Infrared absorbing composition, and photoelectric device, organic sensor and electronic device comprising same

文档序号：1877338 发布日期：2021-11-23 浏览：13次中文

阅读说明：本技术 红外吸收组合物、以及包括其的光电器件、有机传感器和电子设备 (Infrared absorbing composition, and photoelectric device, organic sensor and electronic device comprising same ) 是由朴仁仙金来成林东晰于 2021-05-19 设计创作，主要内容包括：公开了红外吸收组合物、以及包括其的光电器件、有机传感器和电子设备。所述红外吸收组合物包括由化学式1表示的p型半导体化合物和n型半导体化合物。所述n型半导体化合物包括由化学式2A表示的化合物、由化学式2B表示的化合物、由化学式2C表示的化合物、富勒烯衍生物或其组合。所述p型半导体化合物和所述n型半导体化合物提供体异质结(BHJ)结构。(Disclosed are infrared absorbing compositions, and optoelectronic devices, organic sensors, and electronic devices comprising the same. The infrared absorbing composition includes a p-type semiconductor compound and an n-type semiconductor compound represented by chemical formula 1. The n-type semiconductor compound includes a compound represented by chemical formula 2A, a compound represented by chemical formula 2B, a compound represented by chemical formula 2C, a fullerene derivative, or a combination thereof. The p-type semiconductor compound and the n-type semiconductor compound provide a Bulk Heterojunction (BHJ) structure.)

1. An infrared absorbing composition comprising

A p-type semiconductor compound represented by chemical formula 1, and

an n-type semiconductor compound including a compound represented by chemical formula 2A, a compound represented by chemical formula 2B, a compound represented by chemical formula 2C, a fullerene derivative, or a combination thereof,

wherein the p-type semiconductor compound and the n-type semiconductor compound provide a Bulk Heterojunction (BHJ) structure,

[ chemical formula 1]

Wherein, in chemical formula 1,

m is Sn, Ni, V, Al, Zn, Si, Co, or Ge,

x is a halogen, and X is a halogen,

m is an integer of 0 to 4,

n is a number of 0 or 1,

two R^1aTwo R^2aTwo R^3aAnd two R^4aEach independently hydrogen, deuterium, halogen, cyano, C1 to C20 haloalkyl, C1 to C20 cyanoalkyl, C1 to C20 alkyl or C1 to C20 alkoxy, provided that two R are^1aAt least one, two R^2aAt least one, two R^3aAt least one and two R^4aAt least one of (A) is a C1 to C20 alkyl group or a C1 to C20 alkoxy group,

R^1b、R^1c、R^1d、R^2b、R^2c、R^2d、R^3b、R^3c、R^3d、R^4b、R^4cand R^4dEach independently hydrogen, deuterium, halogen, C1 to C20 haloalkyl, cyano, C1 to C20 cyanoalkyl, C1 to C20 alkyl or C1 to C20 alkoxy,

b is an integer of 0 to 2, and

n1, n2, n3 and n4 are each independently an integer of 1 to 4,

[ chemical formula 2A ]

Wherein, in chemical formula 2A,

Ar¹is one of the moieties represented by chemical formula 3,

X¹and X²Each independently S, Se or Te,

Ar¹¹、Ar¹²、Ar²¹and Ar²²Each independently a substituted or unsubstituted C6-C10 aryl or substituted or unsubstituted C3-C10 heteroaryl,

Ar³¹and Ar³²Each independently has a formula selected from the group consisting of C O, C ═ S, C ═ Se, C ═ Te, and C ═ CN₂A substituted or unsubstituted C6 to C30 hydrocarbon ring group having at least one functional group selected from C ═ O, C ═ S, C ═ Se, C ═ Te and C ═ CN₂A substituted or unsubstituted heterocyclic group of C2 to C30, or a condensed ring thereof, and

R¹and R²Each independently hydrogen or C1 to C10 alkyl,

[ chemical formula 3]

Wherein, in chemical formula 3,

X^aand X^bEach independently S, Se or Te,

R^aand R^bEach independently hydrogen or C1 to C20 alkyl, and

a and b are each independently 1 or 2,

[ chemical formula 2B ]

Wherein, in chemical formula 2B,

Ar²is one of the moieties represented by chemical formula 3,

X¹、X²、X³and X⁴Each independently S, Se or Te,

Ar¹¹、Ar¹²、Ar²¹and Ar²²Each independently a substituted or unsubstituted C6-C10 aryl or substituted or unsubstituted C3-C10 heteroaryl,

R¹and R²Each independently hydrogen or C1 to C10 alkyl,

[ chemical formula 2C ]

Wherein, in chemical formula 2C,

Ar³is one of the moieties represented by chemical formula 4,

X¹、X²、X³and X⁴Each independently S, Se or Te,

R³and R⁴Each independently hydrogen, C1 to C20 alkyl, C6 to C10 aryl, or C2 to C10 heteroaryl,

R¹and R²Each independently hydrogen or C1 to C10 alkyl,

[ chemical formula 4]

Wherein, in chemical formula 4,

Y¹is CR^pR^q、NR^rO, S, Se, or Te, wherein R^p、R^qAnd R^rEach independently hydrogen or C1 to C20 alkyl, and

Z¹to Z⁴Each independently is CR^sOr N, wherein R^sIs hydrogen or C1 to C20 alkyl.

2. The infrared absorbing composition as set forth in claim 1, wherein the p-type semiconductor compound represented by chemical formula 1 is one of compounds represented by chemical formulas 1A to 1C:

[ chemical formula 1A ]

[ chemical formula 1B ]

[ chemical formula 1C ]

Wherein, in chemical formulas 1A to 1C,

R^1a、R^1b、R^1c、R^1d、R^2a、R^2b、R^2c、R^2d、R^3a、R^3b、R^3c、R^3d、R^4a、R^4b、R^4c、R^4db, n1, n2, n3 and n4 are the same as in chemical formula 1,

wherein, in chemical formula 1C,

R^5aand R^5bIs hydrogen, C1 to C6 alkyl, or C1 to C6 alkoxy.

3. The infrared absorbing composition as set forth in claim 1, wherein X is Cl in chemical formula 1.

4. The infrared absorbing composition as set forth in claim 1, wherein in chemical formula 1, two R are^1aTwo R^2aTwo R^3aAnd two R^4aIs C1 to C20 alkyl or C1 to C20 alkoxy.

5. The infrared absorbing composition as set forth in claim 1, wherein in chemical formulas 2A and 2B, Ar¹¹、Ar¹²、Ar²¹And Ar²²Each independently is:

c6 to C10 aryl substituted by C1 to C20 alkyl or C1 to C20 alkoxy, or

C3 to C10 heteroaryl substituted with C1 to C20 alkyl or C1 to C20 alkoxy.

6. The infrared absorbing composition as set forth in claim 1, wherein in chemical formulas 2A, 2B and 2C, Ar³¹And Ar³²Is a cyclic group represented by one of chemical formulas 5A to 5F:

[ chemical formula 5A ]

Wherein, in chemical formula 5A,

Z¹and Z²Each independently is O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bEach independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

Z³is N or CR^cWherein R is^cIs hydrogen, deuterium or a substituted or unsubstituted C1 to C10 alkyl group,

R¹¹、R¹²、R¹³、R¹⁴and R¹⁵Each independently is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen, cyano (-CN), a cyano-containing group, or a combination thereof, wherein R is hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a halogen, a cyano (-CN), a cyano-containing group, or a combination thereof¹²、R¹³、R¹⁴And R¹⁵Each independently present or R¹²And R¹³And R¹⁴And R¹⁵Are linked to each other to provide a fused aromatic ring,

n is 0 or 1, and

is the position of the connection point,

[ chemical formula 5B ]

Wherein, in chemical formula 5B,

Z¹and Z²Each independently is O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bEach independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

Z³is O, S, Se, Te or C (R)^a) (CN) wherein R^aIs hydrogen, cyano (-CN), or C1 to C10 alkyl,

R¹¹and R¹²Each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen, cyano (-CN), or a combination thereof, and

is the position of the connection point,

[ chemical formula 5C ]

Wherein, in chemical formula 5C,

Z¹and Z²Each independently is O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bEach independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

R¹¹、R¹²and R¹³Each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen, cyano (-CN), or a combination thereof, and

is the position of the connection point,

[ chemical formula 5D ]

Wherein, in chemical formula 5D,

Z¹and Z²Each independently is O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bEach independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

Z³is N or CR^cWherein R is^cIs hydrogen or substituted or unsubstituted C1 to C10 alkyl,

G¹is O, S, Se, Te, SiR^xR^yOr GeR^zR^wWherein R is^x、R^y、R^zAnd R^wEach independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl,

R¹¹、R¹²and R¹³Each independently is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen, cyano, a cyano-containing group, or a combination thereof, wherein R is hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a halogen, a cyano-containing group, or a combination thereof, wherein R is hydrogen, deuterium, a substituted or unsubstituted C-containing group, or a combination thereof¹²And R¹³Each independently present or linked to each other to provide a fused aromatic ring,

n is a number of 0 or 1,

is the position of the connection point,

[ chemical formula 5E ]

Wherein, in chemical formula 5E,

Z¹and Z²Each independently is O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bEach independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

Z³is N or CR^cWherein R is^cIs hydrogen or substituted or unsubstituted C1 to C10 alkyl,

G²is O, S, Se, Te, SiR^xR^yOr GeR^zR^wWherein R is^x、R^y、R^zAnd R^wEach independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl,

n is 0 or 1, and

is the position of the connection point,

[ chemical formula 5F ]

Wherein, in chemical formula 5F,

Z¹and Z²Each independently is O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bEach independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

R¹¹is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen, cyano (-CN), a cyano-containing group, or a combination thereof, and

G³is O, S, Se, Te, SiR^xR^yOr GeR^zR^wWherein R is^x、R^y、R^zAnd R^wEach independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl.

7. The infrared absorbing composition of claim 1, wherein

The compound represented by chemical formula 2A is a compound represented by chemical formula 2A-1,

the compound represented by chemical formula 2B is a compound represented by chemical formula 2B-1:

[ chemical formula 2A-1]

Wherein, in chemical formula 2A-1,

Ar¹is one of the moieties represented by chemical formula 3,

X¹and X²Each independently S, Se or Te,

R¹and R²Each independently hydrogen or C1 to C10 alkyl,

R¹¹、R¹²、R²¹and R²²Each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl, x1, y1, x2, and y2 each independently are integers from 0 to 5, and

Ar³¹and Ar³²Each independently has a formula selected from the group consisting of C O, C ═ S, C ═ Se, C ═ Te, and C ═ CN₂Has at least one functional group selected from the group consisting of C-O, C, a substituted or unsubstituted C6 to C30 hydrocarbon ring groupSe, C Te and C (CN) S, C₂A substituted or unsubstituted C2 to C30 heterocyclic group of at least one functional group of (A), or a fused ring thereof,

[ chemical formula 2B-1]

Wherein, in chemical formula 2B-1,

Ar²is one of the moieties represented by chemical formula 3,

X¹、X²、X³and X⁴Each independently S, Se or Te,

R¹and R²Each independently hydrogen or C1 to C10 alkyl,

Ar³¹and Ar³²Each independently has a formula selected from the group consisting of C O, C ═ S, C ═ Se, C ═ Te, and C ═ CN₂A substituted or unsubstituted C6 to C30 hydrocarbon ring group having at least one functional group selected from C ═ O, C ═ S, C ═ Se, C ═ Te and C ═ CN₂A substituted or unsubstituted C2 to C30 heterocyclic group of at least one functional group of (a), or a fused ring thereof.

8. The ir-absorbing composition as set forth in claim 1, wherein the fullerene derivative comprises a C60 to C120 fullerene substituted with a first functional group of an aryl or heterocyclic group and a second functional group of an alkyl ester group.

9. The ir-absorbing composition as claimed in claim 1, wherein the fullerene derivative comprises [6,6] -phenyl-C61-butyric acid methyl ester (PC60BM), bis (1- [3- (methoxycarbonyl) propyl ] -1-phenyl) - [6,6] C62 (bis-PCBM), phenyl-C70-butyric acid methyl ester (PC70BM), indene-C60 bis adduct (ICBA), or indene-C60 mono adduct (ICMA).

10. The infrared absorbing composition of claim 1, wherein the p-type semiconductor compound and the n-type semiconductor compound are included in a volume ratio of 1:0.1 to 1:10 p-type semiconductor compound to n-type semiconductor compound.

11. The infrared absorbing composition of claim 1, wherein the infrared absorbing composition has a peak absorption wavelength in the wavelength range of 800nm to 3000 nm.

12. The infrared absorbing composition as set forth in claim 1, wherein n is 0 in chemical formula 1.

13. The infrared absorbing composition as set forth in claim 1, wherein n is 1 in chemical formula 1.

14. The infrared absorbing composition as set forth in claim 1, wherein n1-n4 is 1 in chemical formula 1.

15. The infrared absorbing composition of claim 1, wherein X is in formulas 2A, 2B, and 2C¹、X²、X³And X⁴Is S.

16. The infrared absorbing composition of claim 1, wherein the n-type semiconductor compound comprises a compound represented by chemical formula 2B.

17. An optoelectronic 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 comprises an infrared absorbing composition as set forth in any one of claims 1 to 16.

18. An organic sensor comprising an optoelectronic device according to claim 17.

19. An electronic device, comprising:

an organic sensor according to claim 18 or an optoelectronic device according to claim 17.

Technical Field

Infrared absorbing compositions and optoelectronic devices, organic sensors, and/or electronic devices comprising the same are disclosed.

Background

The imaging apparatus may be used in a digital camera, a camcorder, and the like to capture an image and store it as an electrical signal, and may include a sensor for separating incident light according to wavelength and converting each component into an electrical signal.

Recently, optoelectronic devices in the infrared region have been investigated to improve the sensitivity of the sensor in low light environments and/or for use as biometric devices.

Disclosure of Invention

Some embodiments provide infrared absorbing compositions having improved infrared light absorbing characteristics.

Some embodiments provide an infrared absorbing/blocking film comprising the infrared absorbing composition.

Some embodiments provide an optoelectronic device comprising the infrared absorbing composition.

Some embodiments provide a sensor comprising the infrared absorbing composition or photovoltaic device.

Some embodiments provide an electronic device comprising the optoelectronic device or sensor.

According to some embodiments, the infrared absorbing composition comprises: a p-type semiconductor compound represented by chemical formula 1; and an n-type semiconductor compound selected from a compound represented by chemical formula 2A, a compound represented by chemical formula 2B, a compound represented by chemical formula 2C, a fullerene derivative, or a combination thereof; wherein the p-type semiconductor compound and the n-type semiconductor compound provide a Bulk Heterojunction (BHJ) structure.

[ chemical formula 1]

In the chemical formula 1, the first and second,

m may be Sn, Ni, V, Al, Zn, Si, Co, or Ge,

x may be a halogen or a halogen,

m may be an integer of 0 to 4

n can be either 0 or 1 and,

two R^1aTwo R^2aTwo R^3aAnd two R^4aEach independently hydrogen, deuterium, halogen, cyano (-CN), C1 to C20 haloalkyl, C1 to C20 cyanoalkyl, C1 to C20 alkyl or C1 to C20 alkoxy, provided that two R are^1aAt least one, two R^2aAt least one, two R^3aAt least one and two R^4aAt least one of (A) is a C1 to C20 alkyl group or a C1 to C20 alkoxy group,

R^1b、R^1c、R^1d、R^2b、R^2c、R^2d、R^3b、R^3c、R^3d、R^4b、R^4cand R^4dMay each independently be hydrogen, deuterium, halogen, C1 to C20 haloalkyl, cyano (-CN), C1 to C20 cyanoalkyl, C1 to C20 alkyl or C1 to C20 alkoxy,

b may be an integer of 0 to 2, and

n1, n2, n3 and n4 are each independently an integer of 1 to 4,

[ chemical formula 2A ]

Wherein, in chemical formula 2A,

Ar¹may be one of the moieties represented by chemical formula 3,

X¹and X²May each independently be S, Se or Te,

Ar¹¹、Ar¹²、Ar²¹and Ar²²Each independently a substituted or unsubstituted C6-C10 aryl or substituted or unsubstituted C3-C10 heteroaryl,

Ar³¹and Ar³²Each independently may be a group having a general formula selected from C-O, C-S, C-Se, C-Te and C-CN₂A substituted or unsubstituted C6 to C30 hydrocarbon ring group having at least one functional group selected from C ═ O, C ═ S, C ═ Se, C ═ Te and C ═ CN₂A substituted or unsubstituted heterocyclic group of C2 to C30, or a condensed ring thereof, and

R¹and R²May each independently be hydrogen or a C1 to C10 alkyl group,

[ chemical formula 3]

Wherein, in chemical formula 3,

X^aand X^bMay each independently be S, Se or Te,

R^aand R^bMay each independently be hydrogen or C1 to C20 alkyl, and

a and b may each independently be 1 or 2,

[ chemical formula 2B ]

Wherein, in chemical formula 2B,

Ar²may be one of the moieties represented by chemical formula 3,

X¹、X²、X³and X⁴May each independently be S, Se or Te,

Ar¹¹、Ar¹²、Ar²¹and Ar²²Each independently a substituted or unsubstituted C6-C10 aryl or substituted or unsubstituted C3-C10 heteroaryl,

R¹and R²May each independently be hydrogen or a C1 to C10 alkyl group,

[ chemical formula 2C ]

Wherein, in chemical formula 2C,

Ar³may be one of the moieties represented by chemical formula 4,

X¹、X²、X³and X⁴May each independently be S, Se or Te,

R³and R⁴May each independently be hydrogen, C1 to C20 alkyl, C6 to C10 aryl, or C2 to C10 heteroaryl,

R¹and R²May each independently be hydrogen or a C1 to C10 alkyl group,

[ chemical formula 4]

Wherein, in chemical formula 4,

Y¹may be CR^pR^q、NR^rO, S, Se, or Te, wherein R^p、R^qAnd R^rMay each independently be hydrogen or C1 to C20 alkyl, and

Z¹to Z⁴May each independently be CR^sOr N, wherein R^sMay be hydrogen or a C1 to C20 alkyl group.

In some embodiments, the p-type semiconductor compound represented by chemical formula 1 is one of compounds represented by chemical formulas 1A to 1C: [ chemical formula 1A ]

[ chemical formula 1B ]

[ chemical formula 1C ]

In the chemical formulae 1A to 1C,

R^1a、R^1b、R^1c、R^1d、R^2a、R^2b、R^2c、R^2d、R^3a、R^3b、R^3c、R^3d、R^4a、R^4b、R^4c、R^4db, n1, n2, n3 and n4 are the same as in chemical formula 1,

wherein, in chemical formula 1C,

R^5aand R^5bMay each independently be hydrogen, C1 to C6 alkyl, or C1 to C6 alkoxy.

In some embodiments, in chemical formula 1, X may be Cl.

In some embodiments, in chemical formula 1, two R are^1aTwo R^2aTwo R^3aAnd two R^4aMay be a C1 to C20 alkyl group or a C1 to C20 alkoxy group.

In some embodiments, in chemical formulas 2A and 2B, Ar¹¹、Ar¹²、Ar²¹And Ar²²Each independently may be: c6 to C10 aryl substituted with C1 to C20 alkyl or C1 to C20 alkoxy, or C3 to C10 heteroaryl substituted with C1 to C20 alkyl or C1 to C20 alkoxy.

In some embodiments, in chemical formulas 2A to 2C, Ar³¹And Ar³²May be a cyclic group represented by one of chemical formulas 5A to 5F:

[ chemical formula 5A ]

In the chemical formula 5A, the first and second,

Z¹and Z²May each independently be O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bMay each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

Z³may be N or CR^cWherein R is^cMay be hydrogen, deuterium or a substituted or unsubstituted C1 to C10 alkyl group,

R¹¹、R¹²、R¹³、R¹⁴and R¹⁵Each independently can be hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen, cyano (-CN), a cyano-containing group, or a combination thereof, wherein R is hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a halogen, a cyano (-CN), a cyano-containing group, or a combination thereof¹²、R¹³、R¹⁴And R¹⁵May each independently be present or R¹²And R¹³And R¹⁴And R¹⁵May be linked to each other to provide a fused aromatic ring,

n is 0 or 1, and

may be a connection location.

In an embodiment, CR of formula 5A¹¹、CR¹²、CR¹³、CR¹⁴And CR¹⁵May be replaced by nitrogen (N). That is, the substituted or unsubstituted benzene ring moiety of chemical formula 5A may include a heteroatom, such as nitrogen (N).

[ chemical formula 5B ]

In the chemical formula 5B, the first and second,

Z¹and Z²May each independently be O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bMay each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyanogenThe base group is a group of a compound,

Z³can be O, S, Se, Te or C (R)^a) (CN) wherein R^aIs hydrogen, cyano (-CN), or C1 to C10 alkyl,

R¹¹and R¹²May each independently be hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen, cyano (-CN), or a combination thereof, and

may be a connection location.

[ chemical formula 5C ]

In the chemical formula 5C, the metal oxide,

Z¹and Z²May each independently be O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bMay each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

R¹¹、R¹²and R¹³May each independently be hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen, cyano (-CN), or a combination thereof, and

may be a connection location.

[ chemical formula 5D ]

In the chemical formula 5D, the metal oxide,

Z¹and Z²May each independently be O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bMay each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

Z³may be N or CR^cWherein R is^cMay be hydrogen or substituted or unsubstituted C1 to C10 alkyl,

G¹can be O, S, Se, Te, SiR^xR^yOr GeR^zR^wWherein R is^x、R^y、R^zAnd R^wEach independently can be hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl,

R¹¹、R¹²and R¹³Each independently can be hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen, cyano, a cyano-containing group, or a combination thereof, wherein R is hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a halogen, a cyano-containing group, or a combination thereof, wherein R is hydrogen, a cyano-containing group, a substituted or unsubstituted C-containing group, or a combination thereof¹²And R¹³May each be independently present or attached to each other to provide a fused aromatic ring,

n may be 0 or 1, and

may be a connection location.

[ chemical formula 5E ]

In the chemical formula 5E, the metal oxide,

Z¹and Z²May each independently be O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bMay each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

Z³may be N or CR^cWherein R is^cMay be hydrogen or substituted or unsubstituted C1 to C10 alkyl,

G²can be O, S, Se, Te, SiR^xR^yOr GeR^zR^wWherein R is^x、R^y、R^zAnd R^wEach independently can be hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl,

may be a connection location.

[ chemical formula 5F ]

In the chemical formula 5F, the metal oxide,

Z¹and Z²May each independently be O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bMay each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

G³is O, S, Se, Te, SiR^xR^yOr GeR^zR^wWherein R is^x、R^y、R^zAnd R^wEach independently can be hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl.

In some embodiments, the compound represented by chemical formula 2A may be a compound represented by chemical formula 2A-1.

[ chemical formula 2A-1]

In the chemical formula 2A-1,

Ar¹may be one of the moieties represented by chemical formula 3,

X¹and X²Can each beIndependently S, Se or Te,

R¹and R²May each independently be hydrogen or a C1 to C10 alkyl group,

R¹¹、R¹²、R²¹and R²²May each independently be hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl, x1, y1, x2, and y2 may each independently be an integer of 0 to 5, and

Ar³¹and Ar³²Each independently may be a group having a general formula selected from C-O, C-S, C-Se, C-Te and C-CN₂A substituted or unsubstituted C6 to C30 hydrocarbon ring group having at least one functional group selected from C ═ O, C ═ S, C ═ Se, C ═ Te and C ═ CN₂A substituted or unsubstituted C2 to C30 heterocyclic group of at least one functional group of (a), or a fused ring thereof.

In some embodiments, the compound represented by chemical formula 2B may be a compound represented by chemical formula 2B-1.

[ chemical formula 2B-1]

In the chemical formula 2B-1,

Ar²may be one of the moieties represented by chemical formula 3,

X¹、X²、X³and X⁴May each independently be S, Se or Te,

R¹and R²Each independently may be hydrogen or a C1 to C10 alkyl group,

Ar³¹and Ar³²Each independently may be of the formula selected from C-O, C-S, C-Se, C-Te and C-CN₂By substitution or non-substitution of at least one functional groupSubstituted C6 to C30 hydrocarbon ring groups having a structure selected from C O, C-S, C-Se, C-Te and C (CN)₂A substituted or unsubstituted C2 to C30 heterocyclic group of at least one functional group of (a), or a fused ring thereof.

In some embodiments, the fullerene derivative may include a C60 to C120 fullerene substituted with a first functional group of an aryl or heterocyclic group and a second functional group of an alkyl ester group. The aryl group may be phenyl, naphthyl or anthracenyl. The heterocyclic group can be furyl, thienyl, pyrrolyl,Oxazolyl, pyridyl, pyrimidinyl, quinolinyl, or carbazolyl.

In some embodiments, the fullerene derivative may include [6,6] -phenyl-C61-butyric acid methyl ester (PC60BM), bis (1- [3- (methoxycarbonyl) propyl ] -1-phenyl) - [6,6] C62 (bis-PCBM), phenyl-C70-butyric acid methyl ester (PC70BM), indene-C60 bis adduct (ICBA), or indene-C60 mono adduct (ICMA).

In some embodiments, the p-type semiconductor compound and the n-type semiconductor compound may be included at a volume ratio (p-type semiconductor compound: n-type semiconductor compound) of about 1:0.1 to about 1: 10.

An infrared absorbing composition may include the p-type semiconductor compound and the n-type semiconductor compound, and may exhibit a peak absorption wavelength in a wavelength range of about 800nm to about 3000 nm.

In some embodiments, in chemical formula 1, n may be 0.

In some embodiments, in chemical formula 1, n may be 1.

In some embodiments, in chemical formula 1, n1-n4 may be 1.

In some embodiments, in chemical formulas 2A, 2B and 2C, X¹、X²、X³And X⁴May be S.

In some embodiments, the n-type semiconductor compound may include a compound represented by chemical formula 2B.

According to some embodiments, an optoelectronic device comprises: 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 comprises the infrared absorbing composition comprising the p-type semiconductor compound and the n-type semiconductor compound.

According to some embodiments, a sensor comprising the optoelectronic device is provided.

According to some embodiments, an electronic device comprising the optoelectronic device or sensor is provided.

The infrared absorbing composition can exhibit good light absorption properties in the infrared region and thus can be effectively used in optoelectronic devices and/or sensors.

Drawings

Figure 1 is a cross-sectional view showing an optoelectronic device according to some embodiments,

figure 2 is a cross-sectional view showing an optoelectronic device according to some embodiments,

figure 3 is a cross-sectional view illustrating an image sensor according to one embodiment,

figure 4 is a cross-sectional view illustrating an image sensor according to another embodiment,

figure 5 is a cross-sectional view illustrating an image sensor according to another embodiment,

figure 6 is a cross-sectional view illustrating an image sensor according to another embodiment,

figure 7 is a cross-sectional view illustrating an image sensor according to another embodiment,

figure 8 is a cross-sectional view illustrating an image sensor according to another embodiment,

fig. 9 is a block diagram of a digital camera including an image sensor according to an embodiment; and

fig. 10 is a block diagram of an electronic device according to an embodiment.

Detailed Description

Hereinafter, the embodiments will be described in detail, and can be easily performed by a person having ordinary knowledge in the related art. This disclosure may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

In the drawings, the thickness of layers, films, panels, regions, etc. have been exaggerated for clarity.

It will be understood that when an element such as a layer, film, region or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.

In the drawings, portions irrelevant to the description are omitted for clarity of the embodiment, and the same or similar constituent elements are denoted by the same reference numerals throughout the specification.

Hereinafter, "combination" includes two or more kinds of mutually substituted mixtures, and a laminated structure of two or more kinds.

As used herein, "substituted" when a specific definition is not otherwise provided means that the hydrogen of a compound or functional group is replaced with a substituent selected from the group consisting of: a halogen atom, a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazine group, a hydrazone group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a silyl group, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroaryl group, a C3 to C20 heteroaryl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C3 to C30 heterocycloalkyl group, and a combination thereof.

As used herein, when a specific definition is not otherwise provided, the term "hetero" means that it includes 1 to 4 hetero atoms selected from N, O, S, Se, Te, Si and P.

As used herein, when a definition is not otherwise provided, "aromatic ring" refers to a functional group in which all atoms in the cyclic functional group have p-orbitals, and wherein these p-orbitals are conjugated, and "heteroaromatic ring" refers to an aromatic ring that includes a heteroatom. By "aromatic ring" is meant a C6 to C30 aromatic hydrocarbon group, for example a C6 to C20 aromatic hydrocarbon group, or a C6 to C30 aryl group, for example a C6 to C20 aryl group. "heteroaromatic ring" means a C3 to C30 heteroaromatic hydrocarbon group, for example a C3 to C20 heteroaromatic hydrocarbon group or a C3 to C30 heteroaryl group, for example a C3 to C20 heteroaryl group.

As used herein, "aromatic hydrocarbon group" refers to a hydrocarbon group having an aromatic ring, and includes monocyclic and polycyclic hydrocarbon groups, and the additional rings of the polycyclic hydrocarbon group may be aromatic rings or non-aromatic rings. "heteroaromatic radical" means an aromatic hydrocarbon radical containing from 1 to 3 heteroatoms selected from the group consisting of N, O, S, Se, Te, P and Si in the ring.

As used herein, when a definition is not otherwise provided, "aryl" refers to a group including at least one hydrocarbon aromatic moiety, and may include groups in which all elements of the hydrocarbon aromatic moiety have p-orbitals forming conjugates, such as phenyl, naphthyl, and the like; groups in which two or more hydrocarbon aromatic moieties may be joined by sigma bonds, such as biphenyl, terphenyl, quaterphenyl, and the like; and groups in which two or more hydrocarbon aromatic moieties are fused, directly or indirectly, to provide a non-aromatic fused ring, such as fluorenyl. The aryl group can include monocyclic, polycyclic, or fused polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

As used herein, when a definition is not otherwise provided, "heteroaryl" refers to an aryl group including at least one heteroatom selected from N, O, S, Se, Te, P, and Si in a ring in place of carbon (C). When the heteroaryl group is a fused ring, at least one of the rings of the heteroaryl group may have a heteroatom or each ring may have a heteroatom.

As used herein, when a definition is not otherwise provided, "halogen" may be one of F, Cl, Br, or I, and haloalkyl may be an alkyl in which at least one hydrogen is replaced with halogen, and may be, for example, a perfluoroalkyl such as CF₃。

As used herein, a "hydrocarbon ring group" may include an aromatic ring (aromatic hydrocarbon ring), or a fused ring of an aromatic ring and a non-aromatic ring (alicyclic ring). The aromatic ring may include, for example, a C6 to C30 aryl group, a C6 to C20 aryl group, or a C6 to C10 aryl group, and the condensed ring may include a condensed ring formed by connecting at least one aromatic ring (aromatic hydrocarbon ring) such as a C6 to C30 aryl group, a C6 to C20 aryl group, or a C6 to C10 aryl group with at least one non-aromatic ring (alicyclic ring) such as a C3 to C30 cycloalkyl group, a C3 to C20 cycloalkyl group, or a C3 to C10 cycloalkyl group.

As used herein, "heterocyclic group" refers to a cyclic group comprising a heteroatom selected from N, O, S, Se, Te, P, and Si in place of 1 to 3 carbon atoms in a cyclic group selected from: an aromatic hydrocarbon group (e.g., C6 to C30 aryl, C6 to C20 aryl, or C6 to C10 aryl), an alicyclic hydrocarbon group (e.g., C3 to C30 cycloalkyl, C3 to C20 cycloalkyl, or C3 to C10 cycloalkyl), or a condensed ring thereof. At least one carbon atom of the heterocyclic group may also be replaced by a thiocarbonyl group (C ═ S).

As used herein, "fused ring" refers to a fused ring formed by bonding two or more cyclic groups selected from: aromatic hydrocarbon groups (e.g., C6 to C30 aryl, C6 to C20 aryl, or C6 to C10 aryl) and alicyclic hydrocarbon groups (e.g., C3 to C30 cycloalkyl, C3 to C20 cycloalkyl, or C3 to C10 cycloalkyl).

As used herein, when a definition is not otherwise provided, "cyano-containing group" refers to a monovalent group in which at least one hydrogen is replaced by a cyano group, such as C1 to C30 alkyl, C2 to C30 alkenyl, or C2 to C30 alkynyl. Cyano-containing radicals also mean divalent radicals, e.g. ═ CR^x′-(CR^xR^y)_p-CR^y′(CN)₂Wherein R is^x、R^y、R^x′And R^y′Independently hydrogen or C1 to C10 alkyl, and p can be an integer from 0 to 10 (or 1 to 10). Specific examples of the cyano-containing group may be dicyanomethyl, dicyanovinyl, cyanoethynyl, and the like.

As used herein, when a definition is not otherwise provided, "infrared wavelength region" includes a near-infrared/infrared wavelength region having a wavelength region of about 800nm to about 3000 nm.

When the term "about" or "substantially" is used in this specification in reference to a numerical value, it is intended that the relevant numerical value includes manufacturing or operating tolerances (e.g., ± 10%) around that numerical value. Further, when the words "substantially" and "substantially" are used with respect to a geometric shape, it is intended that the precision of the geometric shape is not required, but that the tolerances (limits) for the shape are within the scope of the present disclosure. Further, whether a value or shape is modified to be "about" or "substantially," it is to be understood that such values and shapes are to be interpreted as including manufacturing or operating tolerances (e.g., ± 10%) around the value or shape.

The expression "at least one of" when preceding or following a list of elements (e.g., A, B and C) modifies the entire list of elements and does not modify individual elements of the list. For example, "at least one of A, B and C", "at least one of A, B or C", "one of A, B, C or a combination thereof", and "one of A, B, C and a combination thereof", respectively, can be construed to encompass any of the following: a; b; a and B; a and C; b and C; and A, B and C.

Hereinafter, infrared absorbing compositions according to some embodiments are described. The infrared absorbing composition includes a p-type semiconductor compound and an n-type semiconductor compound, and the p-type semiconductor compound and the n-type semiconductor compound provide a Bulk Heterojunction (BHJ) structure.

The p-type semiconductor compound may be represented by chemical formula 1.

[ chemical formula 1]

In the chemical formula 1, the first and second,

m may be Sn, Ni, V, Al, Zn, Si, Co, or Ge,

x may be a halogen (e.g., F, Cl, Br, or I),

m may be an integer from 0 to 4, such as 0, 1 or 2,

n can be either 0 or 1 and,

two R^1aTwo R^2aTwo R^3aAnd two R^4aMay each be the same or different from each other, and may each independently be hydrogen, deuterium, halogen, cyano (-CN), C1 to C20 haloalkyl, C1 to C20 cyanoalkyl, C1 to C20 alkyl, or C1 to C20 alkoxy, provided that two R are^1aAt least one, two R^2aAt least one, two R^3aAt least one and two R^4aAt least one of (A) is a C1 to C20 alkyl group or a C1 to C20 alkoxy group,

b may be an integer of 0 to 2, and

n1, n2, n3 and n4 may each independently be an integer of 1 to 4.

In some embodiments, in chemical formula 1, when M is Sn, MX is_mCan be SnX₂(ii) a When M is Ni, MX_mMay be Ni; when M is V, MX_mCan be VX₂(ii) a When M is Al, MX_mCan be AlX; when M is Zn, MX_mCan be Zn; when M is Si, MX_mCan be SiX₂(ii) a When M is Co, MX_mCan be Co; and when M is Ge, MX_mMay be GeX₂。

The p-type semiconductor compound represented by chemical formula 1 may be one of the compounds represented by chemical formulas 1A to 1C.

[ chemical formula 1A ]

[ chemical formula 1B ]

[ chemical formula 1C ]

In the chemical formulae 1A to 1C,

R^1a、R^1b、R^1c、R^1d、R^2a、R^2b、R^2c、R^2d、R^3a、R^3b、R^3c、R^3d、R^4a、R^4b、R^4c、R^4db, n1, n2, n3 and n4 are the same as in chemical formula 1,

wherein, in chemical formula 1C,

R^5aand R^5bMay be hydrogen, C1 to C6 alkyl, or C1 to C6 alkoxy.

In chemical formula 1 or chemical formula 1A, X may be Cl.

In chemical formula 1 or chemical formula 1A, two R^1aMay be the same or different and may each be independently selected from hydrogen, deuterium, halogen, cyano, C1 to C20 haloalkyl, C1 to C20 cyanoalkyl, C1 to C20 alkyl, or C1 to C20 alkoxy, provided that two R are^1aAt least one (e.g., two R)^1aAll) may be C1 to C20 alkyl, such as C1 to C15 alkyl or C3 to C10 alkyl or C1 to C20 alkoxy, such as C1 to C15 alkoxy or C3 to C10 alkoxy (e.g., butoxy). In chemical formula 1 or chemical formula 1A, two R^2aMay be the same or different and may each be independently selected from hydrogen, deuterium, halogen, cyano, C1 to C20 haloalkyl, C1 to C20 cyanoalkyl, C1 to C20 alkyl, or C1 to C20 alkoxy, provided that two R are^2aAt least one (e.g., two R)^1aAll) may be C1 to C20 alkyl, such as C1 to C15 alkyl or C3 to C10 alkyl or C1 to C20 alkoxy, such as C1 to C15 alkoxy or C3 to C10 alkoxy (e.g., butoxy). In chemical formula 1 or chemical formula 1A, two R^3aMay be the same or different and may each be independently selected from hydrogen, deuterium, halogen, cyano, C1 to C20 haloalkyl, C1 to C20 cyanoalkyl, C1 to C20 alkyl, or C1 to C20 alkoxy, provided that two R are^3aAt least one (e.g., two R)^1aAll) may be C1 to C20 alkyl, e.g. C1 to C15 alkyl or C3 to C10 alkyl or C1 to C20 alkoxy, e.g. C1 to C15 alkoxy or C3 to C10 alkoxy (e.g. butoxy)). In chemical formula 1 or chemical formula 1A, two R^4aMay be the same or different and may each be independently selected from hydrogen, deuterium, halogen, cyano, C1 to C20 haloalkyl, C1 to C20 cyanoalkyl, C1 to C20 alkyl, or C1 to C20 alkoxy, provided that two R are^4aAt least one (e.g., two R)^4aAll) may be C1 to C20 alkyl, such as C1 to C15 alkyl or C3 to C10 alkyl or C1 to C20 alkoxy, such as C1 to C15 alkoxy or C3 to C10 alkoxy (e.g., butoxy).

Specific examples of the compound represented by chemical formula 1 may include one of the compounds represented by chemical formula 1A-1, chemical formula 1B-1, or chemical formula 1C-1.

[ chemical formula 1A-1]

In the chemical formula 1A-1,

x is halogen (e.g. F, Cl, Br or I),

two R^1aTwo R^2aTwo R^3aAnd two R^4aMay be the same or different from each other, and may each independently be hydrogen, deuterium, halogen, cyano, C1 to C20 haloalkyl, C1 to C20 cyanoalkyl, C1 to C20 alkyl, or C1 to C20 alkoxy, provided that two R are^1aAt least one, two R^2aAt least one, two R^3aAt least one and two R^4aIs a C1 to C20 alkyl group, such as a C1 to C15 alkyl group or a C3 to C10 alkyl group or a C1 to C20 alkoxy group, such as a C1 to C15 alkoxy group or a C3 to C10 alkoxy group (e.g., butoxy). In some embodiments, two R are^1aTwo R^2aTwo R^3aAnd two R^4aMay each independently be a C1 to C20 alkyl group, such as a C1 to C15 alkyl group or a C3 to C10 alkyl group or a C1 to C20 alkoxy group, such as a C1 to C15 alkoxy group or a C3 to C10 alkoxy group (e.g., butoxy).

[ chemical formula 1B-1]

In the chemical formula 1B-1,

two R^1aTwo R^2aTwo R^3aAnd two R^4aMay be the same or different from each other, and may each independently be hydrogen, deuterium, halogen, cyano, C1 to C20 haloalkyl, C1 to C20 cyanoalkyl, C1 to C20 alkyl, or C1 to C20 alkoxy, provided that two R are^1aAt least one, two R^2aAt least one, two R^3aAt least one and two R^4aIs a C1 to C20 alkyl group, such as a C1 to C15 alkyl group or a C3 to C10 alkyl group or a C1 to C20 alkoxy group, such as a C1 to C15 alkoxy group or a C3 to C10 alkoxy group (e.g., butoxy). In some embodiments, two R are^1aTwo R^2aTwo R^3aAnd two R^4aMay each independently be a C1 to C20 alkyl group, such as a C1 to C15 alkyl group or a C3 to C10 alkyl group, or a C1 to C20 alkoxy group, such as a C1 to C15 alkoxy group or a C3 to C10 alkoxy group (e.g., butoxy).

[ chemical formula 1C-1]

In the chemical formula 1C-1,

R^5aand R^5bMay each independently be hydrogen, C1 to C6 alkyl, or C1 to C6 alkoxy, and

two R^1aTwo R^2aTwo R^3aAnd two R^4aMay be the same or different from each other, and may each independently be hydrogen, deuterium, halogen, cyano, C1 to C20 haloalkyl, C1 to C20 cyanoalkyl, C1 to C20 alkyl, or C1 to C20 alkoxy, provided that two R are^1aAt least one, two R^2aAt least one, two R^3aAt least one and two R^4aIs a C1 to C20 alkyl group, such as a C1 to C15 alkyl group or a C3 to C10 alkyl group, or a C1 to C20 alkoxy group, such as a C1 to C15 alkoxy group or a C3 to C10 alkoxy group (e.g., butoxy). In some embodimentsTwo R^1aTwo R^2aTwo R^3aAnd two R^4aMay each independently be a C1 to C20 alkyl group, such as a C1 to C15 alkyl group or a C3 to C10 alkyl group, or a C1 to C20 alkoxy group, such as a C1 to C15 alkoxy group or a C3 to C10 alkoxy group (e.g., butoxy).

The n-type semiconductor compound may include a compound represented by chemical formula 2A, a compound represented by chemical formula 2B, a compound represented by chemical formula 2C, a fullerene derivative, or a combination thereof.

[ chemical formula 2A ]

In the chemical formula 2A, the metal oxide,

Ar¹may be one of the moieties represented by chemical formula 3,

X¹and X²May each independently be S, Se or Te,

Ar¹¹、Ar¹²、Ar²¹and Ar²²Each independently a substituted or unsubstituted C6-C10 aryl or substituted or unsubstituted C3-C10 heteroaryl,

R¹and R²May each independently be hydrogen or a C1 to C10 alkyl group,

[ chemical formula 3]

Wherein, in chemical formula 3,

X^aand X^bMay each independently be S, Se orTe，

R^aAnd R^bMay each independently be hydrogen or a C1 to C20 alkyl group (e.g., a C1 to C15 alkyl group or a C1 to C10 alkyl group), and

a and b may each independently be 1 or 2.

[ chemical formula 2B ]

In the chemical formula 2B, the first and second,

Ar²may be one of the moieties represented by chemical formula 3,

X¹、X²、X³and X⁴May each independently be S, Se or Te,

Ar¹¹、Ar¹²、Ar²¹and Ar²²Each independently a substituted or unsubstituted C6-C10 aryl or substituted or unsubstituted C3-C10 heteroaryl,

R¹and R²May each independently be hydrogen or a C1 to C10 alkyl group.

[ chemical formula 2C ]

In the chemical formula 2C, the metal oxide,

Ar³may be one of the moieties represented by chemical formula 4,

X¹、X²、X³and X⁴May each independently be S, Se or Te,

R³and R⁴Can be independent of each otherIs hydrogen, C1 to C20 alkyl, C6 to C10 aryl or C2 to C10 heteroaryl,

Ar³¹and Ar³²May be independently selected from the group consisting of C-O, C-S, C-Se, C-Te and C-CN₂A substituted or unsubstituted C6 to C30 hydrocarbon ring group having at least one functional group selected from C ═ O, C ═ S, C ═ Se, C ═ Te and C ═ CN₂A substituted or unsubstituted heterocyclic group of C2 to C30, or a condensed ring thereof, and

R¹and R²May each independently be hydrogen or C1 to C20 alkyl (e.g., C1 to C15 alkyl or C1 to C10 alkyl).

[ chemical formula 4]

In the chemical formula 4, the first and second organic solvents,

Y¹may be CR^pR^q、NR^rO, S, Se, or Te, wherein R^p、R^qAnd R^rMay each independently be hydrogen or a C1 to C20 alkyl group (e.g., a C1 to C15 alkyl group or a C1 to C10 alkyl group), and

Z¹to Z⁴May each independently be CR^sOr N, wherein R^sIs hydrogen or C1 to C20 alkyl (e.g., C1 to C15 alkyl or C1 to C10 alkyl).

In chemical formula 4, Z¹And Z²At least one and/or Z¹To Z⁴At least one, such as at least two, of (a) may be N.

The moiety represented by chemical formula 4 may be one of the moieties represented by chemical formula 4A.

[ chemical formula 4A ]

In the chemical formula 4A, the first and second,

R^scan be hydrogen or C1 to C20 alkyl (e.g., C1 to C15 alkyl or C1)To C10 alkyl).

In chemical formulas 2A and 2B, Ar¹¹、Ar¹²、Ar²¹And Ar²²May each independently be a C6 to C10 aryl group substituted with a C1 to C20 (e.g., C4 to C15 or C4 to C10) alkyl group or a C1 to C20 (e.g., C4 to C15 or C4 to C10) alkoxy group; or C3 to C10 heteroaryl substituted with C1 to C20 (e.g., C4 to C15 or C4 to C10) alkyl or C1 to C20 (e.g., C4 to C15 or C4 to C10) alkoxy.

In some embodiments, R of formula 2C³And R⁴Each independently may be a substituted or unsubstituted branched C3 to C20 alkyl group (e.g., isopropyl, isobutyl, 2-ethylpentyl, 2-propylpentyl, 2-propyloctyl, tert-butyl, isopentyl, neopentyl, 2-ethylbutyl, 2-methylpentyl, 3-methylpentyl, 2, 3-dimethylbutyl, 3-ethylpentyl, 2-methylhexyl, 2, 3-dimethylpentyl, 2, 4-dimethylpentyl, 2-methyloctyl, 2-ethyloctyl, 4-methyloctyl, 3-dimethyloctyl, 4-ethyloctyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 2, 4-trimethylpentyl, 2, 3-dimethylpentyl, 2, 3-ethylpentyl, 2, 3-dimethylpentyl, 3-ethylpentyl, 3-dimethylpentyl, 2, 3-dimethylpentyl, 3-ethylpentyl, 3-methylpentyl, 3-ethylpentyl, 2, 4-ethylpentyl, 2,3, 4, or a, 2, 4-dimethylhexyl, 2-methyl-3-ethylpentyl, 3-methyl-4-methylhexyl, 3,3, 4-trimethylhexyl, 3,4, 5-trimethylhexyl, 4-ethylheptyl, 5-methylnonyl, 3-methyl-2-ethylheptyl, 1-methylnonyl, 2,3, 5-trimethylheptyl, 3-methyl-4-ethylheptyl, 2,3, 3-tetramethylhexyl, 4-propylheptyl or 2, 4-dimethyl-3-ethylhexyl).

In chemical formulae 2A to 2C, Ar³¹And Ar³²May be a cyclic group represented by one of chemical formulas 5A to 5F.

[ chemical formula 5A ]

In the chemical formula 5A, the first and second,

Z¹and Z²May each independently be O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bMay each independently be hydrogen, substituted or unsubstituted C1 toA C10 alkyl group, or a cyano group,

Z³may be N or CR^cWherein R is^cIs hydrogen, deuterium or a substituted or unsubstituted C1 to C10 alkyl group,

R¹¹、R¹²、R¹³、R¹⁴and R¹⁵May be the same or different from each other, and may each independently be hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen (F, Cl, Br, or I), cyano (-CN), cyano-containing group, or a combination thereof, wherein R is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen (F, Cl, Br, or I), cyano (-CN), cyano-containing group, or a combination thereof¹²、R¹³、R¹⁴And R¹⁵May each independently be present or R¹²And R¹³And R¹⁴And R¹⁵May be linked to each other to provide a fused aromatic ring,

n can be 0 or 1, and

may be a connection location.

[ chemical formula 5B ]

In the chemical formula 5B, the first and second,

Z¹and Z²May each independently be O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bMay each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

Z³can be O, S, Se, Te or C (R)^a) (CN) wherein R^aIs hydrogen, cyano (-CN), or C1 to C10 alkyl,

may be a connection location.

[ chemical formula 5C ]

In the chemical formula 5C, the metal oxide,

Z¹and Z²May each independently be O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bMay each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

may be a connection location.

[ chemical formula 5D ]

In the chemical formula 5D, the metal oxide,

Z¹and Z²May each independently be O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bMay each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

Z³may be N or CR^cWherein R is^cMay be hydrogen or substituted or unsubstituted C1 to C10 alkyl,

G¹can be O, S, Se, Te, SiR^xR^yOr GeR^zR^wWherein R is^x、R^y、R^zAnd R^wMay be the same or different and may each independently be hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl,

R¹¹、R¹²and R¹³May be the same as or different from each other, andmay each independently be hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen (F, Cl, Br, or I), a cyano-containing group, or a combination thereof, wherein R is hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a halogen (F, Cl, Br, or I), a cyano-containing group, or a combination thereof¹²And R¹³May each be independently present or attached to each other to provide a fused aromatic ring,

n can be 0 or 1, and

may be a connection location.

[ chemical formula 5E ]

In the chemical formula 5E, the metal oxide,

Z¹and Z²May each independently be O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bMay each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

Z³may be N or CR^cWherein R is^cMay be hydrogen or substituted or unsubstituted C1 to C10 alkyl,

G²can be O, S, Se, Te, SiR^xR^yOr GeR^zR^wWherein R is^x、R^y、R^zAnd R^wMay be the same or different and may each independently be hydrogen, deuterium, halogen (F, Cl, Br, or I), substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl,

n can be 0 or 1, and

may be a connection location.

[ chemical formula 5F ]

In the chemical formula 5F, the metal oxide,

Z¹and Z²May each independently be O, S, Se, Te or CR^aR^bWherein R is^aAnd R^bMay each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or cyano,

R¹¹can be hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C4 to C30 heteroaryl, halogen (F, Cl, Br, or I), cyano (-CN), a cyano-containing group, or a combination thereof, and

G³can be O, S, Se, Te, SiR^xR^yOr GeR^zR^wWherein R is^x、R^y、R^zAnd R^wMay be the same or different and may each independently be hydrogen, deuterium, halogen (F, Cl, Br, or I), substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl.

In some embodiments, the compound represented by chemical formula 2A may be a compound represented by chemical formula 2A-1.

[ chemical formula 2A-1]

In the chemical formula 2A-1,

Ar¹may be one of the moieties represented by chemical formula 3,

X¹and X²May each independently be S, Se or Te,

R¹and R²May each independently be hydrogen or a C1 to C10 alkyl group,

R¹¹、R¹²、R²¹and R²²May each independently be hydrogen, deuterium, halogen, substituted or unsubstituted C1To C20 alkyl, or substituted or unsubstituted C6 to C20 aryl, x1, y1, x2, and y2 may each independently be an integer of 0 to 5, and

Ar³¹and Ar³²Each independently may be a group having a general formula selected from C-O, C-S, C-Se, C-Te and C-CN₂A substituted or unsubstituted C6 to C30 hydrocarbon ring group having at least one functional group selected from C ═ O, C ═ S, C ═ Se, C ═ Te and C ═ CN₂A substituted or unsubstituted C2 to C30 heterocyclic group of at least one functional group of (a), or a fused ring thereof.

In chemical formula 2A-1, Ar³¹And Ar³²May be a cyclic group represented by one of chemical formulas 5A to 5F.

In chemical formula 2A-1, R¹¹、R¹²、R²¹And R²²May be present in the para position of the phenyl ring.

The compound represented by chemical formula 2B may be a compound represented by chemical formula 2B-1.

[ chemical formula 2B-1]

In the chemical formula 2B-1,

Ar²may be one of the moieties represented by chemical formula 3,

X¹、X²、X³and X⁴May each independently be S, Se or Te,

R¹and R²May each independently be hydrogen or a C1 to C10 alkyl group,

Ar³¹and Ar³²Each independently may be a group having a general formula selected from C-O, C-S, C-Se, C-Te and C-CN₂A substituted or unsubstituted C6 to C30 hydrocarbon ring group of at least one functional group ofHaving a formula selected from the group consisting of C-O, C-S, C-Se, C-Te and C-CN₂A substituted or unsubstituted C2 to C30 heterocyclic group of at least one functional group of (a), or a fused ring thereof.

In chemical formula 2B-1, Ar³¹And Ar³²May be a cyclic group represented by one of chemical formulas 5A to 5F.

In chemical formula 2B-1, R¹¹、R¹²、R²¹And R²²May be present in the para position of the phenyl ring.

The compound represented by chemical formula 2A may include a compound represented by one of chemical formulas 2A-1a to 2A-1 d.

[ chemical formula 2A-1a ]

[ chemical formula 2A-1b ]

[ chemical formula 2A-1c ]

[ chemical formulas 2A-1d ]

In the chemical formulas 2A-1a to 2A-1d,

R¹¹、R¹²、R²¹and R²²May each independently be hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 (e.g., C4 to C10 or C6 to C8) alkyl, or substituted or unsubstituted C6 to C20 (e.g., C6 to C10 or C6 to C8) aryl,

hal represents halogen (e.g. F, Cl, Br or I), and

m1 and m2 may be integers from 0 to 4 (e.g., from 0 to 2).

The compound represented by chemical formula 2A may be a compound represented by one of chemical formulae 2A-2A and 2A-2 b.

[ chemical formula 2A-2A ]

[ chemical formulas 2A-2b ]

In chemical formulas 2A-2A and 2A-2b,

hal represents halogen (e.g. F, Cl, Br or I), and

m1 and m2 may be integers from 0 to 4 (e.g., from 0 to 2).

The compound of chemical formula 2A-1a may be a compound of chemical formula 2A-1 aa.

[ chemical formula 2A-1aa ]

The compound represented by chemical formula 2B may be a compound represented by one of chemical formulae 2B-1a to 2B-1 d.

[ chemical formula 2B-1a ]

[ chemical formula 2B-1B ]

[ chemical formula 2B-1c ]

[ chemical formula 2B-1d ]

In the chemical formulas 2B-1a to 2B-1d,

hal represents halogen (e.g. F, Cl, Br or I), and

m1 and m2 may be integers from 0 to 4 (e.g., from 0 to 2).

The compound represented by chemical formula 2B may be a compound represented by chemical formula 2B-2a or 2B-2B.

[ chemical formula 2B-2a ]

[ chemical formula 2B-2B ]

In chemical formulas 2B-2a and 2B-2B,

hal represents halogen (e.g. F, Cl, Br or I), and

m1 and m2 may be integers from 0 to 4 (e.g., from 0 to 2).

The compound of formula 2B-1a may be a compound of formula 2B-1aa or 2B-1 ab.

[ chemical formula 2B-1aa ]

[ chemical formula 2B-1ab ]

The substitution position of F in the formula 2B-1ab may be symmetrical or asymmetrical.

The compound of formula 2B-2a may be a compound of formula 2B-2aa or 2B-2 ab.

[ chemical formula 2B-2aa ]

CH in chemical formula 2B-2aa₃The substitution positions of (b) may be symmetrical or asymmetrical.

[ chemical formula 2B-2ab ]

The compound represented by chemical formula 2C may be a compound of chemical formula 2C-1a or 2C-1 b.

[ chemical formula 2C-1a ]

[ chemical formula 2C-1b ]

In the chemical formulas 2C-1a and 2C-1b,

hal represents halogen (e.g. F, Cl, Br or I),

m1 and m2 may be integers from 0 to 4 (e.g., 0 to 2), and

R³and R⁴May each independently be hydrogen, C1 to C20 alkyl, C6 to C10 aryl, or C2 to C10 heteroaryl.

The fullerene derivative refers to a compound having a substituent on a fullerene. The fullerene may be a C60 to C540 fullerene, particularly, but not limited to, C60, C70, C74, C76, C78, C80, C82, C84, C90, C96, C240, or C540.

The substituent may be a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a combination thereof. The alkyl group can be a C1 to C20 alkyl group, such as a C1 to C10 alkyl group. The aryl group may be a C6 to C20 aryl group, for example, a C6 to C14 aryl group, and specifically, may be a phenyl group, a naphthyl group, or an anthracenyl group. The heterocyclic group may be a C2 to C20 heterocyclic group, such as a C2 to C14 heterocyclic group, and specifically, may be furyl, thienyl, pyrrolyl, or the like,Oxazolyl, pyridyl, quinolinyl, or carbazolyl. The substituted alkyl, substituted aryl and substituted heterocyclic groups may be alkyl, aryl or heterocyclic groups substituted with a carboxyl or ester group.

Specific examples of the fullerene derivative may include [6,6] -phenyl-C61-butyric acid methyl ester (PC60BM), bis (1- [3- (methoxycarbonyl) propyl ] -1-phenyl) - [6,6] C62 (bis-PCBM), phenyl-C70-butyric acid methyl ester (PC70BM), indene-C60 bis adduct (ICBA) or indene-C60 mono adduct (ICMA), but are not limited thereto.

The p-type semiconductor compound and the n-type semiconductor compound may be included at a volume ratio (p-type semiconductor compound: n-type semiconductor compound) of about 1:0.1 to about 1: 10. That is, the volume ratio of n-type semiconductor compound/p-type semiconductor compound can be greater than or equal to about 0.1, greater than or equal to about 0.2, greater than or equal to about 0.3, greater than or equal to about 0.4, greater than or equal to about 0.5, greater than or equal to about 0.6, greater than or equal to about 0.7, greater than or equal to about 0.8, greater than or equal to about 0.9, greater than or equal to about 1, greater than or equal to about 1.1 and less than or equal to about 10, less than or equal to about 9, less than or equal to about 8, less than or equal to about 7, less than or equal to about 6, less than or equal to about 5, less than or equal to about 4, less than or equal to about 3, less than or equal to about 2, less than or equal to about 1.5, less than or equal to about 1.4, or less than or equal to about 1.3. Within the above range, a BHJ structure having excellent infrared absorption properties can be provided.

The infrared absorbing composition can absorb light in the infrared wavelength region and the infrared absorbing composition has a peak absorption wavelength (λ)_{Maximum of}) The wavelength regions can be, for example, as follows: greater than or equal to about 800nm, greater than or equal to about 810nm, greater than or equal to about 820nm, greater than or equal to about 830nm, greater than or equal to about 840nm, greater than or equal to about 850nm, greater than or equal to about 860nm, greater than or equal to about 870nm, greater than or equal to about 880nm, greater than or equal to about 890nm, or greater than or equal to about 900 nm. The peak absorption wavelength (lambda) of the infrared absorbing composition_{Maximum of}) The wavelength regions can be, for example, as follows: less than or equal to about 3000nm, less than or equal to about 2900nm, less than or equal to about 2800nm, less than or equal to about 2700nm, less than or equal to about 2600nm, less than or equal to about 2500nm, less than or equal to about 2400nm, less than or equal to about 2300nm, less than or equal to about 2200nm, or less than or equal to about 2100 nm.

The infrared absorbing composition has excellent photoelectric conversion efficiency of absorbing light and converting it into an electrical signal, and thus can be effectively used as a photoelectric conversion material of an optoelectronic device.

The photoelectric devices currently reported exhibit about 10 in the infrared wavelength region^-2To 10^-3mA/cm²The dark current of (1). However, an opto-electronic device comprising the above infrared absorbing composition may exhibit a pass through of about 10^-4mA/cm²Improves the sensitivity of a sensor comprising the optoelectronic device.

The p-type semiconductor compound and the n-type semiconductor compound may be solution-processed, so that a large-area photoelectric device may be manufactured at low cost.

The infrared absorbing composition can be applied to various fields requiring absorption properties in the infrared wavelength region.

The infrared absorbing composition has both light absorbing properties and photoelectric properties in the infrared wavelength region, and can greatly reduce the dark current of a photoelectric device, and thus can be effectively used as a photoelectric conversion material for a photoelectric device.

Fig. 1 is a cross-sectional view of an optoelectronic device according to some embodiments.

Referring to fig. 1, an optoelectronic device 100 according to some embodiments includes a first electrode 10 and a second electrode 20 facing each other and a photoactive layer 30 between the first electrode 10 and the second electrode 20.

A substrate (not shown) may be disposed at one side of the first electrode 10 or the second electrode 20. The substrate may be made of (e.g., may include, at least in part): inorganic materials such as glass; organic materials such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyether sulfone, or a combination thereof; or a silicon wafer. The substrate may be omitted.

One of the first electrode 10 or the second electrode 20 is an anode, and the other is a cathode. For example, the first electrode 10 may be a cathode, and the second electrode 20 may be an anode.

At least one of the first electrode 10 or the second electrode 20 may be a light-transmitting electrode, and the light-transmitting electrode may be made of, for example: conductive oxides such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), zinc oxide (ZnO), tin oxide (SnO)₂) Aluminum tin oxide (AlTO) and/or fluorine doped tin oxide (FTO); or a single or multiple thin layers of metal. When one of the first electrode 10 and the second electrode 20 is a non-light-transmitting electrode, it may be made of, for example, an opaque conductor such as aluminum (Al), silver (Ag), or gold (Au). For example, the first electrode 10 and the second electrode 20 may all be light-transmitting electrodes. For example, the second powerThe pole 20 may be a light receiving electrode disposed on the light receiving side.

Photoactive layer 30 includes an infrared absorbing composition that includes the above-described p-type semiconductor compound and n-type semiconductor compound.

The photoactive layer 30 is a layer (intrinsic layer, I layer) in which a p-type semiconductor compound and an n-type semiconductor compound form a pn junction, and excitons can be generated by: receives light from the outside (e.g., the outside of the photoactive layer 30), and then separates holes and electrons from the generated excitons.

In addition to the intrinsic layer, the photoactive layer 30 may further include a p-type layer and/or an n-type layer. The p-type layer may include a p-type semiconductor compound, and the n-type layer may include an n-type semiconductor compound. For example, they may be included in various combinations of p-type layer/I-layer, I-layer/n-type layer, p-type layer/I-layer/n-type layer, and the like.

The optoelectronic device 100 may further include an auxiliary layer between the first electrode 10 and the photoactive layer 30 and/or the second electrode 20 and the photoactive layer 30. The auxiliary layer may be a charge-assist layer or an optical-assist layer.

The photovoltaic device is shown in fig. 2. Fig. 2 is a cross-sectional view illustrating an optoelectronic device according to some embodiments.

Referring to fig. 2, an optoelectronic device 100' according to the present embodiment includes a first electrode 10 and a second electrode 20 facing each other and a photoactive layer 30 between the first electrode 10 and the second electrode 20, like the above-described embodiments.

However, unlike the above-described embodiment, the photoelectric device 100' according to the present embodiment further includes charge assist layers 40 and 45 between the first electrode 10 and the photoactive layer 30 and between the second electrode 20 and the photoactive layer 30, respectively. The charge assist layers 40 and 45 facilitate the movement of holes and electrons separated from the photoactive layer 30 to increase efficiency.

The charge assist layers 40 and 45 may include at least one selected from the group consisting of: a Hole Injection Layer (HIL) for facilitating hole injection, a Hole Transport Layer (HTL) for facilitating hole transport, an Electron Blocking Layer (EBL) for preventing electron transport, an Electron Injection Layer (EIL) for facilitating electron injection, an Electron Transport Layer (ETL) for facilitating electron transport, and a Hole Blocking Layer (HBL) for preventing hole transport.

The charge assist layers 40 and/or 45 may comprise, for example, organic, inorganic, or organic-inorganic materials. The organic material may be an organic material having a hole or electron characteristic, and the inorganic material may be, for example, a metal oxide such as molybdenum oxide, tungsten oxide, or nickel oxide.

The charge assist layers 40 and 45 can include, for example, the infrared absorbing compositions described above.

The optical auxiliary layer may be disposed in a light incident direction of the optoelectronic device. For example, when the second electrode 20 is a light receiving electrode, an optical auxiliary layer may be disposed on the photoactive layer 30. For example, an optical assist layer can be disposed between the second electrode 20 and the photoactive layer 30.

The photoelectric devices 100 and 100' may further include an anti-reflection layer (not shown) on one surface of the first electrode 10 or the second electrode 20. The antireflection layer is provided at the light incident side, and reduces the reflectance of light of incident light, and thus light absorption is further improved. For example, when light enters from the first electrode 10, an anti-reflection layer may be disposed on the first electrode 10, and when light enters from the second electrode 20, an anti-reflection layer may be disposed under the second electrode 20.

The anti-reflective layer may include, for example, a material having a refractive index of about 1.6 to about 2.5, and may include, for example, at least one of a metal oxide, a semi-metal oxide, a metal sulfide, and an organic material having a refractive index within the range. The antireflective layer can include, for example, a metal oxide or semimetal oxide such as an aluminum-containing oxide, a molybdenum-containing oxide, a tungsten-containing oxide, a vanadium-containing oxide, a rhenium-containing oxide, a niobium-containing oxide, a tantalum-containing oxide, a titanium-containing oxide, a nickel-containing oxide, a copper-containing oxide, a cobalt-containing oxide, a manganese-containing oxide, a chromium-containing oxide, a tellurium-containing oxide, or combinations thereof; metal sulfides such as zinc sulfide; or organic materials such as amine derivatives, but not limited thereto.

In the optoelectronic devices 100 and 100', excitons may be generated within the photoactive layer 30 when light enters from the first electrode 10 or the second electrode 20 and the photoactive layer absorbs light within a desired and/or alternatively predetermined wavelength region. The exciton is separated into a hole and an electron in the photoactive layer 30, and the separated hole is transported to an anode as one of the first electrode 10 and the second electrode 20, and the separated electron is transported to a cathode as the other of the first electrode 10 and the second electrode 20, so that current flows.

The photoelectric devices 100 and 100' may be applied to sensors such as an image sensor (CMOS image sensor), a photodetector, an optical sensor (infrared light sensor), a solar cell, and the like, but are not limited thereto.

Fig. 3 is a cross-sectional view illustrating an image sensor according to some embodiments.

The image sensor 200 according to the embodiment includes a semiconductor substrate 110, an insulating layer 80, and an optoelectronic device 100. Fig. 3 shows an image sensor 200 comprising the optoelectronic device 100 of fig. 1, but the image sensor 200 may also comprise the optoelectronic device 100' of fig. 2.

The semiconductor substrate 110 may be a silicon substrate and is integrated with a transfer transistor (not shown) and a charge storage 55. The charge storage 55 may be integrated in each pixel. The charge storage 55 is electrically connected to the optoelectronic device 100, and information of the charge storage 55 can be transferred by the transfer transistor.

Metal lines (not shown) and pads (not shown) are formed on the semiconductor substrate 110. In order to reduce signal delay, the metal line and the pad may be made of metal having low resistivity, such as aluminum (Al), copper (Cu), silver (Ag), and alloys thereof, but are not limited thereto. In addition, it is not limited to the structure, and the metal line and the pad may be disposed under the semiconductor substrate 110.

An insulating layer 80 is formed on the metal lines and pads. The insulating layer 80 may be made of an inorganic insulating material such as silicon oxide and/or silicon nitride, or a low dielectric constant (low K) material such as SiC, SiCOH, SiCO, and SiOF. Insulating layer 80 has trenches 85 that expose charge storage 55. Trench 85 may be filled with a filler.

The aforementioned sensor 100 is formed on the insulating layer 80. As described above, the optoelectronic device 100 includes the first electrode 10, the photoactive layer 30, and the second electrode 20. Even though a structure in which the first electrode 10, the photoactive layer 30, and the second electrode 20 are sequentially stacked is illustrated in the drawings as an example, the present disclosure is not limited to the structure, and the second electrode 20, the photoactive layer 30, and the first electrode 10 may be arranged in this order.

The first electrode 10 and the second electrode 20 may both be transparent electrodes, and the photoactive layer 30 is the same as described above. The photoactive layer 30 may selectively absorb light in the infrared wavelength region. Incident light from the second electrode 20 side can be photoelectrically converted by absorbing light mainly in the infrared wavelength region in the photoactive layer 30.

A focusing lens (not shown) may be further formed on the optoelectronic device 100. The focusing lens may control the direction of incident light and concentrate the light in one area. The focusing lens may have a shape of, for example, a cylinder or a hemisphere, but is not limited thereto.

Fig. 4 is a cross-sectional view illustrating an image sensor according to some embodiments.

Referring to fig. 4, an image sensor 300 according to an embodiment includes a semiconductor substrate 110 integrated with light sensing devices 50a, 50b, and 50c, a transfer transistor (not shown), and a charge storage 55, a lower insulating layer 60, color filters 70a, 70b, and 70c, an upper insulating layer 80, and an optoelectronic device 100. Fig. 4 shows an image sensor 300 comprising the optoelectronic device 100 of fig. 1, but the image sensor 300 may also comprise the optoelectronic device 100' of fig. 2.

The semiconductor substrate 110 may be integrated with the photo sensing devices 50a, 50b, and 50c, a transfer transistor (not shown), and a charge storage 55. The light sensing devices 50a, 50b, and 50c may be photodiodes.

The light sensing devices 50a, 50b and 50c, the transfer transistors and/or the charge storage 55 may be integrated in each pixel. For example, the light sensing device 50a may be included in a red pixel, the light sensing device 50b may be included in a green pixel, and the light sensing device 50c may be included in a blue pixel.

The light sensing devices 50a, 50b, and 50c sense light, information sensed by the light sensing devices may be transmitted by the transmission transistors, the charge storage 55 is electrically connected to the photoelectric device 100, and information of the charge storage 55 may be transmitted by the transmission transistors.

Metal lines (not shown) and pads (not shown) are formed on the semiconductor substrate 110. In order to reduce signal delay, the metal line and the pad may be made of metal having low resistivity, such as aluminum (Al), copper (Cu), silver (Ag), and alloys thereof, but are not limited thereto. In addition, it is not limited to the structure, and metal lines and pads may be disposed under the photo-sensing devices 50a and 50 b.

A lower insulating layer 60 is formed on the metal line and the pad.

The color filters 70a, 70b, and 70c are formed on the lower insulating layer 60. The color filters 70a, 70b, and 70c include a red color filter 70a formed in a red pixel, a green color filter 70 formed in a green pixel, and a blue color filter 70c formed in a blue pixel.

An upper insulating layer 80 is formed on the color filters 70a, 70b, and 70 c. The upper insulating layer 80 eliminates steps caused by the color filters 70a, 70b, and 70c and planarizes the surface.

The aforementioned photoelectric device 100 is formed on the upper insulating layer 80. As described above, the optoelectronic device 100 includes the first electrode 10, the photoactive layer 30, and the second electrode 20. Even though a structure in which the first electrode 10, the photoactive layer 30, and the second electrode 20 are sequentially stacked is illustrated in the drawings as an example, the present disclosure is not limited to the structure, and the second electrode 20, the photoactive layer 30, and the first electrode 10 may be arranged in this order.

Incident light from the second electrode 20 side can be photoelectrically converted by mainly absorbing light in the near infrared wavelength region in the photoactive layer 30. Light in the remaining wavelength region may pass through the first electrode 10 and the color filters 70a, 70b, and 70c, light in the red wavelength region passing through the color filter 70a may be sensed by the light sensing device 50a, light in the green wavelength region passing through the color filter 70b may be sensed by the light sensing device 50b, and light in the blue wavelength region passing through the color filter 70c may be sensed by the light sensing device 50 c.

Fig. 5 is a cross-sectional view illustrating an image sensor according to some embodiments.

Referring to fig. 5, the image sensor 400 according to the embodiment includes a semiconductor substrate 110 integrated with an infrared light charge storage 55IR, a blue light charge storage 55B, a green light charge storage 55G, a red light charge storage 55R, and a transfer transistor (not shown), a lower insulating layer 65, a blue light sensing device 100B, a green light sensing device 100G, a red light sensing device 100R, and an infrared light sensing device 100 IR.

The semiconductor substrate 110 may be a silicon substrate, and the infrared light charge storage 55IR, the blue light charge storage 55B, the green light charge storage 55G, the red light charge storage 55R, and the transfer transistor (not shown) are integrated therein. The blue, green, and red light charge memories 55B, 55G, and 55R may be integrated for each of the blue, green, and red pixels.

The charges generated in the infrared light-sensing devices 100IR, the blue light-sensing devices 100B, the green light-sensing devices 100G, and the red light-sensing devices 100R are collected in the infrared light charge storage 55IR, the blue light charge storage, the green light charge storage 55G, and the red light charge storage 55R, which are electrically connected to the infrared light-sensing devices 100IR, the blue light-sensing devices 100B, the green light-sensing devices 100G, and the red light-sensing devices 100R, respectively.

A lower insulating layer 65 may be formed on the metal line and the pad. The lower insulating layer 65 may be made of an inorganic insulating material such as silicon oxide and/or silicon nitride, or a low dielectric constant (low K) material such as SiC, SiCOH, SiCO, and SiOF.

A blue light sensing device 100B, a green light sensing device 100G, a red light sensing device 100R, and a red light sensing device 100IR are formed on the lower insulating layer 65. The blue light sensing device 100B may include a first electrode 10B, a second electrode 20B, and a photoactive layer 30B configured to selectively absorb light in a blue wavelength region. The green light sensing device 100G may include a first electrode 10G, a second electrode 20G, and a photoactive layer 30G configured to selectively absorb light in a green wavelength region. The red light sensing device 100R may include a first electrode 10R, a second electrode 20R, and a photoactive layer 30R configured to selectively absorb light in a red wavelength region. The infrared light sensing device 100IR may include a first electrode 10IR, a second electrode 20IR, and a photoactive layer 30IR configured to selectively absorb light in an infrared light wavelength region.

The first electrodes 10B, 10G, 10R, and 10IR and the second electrodes 20B, 20G, 20R, and 20IR may be light-transmitting electrodes, and may be made of, for example, a transparent conductor such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), zinc oxide (ZnO), tin oxide (SnO)₂) Aluminum tin oxide (AlTO), and fluorine-doped tin oxide (FTO), or may be a metal thin film having a thickness of several nanometers or several tens of nanometers, or a metal thin film having a thickness of several nanometers to several tens of nanometers doped with a metal oxide.

Photoactive layers 30B, 30G, 30R, and 30IR may include p-type semiconductor materials and n-type semiconductor materials. The photoactive layer 30B of the blue light sensing device 100B may include a p-type semiconductor material configured to selectively absorb light in the blue wavelength region and an n-type semiconductor material configured to selectively absorb light in the blue wavelength region, the photoactive layer 30G of the green light sensing device 100G may include a p-type semiconductor material configured to selectively absorb light in the green wavelength region and an n-type semiconductor material configured to selectively absorb light in the green wavelength region, the photoactive layer 30R of the red light sensing device 100R may include a p-type semiconductor material configured to selectively absorb light in the red wavelength region and an n-type semiconductor material configured to selectively absorb light in the red wavelength region, and the photoactive layer 30IR of the infrared light sensing device 100IR may include the infrared absorbing composition described above. The infrared light sensing device 100IR may selectively absorb light in the infrared region of greater than or equal to about 800nm and less than or equal to about 3000nm without absorption in the visible region.

Fig. 6 is a cross-sectional view illustrating an image sensor according to some embodiments.

Referring to fig. 6, the image sensor 500 may include a semiconductor substrate 110 integrated with an infrared light charge storage 55IR, a blue light charge storage 55B, a green light charge storage 55G, a red light charge storage 55R, and a transfer transistor (not shown), a lower insulating layer 65, a blue light sensing device 100B, a green light sensing device 100G, a red light sensing device 100R, and an infrared light sensing device 100 IR. The infrared light sensing device 100IR is formed on the entire front surfaces of the blue light sensing device 100B, the green light sensing device 100G, and the red light sensing device 100R. The remaining configuration is the same as the image sensor shown in fig. 5, except that the infrared light sensing device 100IR also extends on the upper insulating layer 90.

In the configuration of fig. 6, the infrared light-sensing device 100IR may be present on the lower insulating layer 65, and the blue light-sensing device 100B, the green light-sensing device 100G, the red light-sensing device 100R may be disposed thereon, and the upper insulating layer 90 may be provided on a portion of the infrared light-sensing device 100IR above the infrared light charge storage 55 IR. An image sensor 600 having such a configuration is shown in fig. 7.

The infrared light sensing device 100IR may be configured to selectively absorb light in the infrared region greater than or equal to about 800nm and less than or equal to about 3000nm, and have a large absorption area to improve efficiency.

The sensor according to the present embodiment may include a plurality of sensors having different functions. For example, at least one of the plurality of sensors having different functions may be a biometric sensor, and the biometric sensor may be, for example, an iris sensor, a depth sensor, a fingerprint sensor, a blood vessel distribution sensor, etc., but is not limited thereto.

For example, one of the plurality of sensors having different functions may be an iris sensor, and the other may be a depth sensor. The iris sensor identifies a person by: using the unique iris characteristics of each person and, in particular, taking an image of the user's eyes within a suitable distance, processing the image and comparing it with his/her stored image. The depth sensor recognizes the shape and position of an object from its three-dimensional information by taking an image of the object within an appropriate distance from the user and processing it. The depth sensor may be used, for example, as a facial recognition sensor.

In an embodiment, the plurality of sensors may include, for example, a sensor configured to sense having a first wavelength (λ) in the infrared wavelength region₁) And a first infrared light sensor configured to sense light in the infrared wavelength region having a second wavelength (λ) in the infrared wavelength region₂) Is in the infrared region.

A first wavelength (λ)₁) And a second wavelength (λ)₂) May differ, for example, in a wavelength region of about 800nm to about 3000nm, and, for example, a first wavelength (λ [. lambda. ])₁) And a second wavelength (λ)₂) The difference therebetween can be greater than or equal to about 30nm, greater than or equal to about 50nm, greater than or equal to about 70nm, greater than or equal to about 80nm, or greater than or equal to about 90 nm.

For example, the first wavelength (λ)₁) And a second wavelength (λ)₂) One of which may belong to a wavelength region of about 780nm to about 900nm and a first wavelength (λ)₁) And a second wavelength (λ)₂) May belong to a wavelength region of about 830nm to about 1000 nm.

For example, the first wavelength (λ)₁) And a second wavelength (λ)₂) One of which may belong to a wavelength region of about 780nm to about 840nm and a first wavelength (λ)₁) And a second wavelength (λ)₂) May belong to a wavelength region of about 910nm to about 970 nm.

For example, the first wavelength (λ)₁) And a second wavelength (λ)₂) One of which may belong to a wavelength region of about 800nm to about 830nm and a first wavelength (λ)₁) And a second wavelength (λ)₂) May belong to a wavelength region of about 930nm to about 950 nm.

For example, the first wavelength (λ)₁) And a second wavelength (λ)₂) One of which may belong to a wavelength region of about 805nm to about 815nm and a first wavelength (λ)₁) And a second wavelength (λ)₂) May belong to the wavelength region of about 935nm to about 945 nm.

For example, the first wavelength (λ)₁) And a second wavelength (λ)₂) One may be about 810nm and the first wavelength (λ)₁) And a second wavelength (λ)₂) May be about 940 nm.

Fig. 8 is a cross-sectional view illustrating an image sensor including a plurality of sensors according to some embodiments.

The image sensor 700 according to the present embodiment includes the double bandpass filter 95, the first infrared light sensor 100A, the insulating layer 80, and the semiconductor substrate 110 integrated with the second infrared light sensor 120. The first infrared light sensor 100A and the second infrared light sensor 120 are stacked.

The dual bandpass filter 95 may be disposed on a front side of the first infrared light sensor 100A, and may selectively transmit light including a first wavelength (λ @)₁) And including a second wavelength (lambda)₂) And may block and/or absorb other light. Here, the other light may include light in an Ultraviolet (UV) and visible light region.

The first infrared light sensor 100A includes a first electrode 10, a photoactive layer 30, and a second electrode 20. The first infrared light sensor 100A may be the same as the photoelectric device 100 according to the foregoing embodiment.

The second infrared light sensor 120 may be integrated in the semiconductor substrate 110 and may be a light sensing device. The semiconductor substrate 110 may be, for example, a silicon substrate, and may be integrated with the second infrared light sensor 120, the charge storage 55, and a transfer transistor (not shown).

The second infrared light sensor 120 may be a photodiode, and may sense incoming light, and the sensed information is transmitted by the transmission transistor. Here, the light entering the second infrared light sensor 120 is light passing through the dual band-pass filter 95 and the first infrared light sensor 100A, and may be light including a second wavelength ((λ)₂) Desired and/or alternatively predetermined area. At a first wavelength (λ)₁) All of the infrared light in the desired and/or alternatively predetermined region may be absorbed by the photoactive layer 30,and may not reach the second infrared light sensor 120. In this case, it is not separately necessary to provide a separate filter for wavelength selectivity with respect to light entering the second infrared light sensor 120. However, for when the first wavelength (λ) is included₁) When all of the infrared light in the desired and/or alternatively predetermined region is not absorbed by the photoactive layer 30, a filter between the first infrared light sensor 100A and the second infrared light sensor 120 may be further provided.

The sensor according to the present embodiment may include two infrared light sensors that individually perform functions, respectively, and thus may operate as a combined sensor. In addition, two sensors that individually perform functions are stacked in each pixel, and therefore, while maintaining the size, the number of pixels of each sensor that perform functions is increased two times, and as a result, the sensitivity can be greatly improved.

The aforementioned sensor may be applied to, for example, various electronic devices, and the electronic devices may include, for example, a camera, a camcorder, a mobile phone having the same therein, a display device, a security device, or a medical device, but is not limited thereto. Although not shown, the light sensing device and/or the photosensor in the image sensor of fig. 3-8 may be modified to further include charge assist layers 40 and 45, like the optoelectronic device 100' in fig. 2.

Fig. 9 is a block diagram of a digital camera including an image sensor according to an embodiment.

Referring to fig. 9, the digital camera 1000 includes a lens 1010, an image sensor 1020, a motor 1030, and an engine 1040. The image sensor 1020 may be one of the image sensors according to the embodiments shown in fig. 3 to 8.

The lens 1010 concentrates incident light on the image sensor 1020. The image sensor 1020 generates RGB data for the received light through the lens 1010.

In an embodiment, the image sensor 1020 may interface with an engine 1040.

The motor 1030 may adjust the focal length of the lens 1010 or execute a shutter in response to a control signal received from the engine 1040. The engine 1040 may control the image sensor 1020 and the motor 1030.

The engine 1040 may be connected to a host/application 1050.

Fig. 10 is a block diagram of an electronic device according to an embodiment.

Referring to fig. 10, an electronic device 1100 may include a processor 1120, a memory 1130, and an image sensor 1140 electrically coupled together via a bus 1110. The image sensor 1140 may be an image sensor according to one of the previous embodiments. The memory 1130, which may be a non-transitory computer readable medium, may store a program of instructions and/or other information. The memory 1130 may be a non-volatile memory such as a flash memory, a phase change random access memory (PRAM), a magnetoresistive ram (mram), a resistive ram (reram), or a ferroelectric ram (fram), or a volatile memory such as a static ram (sram), a dynamic ram (dram), or a synchronous dram (sdram). Processor 1120 may execute stored programs of instructions to perform one or more functions. For example, processor 1120 may be configured to process electrical signals generated by image sensor 1140. The processor 1120 may be configured to generate an output (e.g., an image to be displayed on a display interface) based on such processing.

One or more of the above disclosed elements may include or be implemented in: processing circuitry, such as hardware including logic circuitry; a hardware/software combination, such as a processor executing software; or a combination thereof. For example, the processing circuitry may more specifically include, but is not limited to, a Central Processing Unit (CPU), an Arithmetic Logic Unit (ALU), a digital signal processor, a microcomputer, a Field Programmable Gate Array (FPGA), a system on a chip (SoC), a programmable logic unit, a microprocessor, an Application Specific Integrated Circuit (ASIC), and so forth.

Hereinafter, embodiments will be explained in more detail with reference to examples. However, these embodiments are not limiting, and the inventive concept is not limited thereto.

Fabrication of optoelectronic devices

Example 1

ITO was sputtered onto a glass substrate to form an approximately 150nm thick anode, and PEDOT (poly (3, 4-ethylenedioxythiophene)) was deposited to form a 45nm thick Hole Transport Layer (HTL). Subsequently, on the Hole Transport Layer (HTL), a solution prepared by dispersing the compound represented by chemical formula 1A-1A (p-type semiconductor compound, octabutoxynaphthalocyanine dichloride) and PC60BM ([6,6] -phenyl-C61-butyric acid methyl ester, n-type semiconductor compound) in a chlorobenzene solvent was spin-coated to form a 150nm thick photoactive layer. Here, a p-type semiconductor compound and an n-type semiconductor compound were used at a volume ratio (p: n) of 1: 3. On the photoactive layer, C60 was deposited to form a 30nm thick auxiliary layer. On the auxiliary layer, Ag was deposited to form a 20nm thick cathode. Subsequently, on the cathode, sealing was performed using a glass plate to manufacture an optoelectronic device.

[ chemical formula 1A-1A ]

In the chemical formula 1A-1A,

two R^1aTwo R^2aTwo R^3aAnd two R^4aIs O (CH)₂)₃CH₃。

Example 2

On a glass substrate, ITO was sputtered to form an anode about 150nm thick, and molybdenum oxide (MoO) was deposited thereon_x,0<x.ltoreq.3) to form a charge-assist layer 20nm thick. On the charge assist layer, a solution obtained by dispersing the compound represented by chemical formula 1A-1A (p-type semiconductor compound) and the compound represented by chemical formula 2B-1aa (n-type semiconductor compound) in a chlorobenzene solvent was spin-coated to form a 150nm thick photoactive layer. Here, a p-type semiconductor compound and an n-type semiconductor compound were used in a volume ratio (p: n) of 1: 1.2. On the photoactive layer, C60 was deposited to form a 30nm thick auxiliary layer. On the auxiliary layer, ITO was deposited to form a 7nm thick cathode. Subsequently, sealing was performed using a glass plate to manufacture an optoelectronic device.

[ chemical formula 2B-1aa ]

Example 3

A photovoltaic device was fabricated according to the same method as in example 2, except that: the compound represented by chemical formula 2B-1ab is used instead of the compound represented by chemical formula 2B-1 aa.

[ chemical formula 2B-1ab ]

The compound represented by chemical formula 2B-1ab is a mixture of a compound having a symmetric substitution site of F and a compound having an asymmetric substitution site of F (FOIC of 1-Material Inc.).

Example 4

A photovoltaic device was fabricated according to the same method as in example 2, except that: PC70BM was used instead of the compound represented by chemical formula 2B-1 aa.

Comparative example 1

On a glass substrate, ITO was sputtered to form an approximately 150nm thick anode, and PEDOT (poly (3, 4-ethylenedioxythiophene)) was deposited thereon to form a 45nm thick Hole Transport Layer (HTL). Subsequently, on the Hole Transport Layer (HTL), a solution prepared by dispersing the compound represented by chemical formula 1A-1A (p-type semiconductor compound) in a chlorobenzene solvent was spin-coated to form a 25nm thick p-type layer, and C60 was deposited to form a 30nm thick n-type layer. On the n-type layer, Ag was deposited to form a 20nm thick cathode. Subsequently, on the cathode, sealing was performed using a glass plate to manufacture an optoelectronic device.

Evaluation of external Quantum efficiency and dark Current

The photoelectric devices according to example 1 and comparative example 1 were evaluated with respect to external quantum efficiency, and the results are shown in table 1. The External Quantum Efficiency (EQE) was evaluated at wavelengths from 400nm to 1500nm at 3V with the incident photon-to-current efficiency (IPCE) method. Here, device calibration was performed based on Si and Ge photodiode references.

(Table 1)

	EQE(％)
		Example 1	46.8
Comparative example 1	2.2

Referring to table 1, the photovoltaic device of example 1 exhibited an increased EQE of 20 times or more compared to the photovoltaic device of comparative example 1. The photoelectric devices according to examples 2 to 4 were evaluated with respect to Dark Current (DC), and the results are shown in table 2. In addition, after the photoelectric devices according to examples 2 to 4 were annealed at 140 ℃, dark currents were evaluated, and the results are shown in table 2. After obtaining a current density-voltage (J-V) curve from-5V to 5V using an apparatus manufactured by Keithley Instruments, dark current was evaluated by using a value at 3V.

(Table 2)

Referring to table 2, the photoelectric devices according to examples 2 to 4 exhibited improved current characteristics and excellent dark current characteristics even after annealing.

While some example embodiments have been described, it is to be understood that the inventive concepts are not limited to the disclosed embodiments. On the contrary, the inventive concept is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

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Infrared absorbing composition, and photoelectric device, organic sensor and electronic device comprising same

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