014OC(O)R6, \u2014R5OC(O)R6, \u2014(R5O)p\u2014OR6, \u2014(OR5)p\u2014OR6, \u2014C(O)\u2014O\u2014C(O)R6, \u2014R5C(O)\u2014O\u2014C(O)R6, \u2014SR6, \u2014R5SR6, \u2014SSR6, \u2014R5SSR6, \u2014S(\u2550O)R6, \u2014R5S(\u2550O)R6, \u2014R5C(\u2550S)R6, \u2014R5C(\u2550S)SR6, \u2014R5SO3R6, \u2014R5N\u2550C\u2550S, \u2014NCO, R5\u2014NCO, \u2014CN, \u2014R5CN, \u2014NNC(\u2550S)R6, \u2014R5NNC(\u2550S)R6, \u2014NO2, \u2014R5NO2,
wherein
R5 is C1 to C20 linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl, vinyl, or halovinyl; C4 to C12 cycloalkyl or halocycloalkyl substituted by hydrocarbon or unsubstituted; C6 to C40 aryl or haloaryl substituted by hydrocarbon or unsubstituted; C7 to C15 aralkyl or haloaralkyl substituted by hydrocarbon or unsubstituted; or C3 to C20 alkynyl or haloalkynyl;
each of R6, R7, and R8 is hydrogen; halogen; C1 to C20 linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl, vinyl, halovinyl, alkoxy, haloalkoxy, carbonyloxy, or halocarbonyloxy; C4 to C12 cycloalkyl or halocycloalkyl substituted by hydrocarbon or unsubstituted; C6 to C40 aryl, haloaryl, aryloxy, or haloaryloxy substituted by hydrocarbon or unsubstituted; C7 to C15 aralkyl or haloaralkyl substituted by hydrocarbon or unsubstituted; or C3 to C20 alkynyl or haloalkynyl;
and p is an integer of 1 to 10.
16. The method for preparing a norbornene-ester based addition polymer according to claim 10, wherein the Group X transition metal compound with an anionic ligand offering \u03c3- and \u03c0-bonds of the step b) is a compound represented by the following Chemical Formula 3 or Chemical Formula 4:
M(R)2\u2003\u2003Chemical Formula 3
wherein
M is a Group X metal;
X is a halogen; and
R is an anionic ligand offering \u03c3- and \u03c0-bonds, such as hydrocarbyl, acetylacetonate R\u2032C(O)CHC(O)R\u2032 or acetate, wherein each of R\u2032 is hydrogen, C1 to C20 linear or branched alkyl, alkenyl, or vinyl; C5 to C12 cycloalkyl substituted by hydrocarbon or unsubstituted; C6 to C40 aryl substituted by hydrocarbon or unsubstituted; C6 to C40 aryl having an hetero atom; C7 to C15 aralkyl substituted by hydrocarbon or unsubstituted; or C3 to C20 alkynyl.
17. The method for preparing a norbornene-ester based addition polymer according to claim 10, wherein the catalyst system of the step b) comprises 12,500 to 1100,000 of catalyst for the monomer in molar ratio.
18. The method for preparing a norbornene-ester based addition polymer according to claim 10, wherein the catalyst system of the step b) further comprises a cocatalyst.
19. The method for preparing a norbornene-ester based addition polymer according to claim 10, wherein the polymerization of the step b) is carried out at a temperature range of \u2212100 to 200\xb0 C.
20. An optical film comprising the norbornene-ester based addition polymer according to claim 1.
21. An optically anisotropic film comprising the norbornene-ester based addition polymer according to claim 1.
22. The optically anisotropic film according to claim 21, whose retardation value (Rth), defined by the following Equation 2, is 70 to 1000 nm:
Rth=\u0394(ny\u2212nz)\xd7d\u2003\u2003Equation 2
wherein
ny is the refractive index in the fast axis direction in a plane measured at a wavelength of 550 nm;
nz is the refractive index in the thickness direction measured at a wavelength of 550 nm; and
d is the film thickness.
23. The optically anisotropic film according to claim 21 which can be used for a negative C-plate type optical compensation film for LCDs, whose refractive indices satisfy the relationship of nx\u2248ny<\u2267nz (nx=the refractive index in the slow axis direction in a plane; ny=the refractive index in the fast axis direction in a plane; nz=the refractive index in the thickness direction).
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
We claim:
1. An apparatus for processing a semiconductor substrate, comprising:
a process chamber having a plurality of walls;
a substrate support to support the substrate within the process chamber;
a radiative heat source positioned outside the process chamber to heat the substrate through the walls when the substrate is positioned on the substrate support; and
a lens provided between the heat source and the substrate when the substrate is positioned on the substrate support, the lens affecting an intensity of radiation from the heat source incident on a portion of the substrate.
2. The apparatus of claim 1, wherein the lens is annular.
3. The apparatus of claim 2, wherein the lens is provided on one of the walls of the process chamber.
4. The apparatus of claim 3, wherein the lens is formed integrally with an upper wall of the process chamber.
5. The apparatus of claim 4, wherein the lens is adapted to focus radiation from the heat source towards an edge portion of the substrate.
6. The apparatus of claim 5, wherein the lens is adapted to focus radiation onto approximately an outer 25 mm periphery of the substrate.
7. The apparatus of claim 5, wherein the lens is adapted to focus radiation onto approximately an outer 5 mm periphery of the substrate.
8. The apparatus of claim 4, wherein the lens is adapted to diffuse radiation from the heat source to reduce the intensity of radiation incident on an interior portion of the substrate.
9. The apparatus of claim 8, wherein the lens is adapted to reduce the intensity of radiation incident on an annular portion of the substrate extending from an outer boundary at about 5 mm to 25 mm from the edge of the substrate to an inner boundary at about 15 mm to 50 mm from the edge of the substrate.
10. The apparatus of claim 8, wherein the lens is adapted to reduce the intensity of radiation incident on an annular portion of the substrate extending from an outer boundary at about 10 mm to 20 mm from the edge of the substrate to an inner boundary at about 25 mm to 40 mm from the edge of the substrate.
11. The apparatus of claim 5, further comprising a second lens provided between the heat source and the substrate when the substrate is positioned on the substrate support, the second lens being adapted to diffuse radiation from the heat source to reduce an intensity of radiation incident on a portion of the substrate inward of the edge portion.
12. The apparatus of claim 5, further comprising a diffusing surface provided between the heat source and the substrate when the substrate is positioned on the substrate support, the diffusing surface being adapted to diffuse radiation from the heat source to reduce an intensity of radiation incident on a portion of the substrate inward of the edge portion.
13. An apparatus for processing a semiconductor substrate, comprising:
a process chamber having a plurality of walls;
a substrate support to support the substrate within the process chamber;
a radiative heat source positioned outside the process chamber to heat the substrate through the walls when the substrate is positioned on the substrate support; and
a diffusing surface provided on a portion of at least one of the walls, the diffusing surface diffusing radiation from the heat source to reduce an intensity of radiation incident on a portion of the substrate.
14. The apparatus of claim 13, wherein the diffusing surface comprises a roughened area on an upper wall of the process chamber.
15. The apparatus of claim 14, wherein the diffusing surface reduces the intensity of radiation incident on the portion of the substrate by at least about 10 percent.
16. The apparatus of claim 14, wherein the diffusing surface reduces the intensity of radiation incident on the portion of the substrate by at least about 25 percent.
17. The apparatus of claim 14, wherein the diffusing surface is provided in an annular pattern above the portion of the substrate inward of the edge portion.
18. The apparatus of claim 14, wherein the diffusing surface is provided above an entire interior portion of the substrate excluding the edge portion of the substrate.
19. An apparatus for processing a semiconductor substrate, comprising:
a process chamber having a plurality of walls;
a substrate support to support the substrate within the process chamber;
a radiative heat source positioned outside the process chamber to heat the substrate through the walls when the substrate is positioned on the substrate support; and
means for altering an intensity of radiation from the heat source incident on one portion of the substrate relative to another portion of the substrate.
20. The apparatus of claim 19, wherein the diffusing means comprises a lens positioned between the heat source and the substrate.
21. The apparatus of claim 19, wherein the diffusing means comprises a roughened surface of one of the walls of the process chamber.
22. The apparatus of claim 21, wherein the diffusing means reduces the intensity of radiation incident on all of the substrate except approximately an outer 5 mm to 25 mm periphery of the substrate.
23. The apparatus of claim 21, wherein the diffusing means reduces the intensity of radiation incident on all of the substrate except approximately an outer 10 mm to 15 mm periphery of the substrate.
24. The apparatus of claim 21, wherein the diffusing means reduces the intensity of radiation incident on an annular portion of the substrate extending from an outer boundary at about 5 mm to 25 mm from the edge of the substrate to an inner boundary at about 15 mm to 50 mm from the edge of the substrate.
25. The apparatus of claim 21, wherein the diffusing means reduces the intensity of radiation incident on an annular portion of the substrate extending from an outer boundary at about 10 mm to 20 mm from the edge of the substrate to an inner boundary at about 25 mm to 40 mm from the edge of the substrate.
26. A method of processing a semiconductor substrate, comprising:
providing a reactor comprising a process chamber having a plurality of walls, a substrate support positioned in the process chamber, and a radiative heat source positioned outside the process chamber;
positioning a substrate on the substrate support; and
altering at least one of the walls to affect an intensity of radiation received at one portion of the substrate relative to another portion of the substrate; and
heating the substrate with the heat source.
27. The method of claim 26, wherein the reactor is adapted to perform a CVD process on the substrate.
28. The method of claim 27, wherein the altering comprises providing a lens on the at least one wall.
29. The method of claim 28, wherein the lens focuses radiation from the heat source towards an edge portion of the substrate.
30. The method of claim 28, wherein the lens diffuses radiation to reduce an intensity of radiation from the heat source incident on an interior portion of the substrate.
31. The method of claim 27, wherein the altering comprises roughening a portion of the at least one wall to reduce an intensity of radiation from the heat source incident on an interior portion of the substrate.