Infrared absorbing polymer, infrared absorbing/blocking film, photoelectric device, organic sensor, and electronic device
An infrared absorbing polymer includes a first structural unit represented by Chemical Formula 1 and a second structural unit including at least one of Chemical Formula 2A to Chemical Formula 2. The infrared absorbing polymer may be included in an infrared absorbing/blocking film, a photoelectric device, a sensor, and an electronic device.
1. An infrared absorbing polymer, comprising:
a first structural unit represented by Chemical Formula 1 and a second structural unit including at least one of Chemical Formula 2A to Chemical Formula 2I:
wherein, in Chemical Formula 1,
Ar is a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heteroaromatic ring, or a combination thereof,
X is O, S, Se, Te, S(═O), S(═O 2 ), NR a , CR b R c , SiR d R e , GeR f R g , CR h ═CR i , or CR hh ═CR ii , wherein R a , R b , R c , R d , R e , R f , R g , R h , and R i are independently hydrogen, deuterium, a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, a C6 to C14 aryl group, a C3 to C12 heteroaryl group, a halogen, a cyano group, or a combination thereof, and R hh and R ii are linked to each other to form an aromatic ring, and
R 1 and R 2 are a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C3 to C30 heteroaryl group, or R 1 and R 2 are linked to each other to form a substituted or unsubstituted C6 to C30 arene group and a substituted or unsubstituted C3 to C30 heteroarene group,
wherein, in Chemical Formula 2A,
X 1 is Se, Te, S(═O), S(═O) 2 , NR a , SiR d R e , or GeR f R g , wherein R a , R b , R c , R d , R e , R f , R g , R h , and R i are independently hydrogen, deuterium, a C1 to C20 alkyl group, a C1 to C20 haloalkyl group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, a halogen, a cyano group, or a combination thereof,
in Chemical Formulas 2B to 2I,
X 1 to X 3 are independently S, Se, Te, S(═O), S(═O) 2 , NR a , SiR d R e , or GeR f R g , wherein R a , R b , R c , R d , R e , R f , R g , R h , and R i are independently hydrogen, deuterium, a C1 to C20 alkyl group, a C1 to C20 haloalkyl group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, a halogen, a cyano group, or a combination thereof, provided that at least one of X 1 and X 2 is not S in Chemical Formulas 2B, 2C, 2F, and 2G, and
X 2 is not SiR d R e or GeR f R g in Chemical Formula 2D,
Z 1 and Z 2 are independently N or CR x , wherein R x is hydrogen, deuterium, a C1 to C10 alkyl group, a C1 to C10 haloalkyl group, a —SiH 3 group, a C1 to C10 alkylsilyl group, a —NH 2 group, a C1 to C10 alkylamine group, a C6 to C12 aryl group, a C3 to C12 heteroaryl group, a halogen, a cyano group, or a combination thereof,
Y 1 and Y 2 are independently O, S, Se, or Te,
in Chemical Formula 2H, n is 1,
in Chemical Formula 2I, n is 0 or 1, and
at least one hydrogen of each aromatic ring is optionally replaced by deuterium, a halogen, a cyano group, a C1 to C30 alkyl group, a C1 to C30 alkoxy group, a C1 to C30 haloalkyl group, a C6 to C30 aryl group, a C6 to C30 aryloxy group, a —SiH 3 group, or a C1 to C30 alkylsilyl group, wherein
the infrared absorbing polymer comprises about 20 mol % to about 50 mol % of the first structural unit and about 50 mol % to 80 mol % of the second structural unit.
2. The infrared absorbing polymer of claim 1 , wherein in Chemical Formula 1, Ar is benzene, a substituted or unsubstituted naphthalene, a substituted or unsubstituted anthracene, a substituted or unsubstituted phenanthrene, a substituted or unsubstituted tetracene, a substituted or unsubstituted pyrene, a substituted or unsubstituted quinoline, a substituted or unsubstituted isoquinoline, a substituted or unsubstituted quinoxaline, a substituted or unsubstituted quinazoline, or a substituted or unsubstituted phenanthroline.
3. The infrared absorbing polymer of claim 1 , wherein in Chemical Formula 1, Ar is one of the moieties represented by Chemical Formula A-1:
wherein, in Chemical Formula A-1,
at least one hydrogen of each aromatic ring is optionally replaced by deuterium, a halogen, a cyano group, a C1 to C10 alkyl group, a C1 to C10 haloalkyl group, a —SiH 3 group, or a C1 to C10 alkylsilyl group, and
* inside the aromatic ring is a portion that is bound to the N—X—N-containing ring and the pyrazine ring of Chemical Formula 1.
4. The infrared absorbing polymer of claim 1 , wherein in Chemical Formula 1, Ar is one of the moieties represented by Chemical Formula A-2:
wherein, in Chemical Formula A-2,
at least one hydrogen of each aromatic ring is optionally replaced by deuterium, a halogen, a cyano group, a C1 to C10 alkyl group, a C1 to C10 haloalkyl group, a —SiH 3 group, or a C1 to C10 alkylsilyl group, and
* inside the aromatic ring is a portion that is bound to the N—X—N-containing ring and the pyrazine ring of Chemical Formula 1.
5. The infrared absorbing polymer of claim 1 , wherein in Chemical Formula 1, the substituted or unsubstituted C6 to C30 arene group and a substituted or unsubstituted C3 to C30 heteroarene group formed by linking R 1 and R 2 to each other is a substituted or unsubstituted benzene, a substituted or unsubstituted naphthalene, a substituted or unsubstituted acenaphthene, a substituted or unsubstituted anthracene, a substituted or unsubstituted phenanthrene, a substituted or unsubstituted tetracene or a substituted or unsubstituted pyrene; or a substituted or unsubstituted quinoline, a substituted or unsubstituted isoquinoline, a substituted or unsubstituted quinoxaline, a substituted or unsubstituted quinazoline, a substituted or unsubstituted phenanthroline, a substituted or unsubstituted pyrimidine, or a substituted or unsubstituted benzodithiophene.
6. The infrared absorbing polymer of claim 1 , wherein in Chemical Formula 1, the substituted or unsubstituted C6 to C30 arene group and a substituted or unsubstituted C3 to C30 heteroarene group formed by linking R 1 and R 2 to each other is one of the moieties represented by Chemical Formula B-1 and Chemical Formula B-2:
wherein, in Chemical Formula B-1,
at least one hydrogen of each aromatic ring is optionally replaced by a halogen, a cyano group, a C1 to C30 alkyl group, a C1 to C30 alkoxy group, a C1 to C30 haloalkyl group, a —SiH 3 group, a C1 to C30 alkylsilyl group, a C6 to C30 aryl group, or a C3 to C30 heteroaryl group, and
* inside the aromatic ring is a portion that is bound to the pyrazine ring of Chemical Formula 1,
wherein, in Chemical Formula B-2,
at least one hydrogen of each aromatic ring is optionally replaced by a halogen, a cyano group, a C1 to C30 alkyl group, a C1 to C30 alkoxy group, a C1 to C30 haloalkyl group, a —SiH 3 group, a C1 to C30 alkylsilyl group, a C6 to C30 aryl group, a C6 to C30 aryloxy group, or a C3 to C30 heteroaryl group, and
* inside the aromatic ring is a portion that is bound to the pyrazine ring of Chemical Formula 1.
7. The infrared absorbing polymer of claim 1 , wherein in Chemical Formula 1, the substituted or unsubstituted C6 to C30 arene group and a substituted or unsubstituted C3 to C30 heteroarene group formed by linking R 1 and R 2 to each other is one of moieties represented by Chemical Formula B-3-1 or Chemical Formula B-3-2:
wherein, in Chemical Formulas B-3-1 and B-3-2,
Ar 11 and Ar 12 are independently a substituted or unsubstituted C6 to C30 arene group or a substituted or unsubstituted C3 to C30 heteroarene group,
in Chemical Formula B-3-1, Z 1 and Z 2 are independently N or CR x , wherein R x is hydrogen, deuterium, a C1 to C10 alkyl group, a C1 to C10 haloalkyl group, a —SiH 3 group, a C1 to C10 alkylsilyl group, a —NH 2 group, a C1 to C10 alkylamine group, a C6 to C10 arylamine group, a C6 to C14 aryl group, a C3 to C12 heteroaryl group, a halogen, a cyano group, or a combination thereof, and
* inside the aromatic ring is a portion that is bound to the pyrazine ring of Chemical Formula 1.
8. The infrared absorbing polymer of claim 7 , wherein
the moiety represented by Chemical Formula B-3-1 is represented by Chemical Formula B-3-11, and
the moiety represented by Chemical Formula B-3-2 is represented by Chemical Formula B-3-21:
wherein, in Chemical Formula B-3-11 and Chemical Formula B-3-21,
at least one hydrogen of each aromatic ring is optionally replaced by a halogen, a cyano group, a C1 to C30 alkyl group, a C1 to C30 alkoxy group, a C1 to C30 haloalkyl group, a —SiH 3 group, a C1 to C30 alkylsilyl group, a C6 to C30 aryl group, a C6 to C30 aryloxy group, or a C3 to C30 heteroaryl group,
X a and X b are independently —O—, —S—, —Se—, —Te—, —NR a —, —SiR b R c —, or —GeR d R e —, wherein R a , R b , R c , R d , and R e are independently hydrogen, a halogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C10 aryl group, and
* inside the aromatic ring is a portion that is bound to the pyrazine ring of Chemical Formula 1.
9. The infrared absorbing polymer of claim 1 , wherein the infrared absorbing polymer further comprises a third structural unit represented by Chemical Formula 3:
wherein, in Chemical Formula 3,
m is an integer of 0 to 3, and
at least one hydrogen of each aromatic ring is optionally replaced by deuterium, a halogen, a cyano group, a C1 to C10 alkyl group, a C1 to C10 haloalkyl group, a —SiH 3 group, or a C1 to C10 alkylsilyl group.
10. The infrared absorbing polymer of claim 9 , wherein the third structural unit is included in an amount of about 40 parts by mole to about 300 parts by mole based on 100 parts by mole of a sum of the first structural unit and the second structural unit.
11. The infrared absorbing polymer of claim 1 , wherein the infrared absorbing polymer exhibits a peak absorption wavelength in a wavelength range of about 750 nm to about 3000 nm.
12. An infrared absorbing/blocking film comprising:
the infrared absorbing polymer of claim 1 .
13. A photoelectric device, comprising:
a first electrode and a second electrode facing each other, and
a photoactive layer between the first electrode and the second electrode,
wherein the photoactive layer includes an infrared absorbing polymer including a first structural unit represented by Chemical Formula 1 and a second structural unit including at least one of Chemical Formula 2A to Chemical Formula 2I,
wherein, in Chemical Formula 1,
Ar is a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heteroaromatic ring, or a combination thereof,
X is O, S, Se, Te, S(═O), S(═O 2 ), NR a , CR b R c , SiR d R e , GeR f R g , CR h ═CR i , or CR hh ═CR ii , wherein R a , R b , R c , R d , R e , R f , R g , R h , and R i are independently hydrogen, deuterium, a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, a C6 to C14 aryl group, a C3 to C12 heteroaryl group, a halogen, a cyano group, or a combination thereof, and R hh and R ii are linked to each other to form an aromatic ring, and
R 1 and R 2 are a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C3 to C30 heteroaryl group, or R 1 and R 2 are linked to each other to form a substituted or unsubstituted C6 to C30 arene group and a substituted or unsubstituted C3 to C30 heteroarene group,
wherein, in Chemical Formula 2A,
X 1 is Se, Te, S(═O), S(═O) 2 , NR a , SiR d R e , or GeR f R g , wherein R a , R b , R c , R d , R e , R f , R g , R h , and R i are independently hydrogen, deuterium, a C1 to C20 alkyl group, a C1 to C20 haloalkyl group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, a halogen, a cyano group, or a combination thereof,
in Chemical Formulas 2B to 2I,
X 1 to X 3 are independently S, Se, Te, S(═O), S(═O) 2 , NR a , SiR d R e , or GeR f R g , wherein R a , R b , R c , R d , R e , R f , R g , R h , and R i are independently hydrogen, deuterium, a C1 to C20 alkyl group, a C1 to C20 haloalkyl group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, a halogen, a cyano group, or a combination thereof, provided that at least one of X 1 and X 2 is not S in Chemical Formulas 2B, 2C, 2F, and 2G, and
X 2 is not SiR d R e or GeR f R g in Chemical Formula 2D,
Z 1 and Z 2 are independently N or CR x , wherein R x is hydrogen, deuterium, a C1 to C10 alkyl group, a C1 to C10 haloalkyl group, a —SiH 3 group, a C1 to C10 alkylsilyl group, a —NH 2 group, a C1 to C10 alkylamine group, a C6 to C12 aryl group, a C3 to C12 heteroaryl group, a halogen, a cyano group, or a combination thereof,
Y 1 and Y 2 are independently O, S, Se, or Te,
in Chemical Formula 2H, n is 1,
in Chemical Formula 2I, n is 0 or 1, and
at least one hydrogen of each aromatic ring is optionally replaced by deuterium, a halogen, a cyano group, a C1 to C30 alkyl group, a C1 to C30 alkoxy group, a C1 to C30 haloalkyl group, a C6 to C30 aryl group, a C6 to C30 aryloxy group, a —SiH 3 group, or a C1 to C30 alkylsilyl group, wherein
the infrared absorbing polymer comprises about 20 mol % to about 50 mol % of the first structural unit and about 50 mol % to 80 mol % of the second structural unit.
14. The photoelectric device of claim 13 , wherein the photoactive layer further comprises fullerene or a fullerene derivative.
15. The photoelectric device of claim 13 , wherein a peak absorption wavelength of the photoactive layer belong to a wavelength region of about 750 nm to about 3000 nm.
16. The photoelectric device of claim 13 , wherein
the photoactive layer comprises the infrared absorbing polymer; and
an n-type semiconductor connected to the infrared absorbing polymer.
17. The photoelectric device of claim 13 , wherein
the infrared absorbing polymer comprises about 20 mol % to about 50 mol % of the first structural unit and about 50 mol % to 80 mol % of the second structural unit, and
the infrared absorbing polymer exhibits a peak absorption wavelength in a wavelength range of about 750 nm to about 3000 nm.
18. A sensor comprising:
the photoelectric device of claim 14 .
19. An electronic device comprising:
the photoelectric device of claim 14 .