KR102558974B1 - Organic photoelectric device, image sensor, and electronic device including the same - Google Patents

Abstract

An organic photoelectric device including a compound represented by Chemical Formula 1, a first electrode and a second electrode facing each other, and an active layer disposed between the first electrode and the second electrode and including the compound represented by Chemical Formula 1, and an image sensor and an electronic device including the organic photoelectric device.

Description

Organic photoelectric device, image sensor and electronic device

It relates to an organic photoelectric device, an image sensor, and an electronic device including a compound for an organic photoelectric device.

A photoelectric device is a device that converts light into an electrical signal using a photoelectric effect, includes a photodiode, a phototransistor, and the like, and may be applied to an image sensor or the like.

An image sensor including a photodiode has a higher resolution day by day, and accordingly, a pixel size is getting smaller. In the case of a silicon photodiode, which is currently mainly used, a decrease in sensitivity may occur because an absorption area decreases as the size of a pixel decreases. Accordingly, organic materials that can replace silicon are being studied.

Since an organic material has a high absorption coefficient and can selectively absorb light in a specific wavelength range according to its molecular structure, it can simultaneously replace a photodiode and a color filter, which is very advantageous for sensitivity improvement and high integration.

One embodiment provides a compound for an organic photoelectric device that can selectively absorb light in a green wavelength region and has excellent thermal stability.

Another embodiment provides an organic photoelectric device capable of selectively absorbing light in a green wavelength region and improving efficiency.

Another embodiment provides an image sensor and an electronic device including the compound for an organic photoelectric device.

According to one embodiment, a compound for an organic photoelectric device represented by Chemical Formula 1 is provided.

[Formula 1]

In Formula 1,

A is a functional group represented by Formula 1-1 or 1-2 below,

R ¹ to R ⁴ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, and combinations thereof, or

Two adjacent functional groups of R ¹ to R ⁴ are connected to each other to form a cycloalkyl group or a heterocycloalkyl group fused with a julolidinyl group,

m and n are each independently an integer from 0 to 6;

R ^a is selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (—CN), and combinations thereof;

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

* represents a position binding to the methine group of Formula 1,

X^Oneand X²are each independently -C (R²²)(R²³)-(where R²²and R²³are each independently selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group, a cyano-containing group, and combinations thereof), -C(=C(R²⁴)(R²⁵))-(where R²⁴and R²⁵are each independently selected from a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (-CN), a cyano-containing group, and combinations thereof), an indanone group, an indandione group, -C(=O)-, -S(=O)₂- and combinations thereof,

R ¹¹ to R ¹⁶ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (-CN), a cyano-containing group, and combinations thereof;

k is an integer of 0 or 1;

R ³⁰ is selected from a halogen, a cyano group (-CN), a cyano-containing group, and combinations thereof;

R ³¹ is selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (-CN), a cyano-containing group, and combinations thereof;

p is an integer from 1 to 5, q is an integer from 0 to 5, and p+q is an integer of 5 or less.

In Formula 1, one aromatic ring may be present in the fused ring moiety including the julolidinyl group.

The total number of rings in the compound for an organic photoelectric device may be 5 to 7.

The compound for an organic photoelectric device may have a maximum absorption wavelength (λ _max ) in a range of about 500 nm to about 600 nm, for example, about 520 nm to about 570 nm in a thin film state.

The compound for an organic photoelectric device may exhibit an absorption curve having a full width at half maximum (FWHM) of about 50 nm to about 100 nm in a thin film state.

X ¹ and X ² in Formula 1-1 are each independently -C(R ²² )(R ²³ )

-(wherein R ²² and R ²³ are each independently selected from -F, -Cl, -Br, -I, a cyano group, a cyano-containing group, and combinations thereof), -C(=C(R ²⁴ )(R ²⁵ ))-(wherein R ²⁴ and R ²⁵ are each independently selected from -F, -Cl, -Br, -I, a cyano group (-CN), a cyano-containing group, and combinations thereof ), -C(=O)-, -S(=O) ₂ - and combinations thereof.

A of Formula 1 may be a functional group represented by Formula 1A below:

[Formula 1A]

In Formula 1A, * represents a binding position to the methine group of Formula 1,

R ^a , R ^b , R ^c and R ^d are each independently selected from hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C1 to C6 haloalkyl group, a halogen, a cyano group (—CN), a cyano-containing group, and combinations thereof;

a is an integer from 0 to 4 and b is an integer from 0 to 2.

A compound for an organic photoelectric device represented by Chemical Formula 2 and having a maximum absorption wavelength (λ _max ) at 500 nm to 600 nm in a thin film state is provided.

[Formula 2]

In Formula 2,

R ¹ to R ⁴ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, and combinations thereof, or

Two adjacent functional groups of R ¹ to R ⁴ are linked to each other to form a cycloalkyl group or a heterocycloalkyl group fused with a juloridinyl group,

m and n are each independently an integer from 0 to 6;

R ^a is selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (—CN), and combinations thereof;

R ¹¹ to R ¹⁶ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (-CN), and a cyano-containing group;

k is an integer of 0 or 1;

One aromatic ring may exist in the fused ring moiety including the juloridinyl group.

The total number of rings in the compound for an organic photoelectric device may be 5 to 7.

The compound for an organic photoelectric device may have a maximum absorption wavelength (λ _max ) in a range of about 520 nm to about 570 nm in a thin film state.

The compound for an organic photoelectric device may exhibit an absorption curve having a full width at half maximum (FWHM) of about 50 nm to about 100 nm in a thin film state.

According to another embodiment, an organic photoelectric device including a first electrode and a second electrode facing each other, and an active layer disposed between the first electrode and the second electrode and including the compound represented by Formula 1 or Formula 2 is provided.

The active layer may further include an n-type semiconductor compound.

The n-type semiconductor compound may be subphthalocyanine, a subphthalocyanine derivative, fullerene or a fullerene derivative, thiophene or a thiophene derivative, or a combination thereof.

The active layer may include an intrinsic layer including the compound represented by Formula 1 or Formula 2 above.

The active layer may include a p-type layer including the compound represented by Formula 1 or Formula 2 above.

The active layer may further include at least one of a p-type layer positioned on one side of the intrinsic layer and an n-type layer positioned on the other side of the intrinsic layer.

The active layer may further include a second p-type semiconductor compound that selectively absorbs green light. Examples of the second p-type semiconductor compound include compounds represented by the following Chemical Formula 6.

[Formula 6]

In Formula 6,

R⁷¹ to R⁷³are each independently hydrogen, a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, a substituted or unsubstituted C2 to C30 aliphatic heterocyclic group, a substituted or unsubstituted C2 to C30 aromatic heterocyclic group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a thiol group, a substituted or unsubstituted C6 to C30 alkylthio group , A substituted or unsubstituted C6 to C30 arylthio group, a cyano group, a cyano-containing group, a halogen group, a halogen-containing group, a substituted or unsubstituted sulfonyl group, or a combination thereof, or R⁷¹ to R⁷³Two adjacent silver are connected to form a fused ring,

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a divalent substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof;

R ⁷⁴ to R ⁷⁶ are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted amine group, a substituted or unsubstituted silyl group, or a combination thereof;

a, b and c are each independently an integer of 0 to 4.

The active layer may include the compound for an organic photoelectric device and C60 in a volume ratio of about 0.9:1 to about 1.1:1, and may have an extinction coefficient of about 8.0×10 ⁴ cm ⁻¹ or more.

According to another embodiment, an image sensor including the organic photoelectric device is provided.

The image sensor may include a semiconductor substrate on which a plurality of first light sensing elements detecting light in a blue wavelength region and a plurality of second light sensing elements sensing light in a red wavelength region are integrated, and the organic photoelectric element disposed on the semiconductor substrate and selectively absorbing light in a green wavelength region.

The first photo-sensing device and the second photo-sensing device may be stacked in a vertical direction on a semiconductor substrate.

The image sensor may further include a color filter layer disposed between the semiconductor substrate and the organic photoelectric device and including a blue filter selectively transmitting light in a blue wavelength region and a red filter selectively transmitting light in a red wavelength region.

A green photoelectric device that is the organic photoelectric device, a blue photoelectric device that selectively absorbs light in a blue wavelength region, and a red photoelectric device that selectively absorbs light in a red wavelength region may be stacked.

According to another embodiment, an electronic device including the compound for an organic photoelectric device is provided.

An organic photoelectric device, an image sensor, and an electronic device capable of improving efficiency by providing a compound capable of selectively absorbing light in a green wavelength region and increasing wavelength selectivity in a green wavelength region by the compound.

1 is a cross-sectional view illustrating an organic photoelectric device according to an embodiment;
2 is a cross-sectional view illustrating an organic photoelectric device according to another embodiment;
3 is a schematic diagram schematically illustrating an organic CMOS image sensor according to an exemplary embodiment;
4 is a cross-sectional view of the organic CMOS image sensor of FIG. 3;
5 is a schematic cross-sectional view of an organic CMOS image sensor according to another embodiment;
6 is a schematic cross-sectional view of an organic CMOS image sensor according to another embodiment;
7 is a schematic diagram schematically illustrating an organic CMOS image sensor according to another embodiment;
8 is a view showing absorption curves of the compounds of Synthesis Examples 4 to 6 in a thin film state;
9 is a diagram showing the external quantum efficiency (EQE) according to the wavelength of the organic photoelectric devices according to Examples 5 and 6;
10 is a diagram illustrating external quantum efficiency (EQE _max ) according to an applied electric field of organic photoelectric devices according to Examples 5 and 6;
11 is a diagram showing a result of measuring crosstalk of an organic photoelectric device according to Example 5;

Hereinafter, embodiments will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In the drawings, the thickness is shown enlarged to clearly express the various layers and regions. Like reference numerals have been assigned to like parts throughout the specification. When a part such as a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the case where it is "directly on" the other part, but also the case where there is another part in between. Conversely, when a part is said to be "directly on" another part, it means that there is no other part in between.

In order to clearly describe this embodiment in the drawings, parts irrelevant to the description are omitted, and the same reference numerals are used for the same or similar components throughout the specification.

Unless otherwise defined herein, "substituted" means that a hydrogen atom in a compound is a halogen atom (F, Br, Cl or I), a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C20 alkynyl group 20 alkoxy groups, C6 to C30 aryl groups, C7 to C30 arylalkyl groups, C1 to C4 alkoxy groups, C1 to C20 heteroalkyl groups, C3 to C20 heteroarylalkyl groups, C3 to C30 cycloalkyl groups, C3 to C15 cycloalkenyl groups, C6 to C15 cycloalkynyl groups, C2 to C20 heterocycloalkyl groups, and combinations thereof.

In addition, unless otherwise defined in this specification, “hetero” means containing 1 to 3 heteroatoms selected from N, O, S and P.

In addition, unless otherwise defined herein, "halogen" means F, Cl, Br or I, and "halogen-containing group" means that at least one of hydrogen is substituted with F, Cl, Br or I. For example, a haloalkyl group means that at least one hydrogen of the alkyl group is substituted with F, Cl, Br or I. Specific examples of haloalkyl groups include fluoroalkyl groups such as perfluoroalkyl groups.

Unless otherwise defined herein, "cyano-containing group" means a monovalent functional group in which at least one hydrogen of a C1 to C30 alkyl group, a C2 to C30 alkenyl group, or a C2 to C30 alkynyl group is substituted with a cyano group. In addition, the cyano-containing group may include a divalent functional group such as a dicyanoalkenyl group represented by =CR ^x' -(CR ^x R ^y ) _p -CR ^y' (CN) ₂ , wherein R ^x , R ^y , R ^{x '} and R ^{y '} are each independently hydrogen or a C1 to C10 alkyl group, and p is an integer of 0 to 10. A specific example of the cyano-containing group is a dicyanomethyl group. ), dicyanovinyl group, and cyanoethynyl group.

Unless otherwise defined herein, “combination” refers to substituents in which one substituent is substituted with another substituent, fused with each other, or linked to each other by a single bond or a C1 to C10 alkylene group. The haloalkyl group may be a C1 to C30 haloalkyl group (eg, a perfluoroalkyl group).

Hereinafter, a compound for an organic photoelectric device according to an embodiment will be described.

A compound for an organic photoelectric device according to an embodiment is represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1,

A is a functional group represented by Formula 1-1 or 1-2 below,

R ¹ to R ⁴ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, and combinations thereof, or

Two adjacent functional groups of R ¹ to R ⁴ are connected to each other to form a cycloalkyl group or a heterocycloalkyl group fused with a julolidinyl group,

m and n are each independently an integer from 0 to 6;

R ^a is selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen (-F, -Cl, -Br, -I), a cyano group (-CN), and combinations thereof.

Two adjacent functional groups among R ¹ to R ⁴ forming a cycloalkyl group or a heterocycloalkyl group fused with the julolidinyl group may be functional groups bonded to different carbon atoms.

In Formula 1, a substituent selected from a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, and combinations thereof may be introduced into R ¹ to R ⁴ to adjust the HOMO/LUMO energy level, band gap, and absorption of the compound. . In one embodiment, the "substitution" is preferably substituted with a substituent selected from -F, -Cl, -Br, -I, a cyano group, a cyano-containing group, and combinations thereof.

In Formula 1, the juloridinyl group is a 2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizinyl group, which is an electron donating functional group.

In Chemical Formula 1, the methine group is bonded to the para position (position 9) with respect to N of the juloridinyl group, so that the electron donating action of the juloridinyl group can be increased.

In Formula 1, A is an electron withdrawing group and may be a functional group represented by Formula 1-1 or 1-2 below.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

* represents a position binding to the methine group of Formula 1,

X^Oneand X²are each independently -C (R²²)(R²³)-(where R²²and R²³are each independently selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group, a cyano-containing group, and combinations thereof), -C(=C(R²⁴)(R²⁵))-(where R²⁴and R²⁵are each independently selected from a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (-CN), a cyano-containing group, and combinations thereof), an indanone group, an indandione group, -C(=O)-, -S(=O)₂- and combinations thereof,

R ¹¹ to R ¹⁶ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (-CN), a cyano-containing group, and combinations thereof;

k is an integer of 0 or 1;

R ³⁰ is selected from a halogen, a cyano group (-CN), a cyano-containing group, and combinations thereof;

R ³¹ is selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (—CN), a cyano-containing group, and combinations thereof;

p is an integer from 1 to 5, q is an integer from 0 to 5, and p+q is an integer of 5 or less.

When the substituent R ² of carbon 7 and the substituent R ³ of carbon 8 of Formula 1 are connected to each other to form a cycloalkyl ring or a heterocycloalkyl ring fused with the benzene ring of the juloridinyl group, the half width of the absorption curve is narrowed, resulting in excellent wavelength selectivity. Here, the cycloalkyl ring means a C5 to C10 cycloalkyl ring, and the heterocycloalkyl ring means a 5-membered to 10-membered heterocycloalkyl ring containing at least one hetero atom selected from N, O and S. The cycloalkyl ring or heterocycloalkyl ring does not form a conjugated structure with the benzene ring of the juloridinyl group. Accordingly, the selective absorption of green light can be improved. The compound for an organic photoelectric device has bipolar characteristics by including an electron donor moiety and an electron acceptor moiety in one molecule.

In the compound for an organic photoelectric device, the total number of rings of the compound may be 5 to 7. Here, the ring means a 5-member to 10-member ring having a closed structure. When the number of rings exceeds 7, the maximum absorption wavelength is shifted to red, and thus the selective absorption of green light is reduced. In addition, when the number of the rings is less than 5, the maximum absorption wavelength shifts to blue, thereby degrading the selective absorption of green light.

The compound for an organic photoelectric device includes a bulky juloridinyl group as an electron donor moiety to reduce intermolecular interactions between molecules in a film state, thereby preventing unnecessary aggregation between molecules during film production. Intermolecular aggregation results in a relatively broad distribution of absorption peaks. Accordingly, the compound for an organic photoelectric device may increase selectivity for a green wavelength region due to the electron donor moiety.

In Chemical Formula 1, one aromatic ring may be present in the fused ring moiety including a juloridinyl group. Here, the aromatic ring means a monocyclic ring or polycyclic ring in which atoms in the ring form a conjugated structure. That is, two adjacent functional groups of R ¹ to R ⁴ are connected to each other to provide a non-aromatic ring structure of a cycloalkyl group or a heterocycloalkyl group fused with a juloridinyl group. When two or more aromatic rings are present, the conjugation length is long, so that desirable green wavelength selectivity cannot be provided, and absorption intensity is also low.

The compound for an organic photoelectric device may exhibit an absorption curve having a relatively small half width of about 50 nm to about 100 nm, specifically about 50 nm to about 95 nm, and more specifically about 50 nm to about 90 nm in a thin film state. Here, the half width is the width of the wavelength corresponding to half of the maximum absorption point, and when the half width is small, it means that light in a narrow wavelength range is selectively absorbed and the wavelength selectivity is high. Selectivity for a green wavelength region may be increased by having a half width within the above range. The thin film may be a thin film deposited under vacuum conditions.

The compound for an organic photoelectric device is a compound that selectively absorbs light in a green wavelength region, and may have a maximum absorption wavelength (λ _max ) at about 500 nm to about 600 nm, specifically about 520 nm to about 570 nm or 525 nm to about 570 nm in a thin film state.

The compound for an organic photoelectric device may have a HOMO level of about 5.2 to about 5.7 eV and a LUMO level of about 3.2 to about 3.7 eV. By having the HOMO level and the LUMO level in the above range, it can be applied as a semiconductor that effectively absorbs light in the green wavelength region, and thus can have high external quantum efficiency (EQE), thereby improving photoelectric conversion efficiency.

The compound for an organic photoelectric device may have a molecular weight of about 300 to about 900, more specifically about 350 to about 700. By having a molecular weight within the above range, it is possible to effectively prevent thermal decomposition of the compound when forming a thin film by vapor deposition while preventing the crystallinity of the compound.

The compound for an organic photoelectric device may have a decomposition temperature of about 220°C or more, more specifically about 250°C or more. Here, the decomposition temperature is the temperature at which a weight loss of about 1% by weight begins to be seen. The decomposition temperature of the compound for an organic photoelectric device should be higher than the melting temperature, and the greater the difference between the melting temperature and the decomposition temperature, the better the thermal stability during the deposition process. In this case, it is possible to provide an organic photoelectric device having excellent photoelectric conversion performance because the film can be stably deposited and decomposition products are reduced.

X ¹ and X ² in Formula 1-1 are each independently -C(R ²² )(R ²³ )-(wherein R ²² and R ²³ are each independently selected from -F, -Cl, -Br, -I, a cyano group, a cyano-containing group, and combinations thereof), -C(=C(R ²⁴ )(R ²⁵ ))-(wherein R ²⁴ and R ²⁵ are Each independently selected from -F, -Cl, -Br, -I, a cyano group (-CN), a cyano-containing group, and combinations thereof), -C(=O)-, -S(=O) ₂ - and combinations thereof.

More specific examples of the above A include functional groups (1) to (7) of Formula 1A.

[Formula 1A]

In Formula 1A,

* represents a position bonded to the methine group of Formula 1, R ^a , R ^b , R ^c and R ^d are each independently selected from hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C1 to C6 haloalkyl group, a halogen, a cyano group (-CN), a cyano-containing group, and combinations thereof;

a is an integer from 0 to 4 and b is an integer from 0 to 2.

In the functional group of Formula 1A, the functional group represented by Formula 1A (1) may be a functional group represented by Formula 1A (8) below.

[Formula 1A (8)]

In Formula 1A (8),

* represents a binding position to the methine group of Formula 1.

The compound for an organic photoelectric device may be represented by Chemical Formula 2 below.

[Formula 2]

In Formula 2,

R ¹ to R ⁴ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, and combinations thereof, or

Two adjacent functional groups of R ¹ to R ⁴ are linked to each other to form a cycloalkyl group or a heterocycloalkyl group fused with a juloridinyl group,

m and n are each independently an integer from 0 to 6;

R ^a is selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (—CN), and combinations thereof;

R ¹¹ to R ¹⁶ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (-CN), and a cyano-containing group;

k is an integer of 0 or 1;

Hereinafter, an organic photoelectric device according to an embodiment including the compound will be described with reference to drawings.

1 is a cross-sectional view illustrating an organic photoelectric device according to an exemplary embodiment.

Referring to FIG. 1 , an organic photoelectric device 100 according to an embodiment includes a first electrode 10 and a second electrode 20 facing each other, and an active layer 30 positioned between the first electrode 10 and the second electrode 20.

One of the first electrode 10 and the second electrode 20 is an anode and the other is a cathode. At least one of the first electrode 10 and the second electrode 20 may be a light-transmitting electrode, and the light-transmitting electrode may be made of a transparent conductor such as indium tin oxide (ITO) or indium zinc oxide (IZO), or a thin single layer or multi-layer metal thin film. When one of the first electrode 10 and the second electrode 20 is an opaque electrode, it may be made of, for example, an opaque conductor such as aluminum (Al).

The active layer 30 is a layer that includes a p-type semiconductor compound and an n-type semiconductor compound to form a pn junction, generates excitons by receiving light from the outside, and then separates the generated excitons into holes and electrons.

The active layer 30 includes the compound represented by Formula 1 above. The compound for an organic photoelectric device may be applied as a p-type semiconductor compound in the active layer 30 .

The compound for an organic photoelectric device is a compound that selectively absorbs light in a green wavelength region, and the active layer 30 including the compound may selectively absorb green wavelength light having a maximum absorption wavelength (λ _max ) at about 500 nm to about 600 nm, specifically about 520 nm to about 570 nm or 525 nm to about 570 nm.

The active layer 30 may exhibit an absorption curve having a relatively small full width at half maximum (FWHM) of about 50 nm to about 100 nm, specifically about 50 nm to about 90 nm. Accordingly, the active layer 30 may have high selectivity for light in the green wavelength region.

The active layer 30 may further include an n-type semiconductor compound for forming a pn junction.

The n-type semiconductor compound may be subphthalocyanine or a subphthalocyanine derivative, fullerene or a fullerene derivative, thiophene or a thiophene derivative, or a combination thereof.

Examples of the fullerene include C60, C70, C76, C78, C80, C82, C84, C90, C96, C240, C540, mixtures thereof, and fullerene nanotubes. The fullerene derivative means a compound having a substituent on the fullerene. The fullerene derivative may include a substituent such as an alkyl group, an aryl group, or a heterocyclic group. Examples of the aryl group and the heterocyclic group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, and benzo Furan ring, benzothiophene ring, isobenzofuran ring, benzimidazole ring, imidazopyridine ring, quinolizidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline An isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathin ring, a phenothiazine ring, or a phenazine ring.

The subphthalocyanine or subphthalocyanine derivative may be represented by Chemical Formula 3 below.

[Formula 3]

In Formula 3,

R ⁶¹ to R ⁶³ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a halogen, a halogen-containing group, or a combination thereof;

a, b and c are integers from 1 to 3;

X is a halogen, for example F or Cl.

The thiophene derivative may be represented by, for example, Formula 4 or Formula 5 below, but is not limited thereto.

[Formula 4]

[Formula 5]

In Formulas 4 and 5,

T ¹ , T ² and T ³ are aromatic rings having a substituted or unsubstituted thiophene moiety,

T ¹ , T ² and T ³ may be independently present or fused,

Y ¹ to Y ⁶ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, a cyano group, or a combination thereof;

EWG ¹ and EWG ² may each independently be an electron withdrawing group.

For example, in Chemical Formula 4, at least one of Y ¹ to Y ⁶ may be an electron withdrawing group, for example, a cyano group or a cyano-containing group.

The active layer 30 may further include a second p-type semiconductor compound that selectively absorbs green light. The second p-type semiconductor compound may include a compound represented by Chemical Formula 6 below.

[Formula 6]

In Formula 6,

R⁷¹ to R⁷³are each independently hydrogen, a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, a substituted or unsubstituted C2 to C30 aliphatic heterocyclic group, a substituted or unsubstituted C2 to C30 aromatic heterocyclic group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a thiol group, a substituted or unsubstituted C1 to C30 alkylthio group , A substituted or unsubstituted C6 to C30 arylthio group, a cyano group, a cyano-containing group, a halogen group, a halogen-containing group, a substituted or unsubstituted sulfonyl group (eg, a substituted or unsubstituted C0 to C30 aminosulfonyl group, a substituted or unsubstituted C1 to C30 alkylsulfonyl group, or a substituted or unsubstituted C6 to C30 arylsulfonyl group), or a combination thereof, or R⁷¹ to R⁷³are two adjacent ones connected to each other to form a fused ring,

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a divalent substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof;

R ⁷⁴ to R ⁷⁶ are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted amine group (eg, a substituted or unsubstituted C1 to C30 alkylamine group or a substituted or unsubstituted C6 to C30 arylamine group), a substituted or unsubstituted A silyl group or a combination thereof,

a, b and c are each independently an integer of 0 to 4.

The second p-type semiconductor compound that selectively absorbs green light is preferably included in an amount of about 500 to about 1500 parts by weight based on 100 parts by weight of the compound of Formula 1.

The active layer 30 may be a single layer or a plurality of layers. The active layer 30 may be, for example, an intrinsic layer (I layer), a p-type layer/I layer, an I-layer/n-type layer, a p-type layer/I layer/n-type layer, or a p-type layer/n-type layer.

The intrinsic layer (I layer) may include a mixture of the compound of Chemical Formula 1 and the n-type semiconductor compound at a thickness (volume) ratio of about 1:100 to about 100:1. It may be included in a thickness (volume) ratio of about 1:50 to 50:1 within the above range, may be included in a thickness (volume) ratio of about 1:10 to 10:1 within the above range, and may be included in a thickness (volume) ratio of about 1:1 within the above range. Having a composition ratio within the above range is advantageous for effective exciton generation and pn junction formation.

The p-type layer may include the semiconductor compound of Chemical Formula 1, and the n-type layer may include the n-type semiconductor compound.

The active layer 30 may have a thickness of about 1 nm to about 500 nm. It may have a thickness of about 5 nm to 300 nm within the above range. By having a thickness within the above range, it is possible to effectively improve photoelectric conversion efficiency by effectively absorbing light and effectively separating and transferring holes and electrons. The optimal film thickness may be determined by considering the light absorption coefficient of the active layer 30, and may have a thickness capable of absorbing light of at least about 70% or more, for example about 80% or more, for example about 90% or more.

The active layer 30 may be formed by depositing the organic photoelectric device compound and an n-type semiconductor compound, for example, C60, in a volume ratio of about 0.9: 1 to about 1.1: 1, for example, 1: 1, and the active layer 30 may have an extinction coefficient of about 8.0 × 10 ⁴ cm ^-1 or more, for example, about 8.5 × 10 ⁴ cm ^{-1 or} more. As such, the active layer 30 having a high extinction coefficient can be implemented with a very thin thickness. When the film thickness of the active layer 30 is thin, the gap between the first electrode 10 and the second electrode 20 can be narrowed. Therefore, when driving by applying a voltage to the organic photoelectric device, the thinner organic photoelectric device can be driven by a strong electric field at the same voltage. In this case, an organic photoelectric device having higher efficiency can be provided.

In the organic photoelectric device 100, when light is incident from the side of the first electrode 10 and/or the second electrode 20 and the active layer 30 absorbs light in a predetermined wavelength region, excitons may be generated inside. Excitons are separated into holes and electrons in the active layer 30, the separated holes move to the anode side of one of the first electrode 10 and the second electrode 20, and the separated electrons move to the cathode side of the other one of the first electrode 10 and the second electrode 20, so that current can flow through the organic photoelectric device.

An organic photoelectric device according to another embodiment will be described below with reference to FIG. 2 .

2 is a cross-sectional view illustrating an organic photoelectric device according to another embodiment.

Referring to FIG. 2 , the organic photoelectric device 200 according to the present embodiment includes a first electrode 10 and a second electrode 20 facing each other, and an active layer 30 positioned between the first electrode 10 and the second electrode 20, as in the above-described embodiment.

However, unlike the above-described embodiment, the organic photoelectric device 200 according to the present embodiment further includes charge auxiliary layers 40 and 45 between the first electrode 10 and the active layer 30 and between the second electrode 20 and the active layer 30, respectively. The auxiliary charge layers 40 and 45 facilitate the movement of holes and electrons separated from the active layer 30 to increase efficiency.

The charge auxiliary layers 40 and 45 include a hole injecting layer (HIL) for facilitating hole injection, a hole transporting layer (HTL) for facilitating hole transport, an electron blocking layer (EBL) for preventing electron movement, an electron injection layer (EIL) for facilitating electron injection, and an electron transporting layer (ETL) for facilitating electron transport. and at least one selected from a hole blocking layer (HBL) that blocks the movement of holes.

The auxiliary charge layers 40 and 45 may include, for example, an organic material, an inorganic material, or an inorganic material. The organic material may be an organic compound having hole or electron injection and/or transfer characteristics, and the inorganic material may be a metal oxide such as molybdenum oxide, tungsten oxide, or nickel oxide.

The hole transport layer (HTL) is, for example, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), PEDOT:PSS), polyarylamine, poly(N-vinylcarbazole) (poly(N-vinylcarbazole), polyaniline, polypyrrole, N,N,N',N'-tetrakis. (4-methoxyphenyl)-benzidine (N,N,N',N'-tetrakis(4-methoxyphenyl)-benzidine, TPD), 4,4′-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl (4,4′-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl, α-NPD), m-MTDATA, 4,4′,4″-tris(N-car Bazolyl) -triphenylamine (4,4', 4″-tris (N-carbazolyl) -triphenylamine, TCTA) and one selected from combinations thereof, but is not limited thereto.

The electron blocking layer (EBL) is, for example, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), PEDOT:PSS), polyarylamine, poly(N-vinylcarbazole) (poly(N-vinylcarbazole), polyaniline, polypyrrole, N,N,N',N'-tetrakis ( 4-methoxyphenyl)-benzidine (N,N,N',N'-tetrakis(4-methoxyphenyl)-benzidine, TPD), 4,4'-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl (4,4'-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl, α-NPD), m-MTDATA, 4,4',4″-tris(N-carboxylate) Zolyl) -triphenylamine (4,4', 4″-tris (N-carbazolyl) -triphenylamine, TCTA) and one selected from combinations thereof, but is not limited thereto.

The electron transport layer (ETL) may include, for example, one selected from 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA), bathocuproine (BCP), LiF, Alq3, Gaq3, Inq3, Znq2, Zn(BTZ)2, BeBq2, and combinations thereof, It is not limited to this.

The hole blocking layer (HBL) may include, for example, one selected from 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA), bassocuproin (BCP), LiF, Alq3, Gaq3, Inq3, Znq2, Zn(BTZ)2, BeBq2, and combinations thereof, but is not limited thereto. .

One of the charge auxiliary layers 40 and 45 may be omitted.

The organic photoelectric device may be applied to a solar cell, an image sensor, an optical detector, an optical sensor, and an organic light emitting diode, but is not limited thereto.

Hereinafter, an example of an image sensor to which the organic photoelectric device is applied will be described with reference to drawings. Here, an organic CMOS image sensor will be described as an example of an image sensor.

FIG. 3 is a plan view schematically illustrating an organic CMOS image sensor according to an exemplary embodiment, and FIG. 4 is a cross-sectional view of the organic CMOS image sensor of FIG. 3 .

3 and 4 , an organic CMOS image sensor 300 according to an embodiment includes a semiconductor substrate 310 on which light sensing devices 50B and 50R, a transfer transistor (not shown) and a charge storage 55 are integrated, a lower insulating layer 60, a color filter layer 70, an upper insulating layer 80, and an organic photoelectric device 100.

The semiconductor substrate 310 may be a silicon substrate, and photo-sensing devices 50B and 50R, a transfer transistor (not shown), and a charge storage 55 are integrated therein. The photo-sensing elements 50R and 50B may be photodiodes.

The photo-sensing elements 50B and 50R, the transfer transistor, and/or the charge storage 55 may be integrated for each pixel. For example, as shown in the drawing, the photo-sensing elements 50B and 50R may be included in the blue and red pixels, and the charge storage 55 may be included in the green pixel.

The photo-sensing devices 50B and 50R sense light, and the sensed information may be transferred by a transfer transistor, and the charge storage 55 may be electrically connected to the organic photoelectric device 100 to be described later, and information of the charge storage 55 may be transferred by the transfer transistor.

In the drawings, a structure in which the light sensing elements 50B and 50R are arranged side by side is exemplarily shown, but is not limited thereto, and the blue light sensing element 50B and the red light sensing element 50R may be vertically stacked.

Metal wiring (not shown) and pads (not shown) are further formed on the semiconductor substrate 310 . The metal wires and pads may be made of metals having low resistivity, such as aluminum (Al), copper (Cu), silver (g), and alloys thereof to reduce signal delay, but are not limited thereto. However, the structure is not limited to the above structure, and metal wires and pads may be positioned below the photo-sensing elements 50B and 50R.

A lower insulating layer 60 is formed on the metal wiring and the pad. The lower insulating layer 60 may be made of an inorganic insulating material such as silicon oxide and/or silicon nitride or a low K material such as SiC, SiCOH, SiCO, and SiOF. Lower insulating layer 60 has trenches exposing charge storage 55 . The trench may be filled with a filling material.

A color filter layer 70 is formed on the lower insulating layer 60 . The color filter layer 70 includes a blue filter 70B formed on a blue pixel and a red filter 70R formed on a red pixel. In this embodiment, an example without a green filter is described, but a green filter may be provided in some cases.

The color filter layer 70 may be omitted in some cases. For example, in a structure in which the blue light sensing device 50B and the red light sensing device 50R are vertically stacked, the blue light sensing device 50B and the red light sensing device 50R can selectively absorb light in each wavelength region according to the stacking depth, so the color filter layer 70 may not be provided.

An upper insulating layer 80 is formed on the color filter layer 70 . The upper insulating layer 80 removes the level difference caused by the color filter layer 70 and flattens it. The upper insulating layer 80 and the lower insulating layer 60 have contacts (not shown) exposing pads and penetrations 85 exposing the charge storage 55 of the green pixel.

The above-described organic photoelectric device 100 is formed on the upper insulating layer 80 . As described above, the organic photoelectric device 100 includes the first electrode 10, the active layer 30, and the second electrode 20.

Both the first electrode 10 and the second electrode 20 may be transparent electrodes, and the active layer 30 is as described above. The active layer 30 may selectively absorb light in a green wavelength region and may replace a color filter of a green pixel.

Light incident from the side of the second electrode 20 may be mainly absorbed and photoelectrically converted in the active layer 30 in the green wavelength range, and light in the remaining wavelength range may pass through the first electrode 10 and be sensed by the photodetectors 50B and 50R.

Since the organic photoelectric device including the compound for an organic photoelectric device has excellent green selective absorption, it can be usefully used in the image sensor having a multilayer structure shown in FIGS. 3 and 4 . As described above, a miniaturized image sensor may be implemented by reducing the size of the image sensor by having a structure in which organic photoelectric devices selectively absorbing light in a green wavelength region are stacked.

Although FIG. 4 shows an example including the organic photoelectric device 100 of FIG. 1 , the present invention is not limited thereto and the same may be applied to a case including the organic photoelectric device 200 of FIG. 2 . FIG. 5 is a cross-sectional view of an organic CMOS image sensor 400 to which the organic photoelectric device 200 of FIG. 2 is applied, showing the structure of an image sensor having such a structure.

6 is a cross-sectional view schematically illustrating an organic CMOS image sensor according to another embodiment.

Referring to FIG. 6 , an organic CMOS image sensor 500 according to the present embodiment includes a semiconductor substrate 310 on which light sensing elements 50B and 50R, a transfer transistor (not shown) and a charge storage 55 are integrated, an insulating layer 80, and an organic photoelectric element 100, as in the above-described embodiment.

However, in the organic CMOS image sensor 500 according to the present embodiment, unlike the above-described embodiment, the blue light sensing element 50B and the red light sensing element 50R are stacked, and the color filter layer 70 may be omitted. The blue light sensing device 50B and the red light sensing device 50R are electrically connected to the charge storage and may be transferred by a transfer transistor (not shown). The blue light sensing device 50B and the red light sensing device 50R may selectively absorb light of each wavelength region according to the stacking depth.

As described above, a miniaturized image sensor can be realized by further reducing the size of the image sensor by having an organic photoelectric device that selectively absorbs light in the green wavelength region and a structure in which a red light sensing device and a blue light sensing device are stacked. Also, as described above, the organic photoelectric device 100 may reduce crosstalk caused by unnecessary absorption of light in a wavelength region other than green and increase sensitivity by increasing green wavelength selectivity.

Although FIG. 6 shows an example including the organic photoelectric device 100 of FIG. 1 , the present invention is not limited thereto and the same may be applied to a case including the organic photoelectric device 200 of FIG. 2 .

7 is a schematic diagram schematically illustrating an organic CMOS image sensor according to another exemplary embodiment.

Referring to FIG. 7 , the organic CMOS image sensor according to the present embodiment has a structure in which a green photoelectric element G selectively absorbing light in a green wavelength region, a blue photoelectric element B selectively absorbing light in a blue wavelength region, and a red photoelectric element R selectively absorbing light in a red wavelength region are stacked.

Although the drawing shows a structure in which a red photoelectric device R, a blue photoelectric device B, and a green photoelectric device G are sequentially stacked, the stacking order is not limited thereto and may be variously changed.

The green photoelectric device G may be the above-described organic photoelectric device 100, the blue photoelectric device B may include electrodes facing each other and an active layer including an organic material interposed therebetween that selectively absorbs light in a blue wavelength region, and the red photoelectric device R may include electrodes facing each other and an active layer including an organic material interposed therebetween that includes an organic material that selectively absorbs light in a red wavelength region.

As described above, by having a structure in which an organic photoelectric device selectively absorbing light in a green wavelength region, an organic photoelectric device selectively absorbing light in a red wavelength region, and an organic photoelectric device selectively absorbing light in a blue wavelength region are stacked, the size of the image sensor can be further reduced to realize a miniaturized image sensor, while increasing sensitivity and reducing crosstalk.

The image sensor may be applied to various electronic devices, such as a mobile phone, a digital camera, and a biosensor, but is not limited thereto.

The embodiments of the present invention described above will be described in more detail through the following examples. However, the following examples are for illustrative purposes only and do not limit the scope of the present invention.

synthesis example

Synthesis Example 1

A compound of Formula 1a is synthesized according to Scheme 1.

[Formula 1a]

[Scheme 1]

1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinoline-9-carbaldehyde (1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinoline-9-carbaldehyde (4.02 g) and compound 1H-indene-1,3(2H)-dione (1H-indene-1,3(2H)-dione) (2.9 2 g) was stirred in ethanol solvent (150 ml) at 50 ° C. under reflux for 4 hours. The obtained solid was filtered, chemically purified using column chromatography, and recrystallized to obtain the desired compound of formula 1a (yield: 79%).

MALDI-TOF: 328.93 (M ⁺ ), 329.14 (calculated for C ₂₂ H ₁₉ NO ₂ ).

Synthesis Example 2

A compound of Formula 1b is synthesized according to Scheme 2.

[Formula 1b]

[Scheme 2]

1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinoline-9-carbaldehyde (4.02 g) and 1H-cyclopenta[b]naphthalene-1,3(2H)-dione (1H-cyclopenta[b]naphthalene- 1,3(2H)-dione) (3.92 g) was stirred at 50 ° C. under reflux for 4 hours in an ethanol solvent (150 ml), and the obtained solid was filtered, chemically purified using column chromatography, and then recrystallized to obtain the desired compound of Formula 1b (74% yield).

MALDI-TOF: 378.96 (M ⁺ ), 379.16 (calculated for C ₂₆ H ₂₁ NO ₂ ).

Synthesis Example 3

A compound of Formula 1c is synthesized according to Scheme 3.

[Formula 1c]

[Scheme 3]

1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinoline-9-carbaldehyde (1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinoline-9-carbaldehyde) (4.02 g) and 4,5,6,7-tetrafluoro-1H-indene-1,3(2H)-dione) (4,5,6,7 -tetrafluoro-1H-indene-1,3(2H)-dione) (4.36 g) was stirred in an ethanol solvent (150 ml) at 50 ° C. under reflux for 4 hours, and the obtained solid was filtered and chemically purified using column chromatography, followed by recrystallization to obtain the desired compound of Formula 1c (79% yield).

MALDI-TOF: 409.06 (M ⁺ ), 401.10 (calculated for C ₂₂ H ₁₅ F ₄ NO ₂ ).

Synthesis Example 4

A compound of Formula 1d is synthesized according to Scheme 4.

[Formula 1d]

[Scheme 4]

1,1,7,7-tetramethyl-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinoline-9-carbaldehyde (1,1,7,7-tetramethyl-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinoline-9-carbaldehyde) (5.14 g) and 1H-indene-1,3(2H)- Dione (1H-indene-1,3 (2H) -dione) (2.92 g) was stirred in an ethanol solvent (150 ml) at 50 ° C. under reflux for 4 hours. The obtained solid was filtered, chemically purified using column chromatography, and then recrystallized to obtain the desired compound of Formula 1d. (87% yield).

MALDI-TOF: 384.18 (M ⁺ ), 385.20 (calculated for C ₂₆ H ₂₇ NO ₂ ).

Synthesis Example 5

A compound of Formula 1e is synthesized according to Scheme 5.

[Formula 1e]

[Scheme 5]

1,1,7,7-tetramethyl-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinoline-9-carbaldehyde (5.14 g) and 1H-cyclopenta[b]naphthalene- 1,3(2H)-dione (1H-cyclopenta[b]naphthalene-1,3(2H)-dione) (3.92 g) was stirred in an ethanol solvent (150 ml) at 50 ° C. under reflux for 4 hours. The resulting solid was filtered, chemically purified using column chromatography, and then recrystallized to obtain the desired compound of Formula 1e. (78% yield).

MALDI-TOF: 435.21 (M ⁺ ), 435.22 (calculated for C ₃₀ H ₂₉ NO ₂ ).

Synthesis Example 6

A compound of Formula 1f is synthesized according to Scheme 6.

[Formula 1f]

[Scheme 6]

1,1,7,7-tetramethyl-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinoline-9-carbaldehyde (5.14 g) and 4,5,6,7-tetrafluoro-1H -Indene-1,3(2H)-dione (4,5,6,7-tetrafluoro-1H-indene-1,3(2H)-dione) (4.36 g) was stirred in an ethanol solvent (150 ml) at 50 ° C. under reflux for 4 hours. The obtained solid was filtered, chemically purified using column chromatography, and recrystallized to obtain the desired compound of formula 1f (82% yield).

MALDI-TOF: 457.17 (M ⁺ ), 457.17 (calculated for C ₂₆ H ₂₃ F ₄ NO ₂ ).

Synthesis Example 7

A compound of Formula 1g is synthesized according to Scheme 7.

[Formula 1g]

[Scheme 7]

1,1,7,7-tetramethyl-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinoline-9-carbaldehyde (5.14 g) and benzo[b]thiophen-3(2H)-one 1,1-dioxide (benzo[b]thiophen-3(2H)-one 1,1-dioxide) (3.64 g) was stirred in an ethanol solvent (150 ml) at 50 ° C. under reflux for 4 hours. After filtering the obtained solid, it was chemically purified using column chromatography, followed by recrystallization to obtain the desired compound of Formula 1g. (82% yield).

MALDI-TOF: 421.16 (M ⁺ ), 421.17 (calculated for C ₂₅ H ₂₇ NO ₃ S).

Comparative Synthesis Example 1 :

A compound of formula 1h is prepared as disclosed in EP 2259359 A2.

[Formula 1h]

Comparative Synthesis Example 2

A compound of formula 1i is prepared as disclosed in EP 2259359 A2.

[Formula 1i]

Comparative Synthesis Example 3

A compound of formula 1j is prepared as described in WO 2014-054255 A1.

[Formula 1j]

Light absorption characteristics of the compounds according to Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 to 3

Light absorption characteristics are performed in solution state and thin film state.

In order to measure light absorption characteristics in a solution state, the compounds obtained in Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 to 3 were dissolved in toluene at 1.0 x 10 ^{- 5} mol/L, respectively, and then evaluated. The maximum absorption wavelength in the solution state is calculated using a UV-2450 UV-Visible Spectrophotometer (manufactured by Shimadzu).

The light absorption characteristics in the thin film state were prepared by thermal evaporation of the compounds of Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 to 3 at a rate of 0.5-1.0 Å / s under high vacuum (< 10 ^-7 Torr) to prepare a thin film with a thickness of 70 nm, and then the maximum absorption wavelength in the thin film state was measured using a UV-2450 UV-Visible Spectrophotometer (manufactured by Shimadzu).

After preparing a 70 nm thick thin film obtained by co-evaporation of the compounds according to Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 to 3 and C60 at a volume ratio of 1: 1, the thin film was prepared with a Cary 5000 UV spectroscopy (manufactured by Varian). Using ultraviolet-visible light (UV-Vis), the extinction coefficient was measured.

The results are shown in Table 1.

8 shows the absorption curves of the compounds according to Synthesis Examples 4 to 6 in a thin film state.

Thermal stability of the compounds according to Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 to 3

The thermal stability of the compounds according to Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 to 3 was evaluated by measuring the thermal decomposition temperature. Thermal degradation temperature (thermal degradation temperature, T _d ) is a temperature at which a compound starts to decompose, and is a temperature at which a compound is transformed without maintaining its original molecular structure. In general, above the thermal decomposition temperature, atoms in molecules constituting the compound are volatilized and lost in the atmosphere or vacuum, so the thermal decomposition temperature can be evaluated as a temperature at which the initial weight of the compound starts to decrease by heat. Here, it is measured by the thermal gravimetric analysis (TGA) method. The results are shown in Table 1 below.

λ _max (nm) FWHM (nm) extinction coefficient
(thin film, X10 ⁴ cm ^-1 ) energy level T _m (℃) T _d (℃) solution pellicle solution pellicle HOMO (eV) LUMO (eV) Synthesis Example 1 516 531 48 83 8.5 5.36 3.24 240 223 Synthesis Example 2 544 569 51 89 8.7 5.54 3.51 227 225 Synthesis Example 3 528 540 44 95 18.0 5.60 3.57 - 227 Synthesis Example 4 513 526 46 90 19.7 5.38 3.24 198 258 Synthesis Example 5 545 550 48 100 22.6 5.54 3.53 250 266 Synthesis Example 6 526 547 47 97 20.0 5.59 3.54 - 267 Synthesis Example 7 513 526 47 98 15.0 5.49 3.35 205 265 Comparative Synthesis Example 1 515 513 69 103 10.5 5.32 3.18 - 282 Comparative Synthesis Example 2 441 452 78 88 6.15 5.85 3.55 240 288 Comparative Synthesis Example 3 534 558 79 112 5.4 5.64 3.06 310 -

From the results of Table 1, the compounds of Synthesis Examples 1 to 7 each have a maximum absorption wavelength (λ _max ) at 526 nm to 569 nm in a thin film state and a full width at half maximum of 83 nm to 100 nm, so that selective absorption for light in the green wavelength region is excellent. Also, as shown in FIG. 8, it was confirmed that the absorption curve was similar to the Gaussian distribution.

In contrast, the compound of Comparative Synthesis Example 1 showed the maximum absorption wavelength in the middle of the blue wavelength and the green wavelength, the compound of Comparative Synthesis Example 2 showed the maximum absorption wavelength in the blue wavelength range, and the compound of Comparative Synthesis Example 3 showed the maximum absorption wavelength in the green wavelength range, but it can be seen that the half width is wide and the extinction coefficient is low.

In addition, from the results of Table 1, it can be seen that the compounds of Synthesis Examples 1 to 7 have high melting points and/or decomposition temperatures, and thus are suitable for deposition processes due to excellent thermal stability of the compounds.

Fabrication of organic photoelectric devices

Example 1

ITO is deposited on a glass substrate by sputtering to form an anode with a thickness of about 150 nm, and a molybdenum oxide (MoO _x , 0<x≤3) thin film is deposited to a thickness of 20 nm as a charge auxiliary layer thereon. Subsequently, the compound according to Synthesis Example 1 (p-type semiconductor compound) and C60 (n-type semiconductor compound) were co-deposited at a thickness ratio of 1:1 on a molybdenum oxide (MoO _x ) thin film to form an active layer having a thickness of 85 nm. Subsequently, ITO was deposited on the active layer by sputtering to form a cathode having a thickness of 7 nm to fabricate an organic photoelectric device.

Examples 2 to 7

An organic photoelectric device was manufactured in the same manner as in Example 1, except that the compounds (p-type semiconductor compound) according to Synthesis Examples 2 to 7 were used instead of the compound (p-type semiconductor compound) according to Synthesis Example 1.

Comparative Examples 1 to 3

An organic photoelectric device was fabricated in the same manner as in Example 1, except that the compounds (p-type semiconductor compound) according to Comparative Synthesis Examples 1 to 3 were used instead of the compound (p-type semiconductor compound) according to Synthesis Example 1.

External Quantum Efficiency (EQE)

External quantum efficiency (EQE) of the organic photoelectric devices according to Examples 1 to 7 and Comparative Examples 1 to 3 according to wavelength and voltage was evaluated.

External quantum efficiency is measured using an IPCE measurement system (McScience, Korea) equipment. First, after calibrating the equipment using a Si photodiode (Hamamatsu, Japan), the organic photoelectric devices according to Examples 1 to 7 and Comparative Examples 1 to 3 are installed in the equipment, and the external quantum efficiency is measured in a wavelength range of about 300 to 700 nm.

Of these, the external quantum efficiency (EQE) of the organic photoelectric device according to Examples 5 and 6 according to wavelength is shown in FIG. 9, and the external quantum efficiency (EQE _max ) according to the applied electric field of the organic photoelectric device according to Examples 5 and 6 is shown in FIG. 10.

Referring to FIG. 9 , it can be seen that the organic photoelectric devices according to Examples 5 and 6 have good external quantum efficiency (EQE) in a green wavelength region of about 500 nm to 600 nm. Also, referring to FIG. 10 , it can be seen that the external quantum efficiency according to the applied electric field of the organic photoelectric devices according to Examples 5 and 6 is excellent.

crosstalk

Crosstalk of the organic photoelectric devices according to Examples 1 to 7 and Comparative Examples 1 to 3 was measured. The organic photoelectric devices according to Examples 1 to 7 and Comparative Examples 1 to 3 are stacked on the red silicon photodiode and the blue silicon photodiode, respectively, and voltage is applied to measure the photocurrent (electrical signal). Among them, the measured photocurrent of the organic photoelectric device according to Example 5 was converted into EQE, and the result is shown in FIG. 11 .

As shown in FIG. 11, it can be seen that the electrical signals of the organic photoelectric device according to Example 5 do not overlap much with the red and blue electrical signals at 500 nm to 600 nm. From this, it can be seen that crosstalk hardly occurs.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also within the scope of the present invention.

10: first electrode 20: second electrode
30: active layer 40, 45: charge auxiliary layer
100, 200: organic photoelectric device 300, 400, 500: organic CMOS image sensor
310: semiconductor substrate 70B: blue filter 70R: red filter
70: color filter layer 85: penetrating portion
60: lower insulating layer 80: upper insulating layer
50B, 50R: photo-sensing element 55: charge storage

Claims (27)

A first electrode and a second electrode facing each other, and
Active layer positioned between the first electrode and the second electrode
including,
The active layer includes a compound represented by Formula 1 and an n-type semiconductor compound,
Organic photovoltaic devices:
[Formula 1]

In Formula 1,
A is a functional group represented by Formula 1-1 or 1-2 below,
R ¹ to R ⁴ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, and combinations thereof, or
Two adjacent functional groups of R ¹ to R ⁴ are connected to each other to form a cycloalkyl group or a heterocycloalkyl group fused with a julolidinyl group,
m and n are each independently an integer from 0 to 6;
R ^a is selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (—CN), and combinations thereof;
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,
* represents a position binding to the methine group of Formula 1,
X ¹ 과 X ² 는 각각 독립적으로 -C(R ²² )(R ²³ )-(여기에서 R ²² 과 R ²³ 은 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 치환 또는 비치환된 C1 내지 C10 할로알킬기, 할로겐, 시아노기, 시아노 함유기 및 이들의 조합에서 선택됨), -C(=C(R ²⁴ )(R ²⁵ ))-(여기에서 R ²⁴ 와 R ²⁵ 는 각각 독립적으로 치환 또는 비치환된 C1 내지 C10 알킬기, 치환 또는 비치환된 C1 내지 C10 할로알킬기, 할로겐, 시아노기(-CN), 시아노 함유기 및 이들의 조합에서 선택됨), 인다논기(indanone group), 인단디온기(indandione group), -C(=O)-, -S(=O) ₂ - 및 이들의 조합에서 선택되고,
R ¹¹ to R ¹⁶ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (-CN), a cyano-containing group, and combinations thereof;
k is an integer of 0 or 1;
R ³⁰ is selected from a halogen, a cyano group (-CN), a cyano-containing group, and combinations thereof;
R ³¹ is selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (-CN), a cyano-containing group, and combinations thereof;
p is an integer from 1 to 5, q is an integer from 0 to 5, and p+q is an integer of 5 or less. In paragraph 1,
An organic photoelectric device, wherein one aromatic ring is present in the fused ring moiety including a julolidinyl group in Chemical Formula 1. In paragraph 1,
The organic photoelectric device, wherein the total number of rings in the compound is 5 to 7. In paragraph 1,
The compound has a maximum absorption wavelength (λ _max ) at 500 nm to 600 nm in a thin film state, an organic photoelectric device. In paragraph 1,
The organic photoelectric device, wherein the compound has a maximum absorption wavelength (λ _max ) at 520 nm to 570 nm in a thin film state. In paragraph 1,
The organic photoelectric device, wherein the compound exhibits an absorption curve having a full width at half maximum (FWHM) of 50 nm to 100 nm in a thin film state. In paragraph 1,
X ¹ and X ² in Formula 1-1 are each independently -C(R ²² )(R ²³ )-(wherein R ²² and R ²³ are each independently selected from -F, -Cl, -Br, -I, a cyano group, a cyano-containing group, and combinations thereof), -C(=C(R ²⁴ )(R ²⁵ ))-(wherein R ²⁴ and R ²⁵ are Each independently selected from -F, -Cl, -Br, -I, a cyano group (-CN), a cyano-containing group, and combinations thereof), -C(=O)-, -S(=O) ₂ -, and combinations thereof. An organic photoelectric device. In paragraph 1,
A of Formula 1 is a functional group represented by Formula 1A, an organic photoelectric device:
[Formula 1A]

In Formula 1A,
* represents a position binding to the methine group of Formula 1,
R ^a , R ^b , R ^c and R ^d are each independently selected from hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C1 to C6 haloalkyl group, a halogen, a cyano group (—CN), a cyano-containing group, and combinations thereof;
a is an integer from 0 to 4 and b is an integer from 0 to 2. A first electrode and a second electrode facing each other, and
An active layer positioned between the first electrode and the second electrode,
The active layer is represented by Formula 2 below and includes a compound having a maximum absorption wavelength (λ _max ) at 500 nm to 600 nm in a thin film state and an n-type semiconductor compound,
Organic photovoltaic devices:
[Formula 2]

In Formula 2,
R ¹ to R ⁴ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, and combinations thereof, or
Two adjacent functional groups of R ¹ to R ⁴ are connected to each other to form a cycloalkyl group or a heterocycloalkyl group fused with a julolidinyl group,
m and n are each independently an integer from 0 to 6;
R ^a is selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (—CN), and combinations thereof;
R ¹¹ to R ¹⁶ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 haloalkyl group, a halogen, a cyano group (-CN), and a cyano-containing group;
k is an integer of 0 or 1; In paragraph 9,
An organic photoelectric device, wherein one aromatic ring is present in the fused ring moiety including the julolidinyl group. In paragraph 9,
The organic photoelectric device, wherein the total number of rings in the compound is 5 to 7. In paragraph 9,
The organic photoelectric device, wherein the compound has a maximum absorption wavelength (λ _max ) at 520 nm to 570 nm in a thin film state. delete delete In paragraph 1,
The n-type semiconductor compound is subphthalocyanine or a subphthalocyanine derivative, fullerene or a fullerene derivative, thiophene or a thiophene derivative, or a combination thereof. In paragraph 1,
The organic photoelectric device according to claim 1 , wherein the active layer includes an intrinsic layer including the compound represented by Chemical Formula 1. In clause 16,
The organic photoelectric device of claim 1 , wherein the active layer further includes at least one of a p-type layer positioned on one side of the intrinsic layer and an n-type layer positioned on the other side of the intrinsic layer. In paragraph 1,
The organic photoelectric device of claim 1 , wherein the active layer further includes a second p-type semiconductor compound that selectively absorbs green light. In paragraph 18,
The second p-type semiconductor compound is an organic photoelectric device having a compound of Formula 6:
[Formula 6]

In Formula 6,
R ⁷¹ 내지 R ⁷³ 은 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C30 지방족 탄화수소기, 치환 또는 비치환된 C6 내지 C30 방향족 탄화수소기, 치환 또는 비치환된 C2 내지 C30 지방족 헤테로고리기, 치환 또는 비치환된 C2 내지 C30 방향족 헤테로고리기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 티올기, 치환 또는 비치환된 C1 내지 C30 알킬티오기, 치환 또는 비치환된 C6 내지 C30 아릴티오기, 시아노기, 시아노 함유기, 할로겐기, 할로겐 함유기, 치환 또는 비치환된설포닐기 또는 이들의 조합이고, 또는 R ⁷¹ 내지 R ⁷³ 는 인접한 두 개가 연결되어 융합고리를 형성하고,
L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a divalent substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof;
R ⁷⁴ to R ⁷⁶ are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted amine group, a substituted or unsubstituted silyl group, or a combination thereof;
a, b and c are each independently an integer of 0 to 4. In paragraph 1,
The active layer includes the compound and C60 in a volume ratio of 0.9: 1 to 1.1: 1 and has an extinction coefficient of 8.0×10 ⁴ cm ⁻¹ or more. An image sensor comprising the organic photoelectric device according to any one of claims 1 to 12 and 15 to 20. In paragraph 21,
A semiconductor substrate on which a plurality of first photo-sensing elements for detecting light in a blue wavelength region and a plurality of second photo-sensing elements for detecting light in a red wavelength region are integrated; and
The organic photoelectric device positioned on the semiconductor substrate and selectively absorbing light in a green wavelength region
An image sensor comprising a. In paragraph 22,
and a color filter layer disposed between the semiconductor substrate and the organic photoelectric device and including a blue filter selectively absorbing light in a blue wavelength region and a red filter selectively absorbing light in a red wavelength region. In paragraph 21,
a semiconductor substrate on which at least one photo-sensing element is integrated;
An image sensor including the organic photoelectric device positioned on the semiconductor substrate. In paragraph 24,
The light-sensing element includes a first light-sensing element for detecting light in a blue wavelength region and a second light-sensing element for detecting light in a red wavelength region;
The first photo-sensing element and the second photo-sensing element are stacked in a vertical direction on a semiconductor substrate. In paragraph 21,
An image sensor in which the green photoelectric element as the organic photoelectric element, the blue photoelectric element selectively absorbing light in a blue wavelength region, and the red photoelectric element selectively absorbing light in a red wavelength region are stacked. An electronic device comprising the image sensor according to claim 21 .