Patent Description:
Fullerene is a closed-cage molecule made of carbon and is used in various fields because of its stable structure and good electrical properties.

An organic photoelectric device is a device that converts light into an electrical signal using a photoelectric effect. The organic photoelectric device includes a photodiode and a phototransistor, and may be applied to an electronic device such as an image sensor. The organic photoelectric device may include fullerene in the active layer having high light absorption properties and good electrical properties.

However, fullerene may absorb light in a blue region and reduce color clarity of the organic photoelectric device to which the fullerene is applied.

Therefore, a method for controlling blue region absorption of fullerene may be desired. Compositions comprising a fullerene and a corannulene have been mentioned by <NPL>; and by <NPL>.

Example embodiments provide an N-type semiconductor composition capable of improving color clarity of an organic photoelectric device.

Example embodiments also provide an organic photoelectric device including the N-type semiconductor composition.

Example embodiments also provide an image sensor and an electronic device including the organic photoelectric device.

According to example embodiments, an N-type semiconductor composition includes fullerene or a fullerene derivative; and a fullerene subunit derivative represented by Chemical Formula <NUM>.

In Chemical Formula <NUM>,
Cy is a cyclic group selected from a C3 to C20 alicyclic group and a C6 to C20 aromatic group, or a fused cyclic group of two or more cyclic groups, wherein the cyclic group in Cy is a heterocyclic group including at least one functional group selected from -N=, -NR-, -O-, -S-, -Se-, -Te-, -C(=O)-, -C(=S)-, - C(=Se)-, -C(=Te)-, -C(=C(CN)<NUM> )-, and -C(=NR)- wherein R is a C1 to C10 alkyl group, X is at least one bulky substituent selected from a substituted or unsubstituted C3 to C30 branched alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted C2 to C30 heteroaryl group, R<NUM> and R<NUM> are a bulky substituent selected from a substituted or unsubstituted C3 to C20 branched alkyl group, a substituted or unsubstituted C3 to C20 branched alkoxy group, a substituted or unsubstituted C3 to C20 branched alkylsilyl group, a substituted or unsubstituted C3 to C20 branched heteroalkyl 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 C3 to C30 heterocycloalkyl group, and a combination thereof, and R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, and R<NUM> are hydrogen, deuterium, a halogen, a cyano group, a C1 to C20 linear alkyl group, or a combination thereof.

In some embodiments, in Chemical Formula <NUM>, Cy may be pyrrole, furan, pyrroline, pyrrolidinedione, cyclopentanedione, pyrrolo imidazole pyrrolo imidazole including ketone (C=O) group in the ring, pyridine, pyrimidine, indole, phthalimide, benzimidazole, benzothiazole, or a fused ring of these rings and benzene rings.

In some embodiments, in Chemical Formula <NUM>, Cy may be selected from moieties represented by Chemical Formulae 2A to 2C.

*=* is a linking portion with Chemical Formula <NUM>.

In Chemical Formula <NUM>, Cy may be selected from moieties represented by Chemical Formulae 3A to 3D.

In some embodiments, in Chemical Formula <NUM>, Cy may be selected from moieties represented by Chemical Formulae 4A to 4C.

In some embodiments, in Chemical Formula <NUM>, at least one of R<NUM> and R<NUM> independently may be a group represented by Chemical Formula 5A.

In some embodiments, at least one of R<NUM> and R<NUM> independently may be a group represented by Chemical Formula 5B,
<CHM>.

In some embodiments, in Chemical Formula <NUM>, at least one of R<NUM> and R<NUM> independently may be a group represented by Chemical Formula 5C.

In some embodiments, in Chemical Formula <NUM>, at least one of R<NUM> and R<NUM> independently may be an isopropyl group, a <NUM>-methylpropyl group, an isobutyl group, a <NUM>-methylbutyl group, a <NUM>-ethylbutyl group, a <NUM>-propylbutyl group, an isopentyl group, a <NUM>-methylpentyl group, a <NUM>-ethylpentyl group, a <NUM>-propylpentyl group, a <NUM>-methylpentyl group, a <NUM>-ethylpentyl group, a <NUM>-propylpentyl group, a <NUM>-methylpentyl group, a <NUM>-ethylpentyl group, a <NUM>-propylpentyl group, an isohexyl group, a <NUM>-methylhexyl group, a <NUM>-ethylhexyl group, a <NUM>-propylhexyl group, a <NUM>-methylhexyl group, a <NUM>-ethylhexyl group, a <NUM>-propylhexyl group, a <NUM>-methylhexyl group, a <NUM>-ethylhexyl group, a <NUM>-propylhexyl group, an isoheptyl group, a <NUM>-methylheptyl group, a <NUM>-ethylheptyl group, a <NUM>-propylheptyl group, a <NUM>-methylheptyl group, a <NUM>-ethylheptyl group, a <NUM>-propylheptyl group, a <NUM>-methylheptyl group, a <NUM>-ethylheptyl group, a <NUM>-propylheptyl group, an isooctyl group, a <NUM>-methyloctyl group, a <NUM>-ethyloctyl group, a <NUM>-propyloctyl group, a <NUM>-methyloctyl group, a <NUM>-ethyloctyl group, a <NUM>-propyloctyl group, a <NUM>-methyloctyl group, a <NUM>-ethyloctyl group, a <NUM>-propyloctyl group, a <NUM>-methylnonyl group, a <NUM>,<NUM>-dimethylnonyl group, a t-butyl group, a t-pentyl group, a t-hexyl group, a neopentyl group, or a neohexyl group.

In some embodiments, the fullerene subunit derivative may have an average distance of less than or equal to about <NUM>Å from a P-type semiconductor.

According to another embodiment, a thin film including the N-type semiconductor composition is provided.

In some embodiments, an absorption coefficient at a wavelength of about <NUM> of the thin film may be smaller than an absorption coefficient at a wavelength of about <NUM> of the thin film including unsubstituted C60 fullerene.

Another embodiment provides an organic photoelectric device including a first electrode and a second electrode facing each other, and an organic layer between the first electrode and the second electrode, wherein the organic layer includes the N-type semiconductor composition.

In some embodiments, an organic layer may include an active layer, and the active layer may include a P-type semiconductor and an N-type semiconductor forming a pn junction, and the N-type semiconductor may include the N-type semiconductor composition.

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

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

In some embodiments, the fullerene or the fullerene derivative may be the fullerene.

In some embodiments, the fullerene or the fullerene derivative may be the fullerene derivative.

In some embodiments, an organic photoelectric device may include first electrode and a second electrode facing each other, and an organic layer between the first electrode and the second electrode. The organic layer includes the N-type semiconductor composition.

In some embodiments, an image sensor may include organic photoelectric device.

The N-type semiconductor composition may improve color clarity of the organic photoelectric device by reducing absorption of the blue region of the fullerene or the fullerene derivative.

Hereinafter, example embodiments of the present disclosure will be described in detail so that a person skilled in the art would understand the same. This disclosure may, however, be embodied in many different forms and is not construed as limited to the example embodiments set forth herein.

In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. Like reference numerals designate like elements throughout the specification. 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 the drawings, parts having no relationship with the description are omitted for clarity of the embodiments, and the same or similar constituent elements are indicated by the same reference numeral throughout the specification.

As used herein, "combination" includes two or more mixtures, intersubstitutions, and two or more stacked structures.

As used herein, when specific definition is not otherwise provided, "substituted" refers to replacement of a hydrogen of a compound, a functional group, or a moiety by a halogen atom (-F, -Cl, -Br, or -I), a hydroxyl group, 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 carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid group or a salt thereof, a C1 to C20 alkyl group, a C1 to C20 alkoxy 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 C20 alkoxy group, a C3 to C20 heteroarylalkyl 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, or a combination thereof (e.g., a C1 to C20 haloalkyl group such as a C1 to C20 trifluoroalkyl group).

As used herein, when a definition is not otherwise provided, "hetero" refers to one including one to three heteroatoms selected from N, O, S, P, and Si, and remaining carbons in a compound, a functional group, or a moiety.

As used herein, when a definition is not otherwise provided, "aryl group" refers to a group including at least one hydrocarbon aromatic moiety, for example all the elements of the hydrocarbon aromatic moiety having p-orbitals which form conjugation such as a phenyl group or a naphthyl group; two or more hydrocarbon aromatic moieties linked by a sigma bond such as a biphenyl group, a terphenyl group, or a quarterphenyl group; and two or more hydrocarbon aromatic moieties fused directly or indirectly to provide a non-aromatic fused ring such as a fluorenyl group.

As used herein, when a definition is not otherwise provided, "heterocyclic group" is a generic concept of a C2 to C30 (e.g., C2 to C20) heteroaryl group, a C2 to C30 (e.g., C2 to C20) heterocycloalkyl group, or a fused cyclic group thereof, and may include at least one (e.g., <NUM> to <NUM>) heteroatom instead of carbon (C) in a ring such as an aryl group, a cycloalkyl group, a fused cyclic group thereof, or a combination thereof, wherein the heteroatom may be for example N, O, S, P, and/or Si, but is not limited thereto. When the heterocyclic group is a fused cyclic group, at least one (e.g., <NUM> to <NUM>) heteroatom may be included in an entire ring or each ring of the heterocyclic group
As used herein, when a definition is not otherwise provided, "heteroaryl group" refers to an aryl group including at least one heteroatom, wherein the heteroatom may be for example N, O, S, P, and/or Si, but is not limited thereto. At least two heteroaryl groups may be linked directly through a sigma bond or at least two heterocyclic groups may be fused with each other. When the heteroaryl group is a fused ring, each ring may include one to three heteroatoms.

As used herein, when a definition is not otherwise provided, "heteroalkyl group" refers to an alkyl group including at least one heteroatom in the main chain of the alkyl group and may be specifically an alkyl group in which at least one methylene group is replaced by -O-, -S-, -C(=O)-, -C(=S)-, -OC(=O)-, and -C(=O)O-.

As used herein, when a definition is not otherwise provided, "cyclic hydrocarbon group" refers to a C3 to C20 alicyclic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group, a fused cyclic group of two or more cyclic hydrocarbon groups, or a heterocyclic group including a heteroatom therein.

As used herein, when a definition is not otherwise provided, "alicyclic hydrocarbon group" refers to at least one non-aromatic ring (alicyclic ring) or a fused ring in which these non-aromatic rings are fused to each other which is selected from a C3 to C30 cycloalkyl group, for example a C3 to C20 cycloalkyl group or a C3 to C10 cycloalkyl group; a C3 to C30 cycloalkenyl group, for example a C3 to C20 cycloalkenyl group or a C3 to C10 cycloalkenyl group; and a C2 to C30 heterocycloalkyl group, for example a C2 to C20 heterocycloalkyl group or a C3 to C10 heterocycloalkyl group.

As used herein, when a definition is not otherwise provided, "aromatic hydrocarbon group" may include at least one aromatic ring (arene ring) or a fused ring thereof such as a C6 to C30 aryl group, for example a C6 to C20 aryl group or a C6 to C10 aryl group.

As used herein, when a definition is not otherwise provided, "bulky substituent" refers to a substituted or unsubstituted branched alkyl group, a substituted or unsubstituted branched alkoxy group, a substituted or unsubstituted branched alkylsilyl group, a substituted or unsubstituted branched heteroalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group, or a combination thereof. In some embodiment, the "bulky substituent" refers to a substituted or unsubstituted C3 to C20 (e.g., C4 to C20) branched alkyl group, a substituted or unsubstituted C3 to C20 (e.g., C4 to C20) branched alkoxy group, a substituted or unsubstituted C3 to C20 (e.g., C4 to C20) branched alkylsilyl group, a substituted or unsubstituted C3 to C20 (e.g., C4 to C20) branched heteroalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 (e.g., C3 to C20) heteroaryl group, a substituted or unsubstituted C3 to C30 (e.g., C4 to C20) cycloalkyl group, a substituted or unsubstituted C3 to C30 (e.g., C4 to C20) heterocycloalkyl group, and a combination thereof.

Expressions such as "at least one of," when preceding a list of elements (e.g., A, B, and C), modify the entire list of elements and do not modify the 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, may be construed as covering any one of the following combinations: A; B; A and B; A and C; B and C; and A, B, and C.

When the term "about" is used in this specification in connection with a numerical value, it is intended that the associated numerical value include a tolerance of ±<NUM>% around the stated numerical value. When ranges are specified, the range includes all values therebetween such as increments of <NUM>%.

Hereinafter, an N-type semiconductor composition according to an embodiment is described.

N-type semiconductor composition in accordance with the invention are as defined in claim <NUM>. According to a general embodiment, an N-type semiconductor composition includes fullerene or a fullerene derivative; and a fullerene subunit derivative represented by Chemical Formula <NUM>.

The fullerene subunit derivative of Chemical Formula <NUM> includes a cyclic hydrocarbon group (Cy) having at least one bulky substituent (X) and further includes at least one bulky substituent at a position (at least one of R<NUM> to R<NUM>) besides Cy and thereby crystallinity of the fullerene subunit derivatives may be suppressed effectively. The fullerene subunit derivative of Chemical Formula <NUM> may interact with the fullerene or fullerene derivative, and thereby aggregation of the fullerene or fullerene derivative may be suppressed effectively. Light absorption in a blue region (about <NUM> to about <NUM>) may be significantly reduced by suppressing the aggregation of the fullerene or the fullerene derivative, thereby improving color clarity of the device.

The bulky substituent (X) may effectively control steric hindrance between the fullerene subunit derivatives to maintain a constant interval. The bulky substituents of at least one of R<NUM> to R<NUM> may lower crystallinity of the fullerene subunit derivative and may be mixed well with the P-type semiconductor and the N-type semiconductor (fullerene or fullerene derivative) in an active layer. In addition, the bulky substituents of at least one of R<NUM> to R<NUM> may inhibit aggregation of the fullerene or fullerene derivative by allowing a corannulene skeleton of the derivative to surround the fullerene or fullerene derivative well. In addition, the bulky substituent of at least one of R<NUM> to R<NUM> may improve thermal stability of the fullerene subunit derivative which may improve high temperature characteristics when applied to a device.

The fullerene subunit derivative of Chemical Formula <NUM> has a structure capable of inhibiting aggregation of the fullerene or fullerene derivative, but does not expand the conjugated structure of corannulene, thereby suppressing an increase in crystallinity and enabling sublimation purification to be advantageous in a thin film formation process.

The cyclic hydrocarbon group may include one or more heteroatoms in the ring. Specifically, the cyclic hydrocarbon group may be a heterocyclic group including at least one functional group selected from -N=, -NR-, -O-, -S-, -Se-, -Te-, - C(=O)-, -C(=S)-, -C(=Se)-, -C(=Te)-, -C(=C(CN)<NUM>)-, and -C(=NR)- wherein R is a C1 to C10 alkyl group. As such, when Cy is a heterocyclic group, N-type properties of the fullerene subunit derivative may be further enhanced.

The HOMO/LUMO levels of the fullerene subunit derivative may be adjusted by a combination of the cyclic hydrocarbon group and the bulky substituent (X) substituted therein. For example, when Cy is a hydrocarbon group that does not include an electron withdrawing functional group (e.g., -C(=O)-, -N=, -NR-, etc.), an electron withdrawing functional group may be introduced into the bulky substituent (X). Examples of the bulky substituent (X) having an electron withdrawing functional group include an N-containing cyclic group such as a pyrrolyl group, a pyridyl group, a pyrimidyl group, a triazinyl group, and the like; or a C6 to C20 aryl group substituted with a fluorine (F) group, a cyano (CN) group, a C1 to C10 carboxyl group or an ester group (e.g., acetate group) or a C1 to C10 trifluoroalkyl group (e.g., trifluoromethyl (CF<NUM>)).

At least two, for example three or four of R<NUM> to R<NUM> may be a bulky substituent selected from a substituted or unsubstituted C3 to C20 branched alkyl group, a substituted or unsubstituted C3 to C20 branched alkoxy group, a substituted or unsubstituted C3 to C20 branched alkylsilyl group, a substituted or unsubstituted C3 to C20 branched heteroalkyl 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 C3 to C30 heterocycloalkyl group, and a combination thereof.

In Chemical Formula <NUM>, at least one of R<NUM> to R<NUM> and at least one of R<NUM> to R<NUM> may be the same or different, and may be a bulky substituent selected from a substituted or unsubstituted C3 to C20 branched alkyl group, a substituted or unsubstituted C3 to C20 branched alkoxy group, a substituted or unsubstituted C3 to C20 branched alkylsilyl group, a substituted or unsubstituted C3 to C20 branched heteroalkyl 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 C3 to C30 heterocycloalkyl group, and a combination thereof.

At least one bulky substituent of R<NUM> to R<NUM> and at least one bulky substituent of R<NUM> to R<NUM> may be present at positions symmetrical with respect to Cy.

In Chemical Formula <NUM>, at least two of R<NUM> to R<NUM> may be a bulky substituent selected from a substituted or unsubstituted C3 to C20 branched alkyl group, a substituted or unsubstituted C3 to C20 branched alkoxy group, a substituted or unsubstituted C3 to C20 branched alkylsilyl group, a substituted or unsubstituted C3 to C20 branched heteroalkyl 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 C3 to C30 heterocycloalkyl group, and a combination thereof.

In Chemical Formula <NUM>, when including two or more bulky substituents at positions symmetrical with respect to Cy, the fullerene subunit derivative may effectively cover the fullerene or the fullerene derivative, thereby suppressing their aggregation.

The fullerene may be fullerenes of C60 to C120, and specifically, may be C60, C70, C74, C76, C78, C80, C82, C84, C90, or C96, but is not limited thereto.

The fullerene derivative refers to a compound having a substituent on the fullerene. Examples of the substituent may be an alkyl group, an aryl group. or a heterocyclic group. The alkyl group may be a C1 to C12 alkyl group, for example, a C1 to C5 alkyl group. The aryl group may be a phenyl group, a naphthyl group, or an anthracenyl group. Herein, the heterocyclic group may be a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a quinolyl group, or a carbazolyl group.

Specific examples of the fullerene derivative may include phenyl-C61-butyric acid methylester (PCBM, [<NUM>,<NUM>]-phenyl-C61-butyric acid methyl ester), and ICBA (indene-C60 bisadduct), and ICMA (indene-C60 monoadduct), but are not limited thereto.

In Chemical Formula <NUM>, at least one of R<NUM> to R<NUM> and at least one of R<NUM> to R<NUM> may be the same or different, and may be a bulky substituent selected from a substituted or unsubstituted C3 to C20 branched alkyl group, a substituted or unsubstituted C3 to C20 branched alkoxy group, a substituted or unsubstituted C3 to C20 branched alkylsilyl group, a substituted or unsubstituted C3 to C20 branched heteroalkyl 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 C3 to C30 heterocycloalkyl group, and a combination thereof. In this case, steric hindrance may be effectively controlled to suppress aggregation of fullerene or fullerene derivative in the deposition process.

In Chemical Formula <NUM>, at least one of R<NUM> and R<NUM> and at least one of R<NUM> and R<NUM> may be the same or different, and may be a bulky substituent selected from a substituted or unsubstituted C3 to C20 branched alkyl group, a substituted or unsubstituted C3 to C20 branched alkoxy group, a substituted or unsubstituted C3 to C20 branched alkylsilyl group, a substituted or unsubstituted C3 to C20 branched heteroalkyl 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 C3 to C30 heterocycloalkyl group, and a combination thereof, and R<NUM>, R<NUM>, R<NUM>, and R<NUM> may be hydrogen, deuterium, a halogen, a cyano group, a C1 to C20 linear alkyl group, or a combination thereof. In this case, steric hindrance may be effectively controlled to suppress aggregation of fullerene or fullerene derivative in the deposition process.

In Chemical Formula <NUM> R<NUM> and R<NUM> may be a bulky substituent selected from a substituted or unsubstituted C3 to C20 branched alkyl group, a substituted or unsubstituted C3 to C20 branched alkoxy group, a substituted or unsubstituted C3 to C20 branched alkylsilyl group, a substituted or unsubstituted C3 to C20 branched heteroalkyl 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 C3 to C30 heterocycloalkyl group, and a combination thereof, and R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, and R<NUM> may be hydrogen, deuterium, a halogen, a cyano group, a C1 to C20 linear alkyl group, or a combination thereof. In this case, by having a bulky substituent on both sides with respect to Cy, the steric hindrance effect may be effectively controlled to suppress aggregation of fullerene or fullerene derivative in the deposition process.

According to an embodiment, in Chemical Formula <NUM>, two adjacent substituents of R<NUM> to R<NUM> and two adjacent substituents of R<NUM> to R<NUM> may be linked to each other to form a C3 to C20 alicyclic hydrocarbon group. Such C3 to C20 alicyclic hydrocarbon group may inhibit expansion of the conjugated structure of corannulene to inhibit an increase in crystallinity. The C3 to C20 alicyclic hydrocarbon group may be fused with a C6 to C20 aromatic hydrocarbon group.

In Chemical Formula <NUM>, R<NUM> and R<NUM> may be linked to each other to form a C3 to C20 alicyclic hydrocarbon group, and R<NUM> and R<NUM> may be linked to each other to form a C3 to C20 alicyclic hydrocarbon group. The C3 to C20 alicyclic hydrocarbon group may be fused with a C6 to C20 aromatic hydrocarbon group. The C3 to C20 alicyclic hydrocarbon group may be a pentagonal ring, and a structure in which the pentagonal ring may be fused with a benzene ring is represented by Chemical Formula 1A.

In Chemical Formula <NUM>, Cy may be pyrrole, furan, pyrroline, pyrrolidinedione, cyclopentanediene, cyclopentanedione, pyrrolo imidazole, pyrrolo imidazole including a ketone (C=O) group in the ring, pyridine, pyrimidine, indole, pyridine, phthalimide, benzimidazole, benzothiazole, or a fused ring of these and benzene rings.

In Chemical Formula <NUM>, Cy may be a moiety represented by Chemical Formula 2A.

For example, the moiety represented by Chemical Formula 2A may be a moiety represented by Chemical Formula 2A-<NUM>.

When Z<NUM> is NRd and Rd is linked to Y<NUM> of Chemical Formula 2A to form a fused ring, Chemical Formula 2A may be a moiety represented by Chemical Formula 2A-<NUM>.

For example, the moiety represented by Chemical Formula 2B may be a moiety represented by Chemical Formula 2B-<NUM>.

For example, the moiety represented by Chemical Formula 2B may be selected from moieties represented by Chemical Formula 2B-<NUM>.

In Chemical Formula <NUM>, Cy may be a moiety represented by Chemical Formula 2C.

For example, the moiety represented by Chemical Formula 2C may be a moiety represented by Chemical Formula 2C-<NUM>.

In Chemical Formula <NUM>, Cy may be a moiety represented by Chemical Formula 4A.

For example, the moiety represented by Chemical Formula 4A may be a moiety represented by Chemical Formula 4A-<NUM>. Chemical Formula 4A-<NUM> illustrates the case where n of Chemical Formula 4A is <NUM>, but the compound where n of Chemical Formula 4A is <NUM> or <NUM> may be represented in the same manner as in Chemical Formula 4A-<NUM>.

In Chemical Formula <NUM>, Cy may be a moiety represented by Chemical Formula 4B.

For example, the moiety represented by Chemical Formula 4B may be a moiety represented by Chemical Formula 4B-<NUM>. Chemical Formula 4B-<NUM> illustrates the case where n of Chemical Formula 4B is <NUM>, but the compound where n of Chemical Formula 4B is <NUM> or <NUM> may be represented in the same manner as in Chemical Formula 4B-<NUM>.

In Chemical Formula <NUM>, Cy may be selected from a moiety represented by Chemical Formula 4C.

For example, the moiety represented by Chemical Formula 4C may be a moiety represented by Chemical Formula 4C-<NUM>. Chemical Formula 4C-<NUM> illustrates the case where n of Chemical Formula 4C is <NUM>, but the compound where n of Chemical Formula 4C is <NUM> or <NUM> may be represented in the same manner as in Chemical Formula 4C-<NUM>.

In an embodiment, the substituted or unsubstituted C3 to C20 branched alkyl group and a substituted or unsubstituted C3 to C20 branched alkoxy group may be represented by Chemical Formula 5A.

In an embodiment, the substituted or unsubstituted C3 to C20 branched alkylsilyl group may be represented by Chemical Formula 5C.

Specific examples of the fullerene subunit derivatives include compounds of Groups <NUM> to <NUM>. <CHM>
<CHM>
<CHM>
<CHM>.

Branched alkyl groups such as an isopropyl (iPr) group, a tertiary butyl (tBu) group, a <NUM>-methyl propyl group, a trimethylsilyl (TMS) group, etc. may be substituted instead of the two substituents (OtBu) groups of the corannulene of Group <NUM>. Group <NUM> illustrates structures which are substituted with a tertiary butyl (tBu) group instead of the two substituents (OtBu) groups of corannulene in Group <NUM> and Group <NUM> illustrates structures which are substituted with a trimethylsilyl (TMS) group. <CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

Group <NUM> illustrates structures which are substituted with a phenyl group instead of the two substituents (OtBu) groups of the corannulene of Group <NUM>. <CHM>
<CHM>
<CHM>
<CHM>.

In Group <NUM>, two phenyl (Ph) groups which are substituents of corannulene are substituted with at least one substituent selected from a C1 to C20 linear alkyl group, a C3 to C20 branched alkyl group, a C6 to C12 aryl group, and a C3 to C12 heteroaryl group. These substituents may be present in plural, in which case they may be the same or different from one another. The positions of the substituents may be at an ortho, meta, or para position. For example, structures which substituted with an isopropyl group or t-butyl group at an ortho position are shown in Group <NUM>. <CHM>
<CHM>
<CHM>
<CHM>.

The corannulene of Group <NUM> may be substituted with a substituted or unsubstituted C2 to C30 heteroaryl group (for example, pyridyl group, pyrimidyl group, triazinyl group, thienyl group, etc.) instead of the two substituents (OtBu). The position of the heteroatom (for example, nitrogen, sulfur, etc.) of the substituted or unsubstituted C2 to C30 heteroaryl group may be present at the ortho, meta, or para position with respect to the bonding position. The heteroaryl group may be substituted with at least one substituent selected from a C1 to C20 linear alkyl group, a C3 to C20 branched alkyl group, a C6 to C12 aryl group, and a C3 to C12 heteroaryl group.

Group <NUM> exemplifies a structure which substituted with a pyridyl group as the heteroaryl group and Group <NUM> exemplifies structure which substituted with a thienyl group, a furanyl group, a pyrroylyl group, a selenophenyl group, or a tellurophenyl group as the heteroaryl group. <CHM>
<CHM>
<CHM>
<CHM>.

In Group <NUM>, the pyridyl group may be substituted with at least one substituent selected from a C1 to C20 linear alkyl group, a C3 to C20 branched alkyl groups, a C6 to C12 aryl group, and a C3 to C12 heteroaryl group.

In Group <NUM>, the thienyl group, furanyl group, pyrroyl group, selenophenyl group, or tellurophenyl group may be substituted with at least one substituent selected from a C1 to C20 linear alkyl group, a C3 to C20 branched alkyl group, a C6 to C12 aryl group, and a C3 to C12 heteroaryl group. In addition, the hydrogen of the pyrrolyl group may be substituted with at least one substituent selected from a C1 to C20 linear alkyl group, a C3 to C20 branched alkyl group, a C6 to C12 aryl group, and a C3 to C12 heteroaryl group.

The phenyl (Ph) group of Group <NUM> or the pyridyl group of Group <NUM> may be fused to corannulene through an alicyclic hydrocarbon group such as cyclopentadiene. These structures (not forming part of the claimed invention) are illustrated in Group <NUM>.

The fullerene subunit derivative (N-type semiconductor) may have an average distance from the P-type semiconductor of less than or equal to about <NUM>Å, for example, less than or equal to about <NUM>Å, or less than or equal to about <NUM>Å. The fullerene subunit derivative may adjust the average distance from the P-type semiconductor within the above range by including a bulky substituent (X) and an additional bulky substituent on the side. When the average distance from the P-type semiconductor is maintained within the above range, the fullerene subunit derivative (N-type semiconductor) and the P-type semiconductor may be well mixed to form a bulk hetero junction (BHJ).

The fullerene subunit derivative may be included in an amount of greater than or equal to about <NUM> parts by volume, for example, greater than or equal to about <NUM> parts by volume, or greater than or equal to about <NUM> parts by volume and less than or equal to about <NUM> parts by volume, for example, less than or equal to about <NUM> parts by volume, or less than or equal to about <NUM> parts by volume based on <NUM> parts by volume of the fullerene or a fullerene derivative. Within the above range, the fullerene subunit derivative effectively suppresses aggregation of the fullerene or the fullerene derivative, thereby reducing unnecessary absorption in the blue region and increasing the absorption in the green region.

The fullerene subunit derivative may be formed into a thin film by vacuum deposition using sublimation together with the fullerene or the fullerene derivative. While maintaining the intrinsic properties of the fullerene or the fullerene derivative during the deposition process, it is possible to prevent optical properties from being deformed by aggregation of the fullerene or fullerene derivative generated during the film formation of the thin film. Thin film made of the N-type semiconductor composition including the fullerene or fullerene derivative and the fullerene subunit derivative may reduce abnormal absorption in a short wavelength region of visible light from about <NUM> to about <NUM>. For example, an absorption coefficient at a <NUM> wavelength of the thin film including the N-type semiconductor composition may be smaller than the absorption coefficient at a <NUM> wavelength of the thin film including unsubstituted fullerene (e.g., C60 fullerene). For example, the absorption coefficient at <NUM> of the thin film including the N-type semiconductor composition may be about <NUM>% or less of the absorption coefficient at a <NUM> wavelength of the thin film including the unsubstituted fullerene (e.g., C60 fullerene).

Hereinafter, an organic photoelectric device including the aforementioned N-type semiconductor composition is described.

<FIG> is a cross-sectional view illustrating an organic photoelectric device according to an embodiment.

Referring to <FIG>, an organic photoelectric device <NUM> according to an embodiment includes a first electrode <NUM> and a second electrode <NUM> facing each other and an organic layer <NUM> disposed between the first electrode <NUM> and the second electrode <NUM>.

A substrate (not shown) may be disposed at the side of the first electrode <NUM> or the second electrode <NUM>. The substrate may be for example made of an inorganic material such as glass; an organic material such as polycarbonate, polymethylmethacrylate, polyethyleneterephthalate, polyethylenenaphthalate, polyamide, polyethersulfone, or a combination thereof; or a silicon wafer. The substrate may be omitted.

One of the first electrode <NUM> and the second electrode <NUM> is an anode and the other is a cathode. For example, the first electrode <NUM> may be a cathode and the second electrode <NUM> may be an anode.

At least one of the first electrode <NUM> and the second electrode <NUM> may be a light-transmitting electrode and the light-transmitting electrode may be for example made of a conductive oxide such as an indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO), aluminum tin oxide (AlTO), and fluorine doped tin oxide (FTO), or a metal thin layer of a single layer or a multilayer. When one of the first electrode <NUM> and the second electrode <NUM> 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 <NUM> and the second electrode <NUM> may be all light-transmitting electrodes. For example, the second electrode <NUM> may be a light receiving electrode disposed at a light receiving side.

The organic layer <NUM> may include an active layer.

The active layer is a layer including a P-type semiconductor and an N-type semiconductor to provide a pn junction, which is a layer producing excitons by receiving light from outside and then separating holes and electrons from the produced excitons.

Each of the P-type semiconductor and the N-type semiconductor may be a light absorbing material that absorbs at least a portion of the light in the visible region. For example, the P-type semiconductor may be a light absorbing material capable of selectively absorbing any one of a wavelength region of greater than or equal to about <NUM> to less than about <NUM>, a wavelength region of about <NUM> to about <NUM>, and/or a wavelength region of greater than about <NUM> and less than or equal to about <NUM> and the N-type semiconductor may be the aforementioned N-type semiconductor composition.

In one example, the P-type semiconductor selectively absorbs any one of light in a wavelength region of greater than or equal to about <NUM> to less than about <NUM>, a wavelength region of about <NUM> to about <NUM>, and a wavelength region of greater than about <NUM> and less than or equal to about <NUM>. It may be a light absorbing material, and the N-type semiconductor may be the aforementioned N-type semiconductor composition. For example, the P-type semiconductor may be an absorbing material that selectively absorbs light in a wavelength region of about <NUM> to about <NUM> and the N-type semiconductor may be the aforementioned N-type semiconductor composition.

For example, the P-type semiconductor may be, for example, a light absorbing material having a LUMO energy level of about <NUM> eV to about <NUM> eV and a HOMO energy level of about <NUM> eV to about <NUM> eV. Within this range, the P-type semiconductor may be, for example, a light absorbing material having a LUMO energy level of about <NUM> eV to about <NUM> eV and a HOMO energy level of <NUM> eV to about <NUM> eV.

For example, the P-type semiconductor may be a light absorbing material having a core structure including, for example, an electron donating moiety, a pi conjugated linking group, and an electron accepting moiety.

The P-type semiconductor may include, for example, a compound represented by Chemical Formula <NUM> as the compound having the core structure, but is not limited thereto.

The P-type semiconductor may be, for example, a light absorbing material represented by Chemical Formula 8A, but is not limited thereto.

The P-type semiconductor may be for example a light absorbing material represented by one of Chemical Formulae 8A-<NUM> to 8A-<NUM>, but is not limited thereto. <CHM>
<CHM>
<CHM>
<CHM>.

In Chemical Formulae 8A-<NUM> to 8A-<NUM>,.

The light absorbing material represented by one of Chemical Formulae 8A-<NUM> to 8A-<NUM> may be for example one of compounds of Group <NUM> to Group <NUM>, but is not limited thereto. <CHM>
<CHM>
<CHM>
<CHM>.

The aforementioned N-type semiconductor composition may be used as the N-type semiconductor.

The fullerene or fullerene derivative has LUMO energy level, HOMO energy level, and bandgap energy which are effective for electrical matching with the aforementioned P-type semiconductor.

The P-type semiconductor and the N-type semiconductor composition may be formed into the active layer by codeposition using sublimation.

For example, the light absorption characteristics of the active layer including the N-type semiconductor composition may be different from the light absorption characteristics of the active layer including an unsubstituted fullerene (e.g., C60 fullerene), and an active layer including an N-type semiconductor composition may have reduced abnormal absorption in a short wavelength region of visible light, for example from about <NUM> to about <NUM>. For example, the absorption coefficient at a <NUM> wavelength of the active layer including the N-type semiconductor composition may be smaller than the absorption coefficient at a <NUM> wavelength of the active layer including unsubstituted fullerene (e.g., C60 fullerene). For example, the absorption coefficient at a <NUM> wavelength of the active layer including the N-type semiconductor composition may be, for example, about <NUM>% or less of the absorption coefficient at a <NUM> wavelength of the active layer including unsubstituted fullerene (e.g., C60 fullerene).

The light absorption characteristics of the active layer may be expressed by a combination of light absorption characteristics by the P-type semiconductor and light absorption characteristics by the N-type semiconductor composition. Accordingly, the active layer including the P-type semiconductor selectively absorbing light in a wavelength region of about <NUM> to about <NUM> and the N-type semiconductor composition may increase wavelength selectivity due to easy separation of an absorption peak compared with the active layer including the P-type semiconductor selectively absorbing in a wavelength region of about <NUM> to about <NUM> and the unsubstituted fullerene (e.g., C60 fullerene). Accordingly, the former active layer may be effectively used for an organic photoelectric device requiring wavelength selectivity.

The active layer may include an intrinsic layer (I layer) formed by codepositing the aforementioned P-type semiconductor and N-type semiconductor composition. The P-type semiconductor and N-type semiconductor composition may be included in a volume ratio of about <NUM>:<NUM> to about <NUM>:<NUM>, about <NUM>:<NUM> to about <NUM>:<NUM>, about <NUM>:<NUM> to about <NUM>:<NUM>, about <NUM>:<NUM> to about <NUM>:<NUM>, or about <NUM>:<NUM>.

The active layer may further include a P-type layer and/or an N-type layer in addition to the intrinsic layer. The P-type layer may include the P-type semiconductor and the N-type layer may include the aforementioned N-type semiconductor composition. For example, the active layer may include various combinations of a P-type layer/an I layer, an I layer/an N-type layer, a P-type layer/an I layer/an N-type layer, and the like.

The organic photoelectric device <NUM> may further include a charge auxiliary layer (not shown) between the first electrode <NUM> and the active layer and/or a charge auxiliary layer between the second electrode <NUM> and the active layer. The organic photoelectric device is illustrated in <FIG>.

<FIG> is a cross-sectional view showing an organic photoelectric device according to another example embodiment.

Referring to <FIG>, an organic photoelectric device <NUM> according to the present embodiment includes a first electrode <NUM> and a second electrode <NUM> facing each other, and an organic layer <NUM> between the first electrode <NUM> and the second electrode <NUM>, like the above embodiment.

However, the organic photoelectric device <NUM> according to the present embodiment further includes charge auxiliary layers <NUM> and <NUM> between the first electrode <NUM> and the active layer, and the second electrode <NUM> and the organic layer <NUM>, unlike the above embodiment.

The charge auxiliary layers <NUM> and <NUM> may make holes and electrons separated in the organic layer <NUM> be transported easily to improve efficiency.

The charge auxiliary layers <NUM> and <NUM> may include at least one selected from a hole injection layer for facilitating hole injection, a hole transport layer for facilitating hole transport, an electron blocking layer for preventing electron transport, an electron injection layer for facilitating electron injection, an electron transport layer for facilitating electron transport, and a hole blocking layer for preventing hole transport.

The charge auxiliary layers <NUM> and <NUM> may include for example an organic material, an inorganic material, or an organic/inorganic material. The organic material may be an organic material having hole or electron characteristics and the inorganic material may be for example a metal oxide such as a molybdenum oxide, a tungsten oxide, or a nickel oxide.

The charge auxiliary layers <NUM> and <NUM> may include the aforementioned N-type semiconductor composition.

The organic photoelectric devices <NUM> and <NUM> may further include an anti-reflection layer (not shown) on one surface of the first electrode <NUM> or the second electrode <NUM>. The anti-reflection layer is disposed at a light incidence side and lowers reflectance of light of incident light and thereby light absorbance is further improved. For example, when light enters from the first electrode <NUM>, the anti-reflection layer may be disposed on the first electrode <NUM> while when light enters from the second electrode <NUM>, the anti-reflection layer may be disposed under the second electrode <NUM>.

The anti-reflection layer may include, for example a material having a refractive index of about <NUM> to about <NUM>, and may include for example at least one of a metal oxide, a metal sulfide, and an organic material having a refractive index within the ranges. The anti-reflection layer may include, for example a metal 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 a combination thereof; a metal sulfide such as zinc sulfide; or an organic material such as an amine derivative, but is not limited thereto.

In the organic photoelectric devices <NUM> and <NUM>, when light enters from the first electrode <NUM> or second electrode <NUM> and the organic layer <NUM> (e.g., active layer) absorbs light in a predetermined wavelength region, excitons may be produced from the inside. The excitons are separated into holes and electrons in the organic layer <NUM>, and the separated holes are transported to an anode that is one of the first electrode <NUM> and the second electrode <NUM> and the separated electrons are transported to the cathode that is the other of the first electrode <NUM> and the second electrode <NUM> so as to flow a current.

The organic photoelectric devices <NUM> and <NUM> may be applied to a solar cell, an image sensor, a photodetector, a photosensor, and an organic light emitting diode (OLED), but is not limited thereto.

The organic photoelectric device may be for example applied to an image sensor.

Hereinafter, an example of an image sensor including the photoelectric device is described referring to drawings. As an example of an image sensor, an organic CMOS image sensor is described.

<FIG> is a schematic top plan view of an organic CMOS image sensor according to an embodiment and <FIG> is a cross-sectional view showing one example of the organic CMOS image sensor of <FIG>.

Referring to <FIG> and <FIG>, an organic CMOS image sensor <NUM> according to an example embodiment includes a semiconductor substrate <NUM> integrated with photo-sensing devices 50a and 50b, a transmission transistor (not shown) and a charge storage <NUM>, a lower insulation layer <NUM>, a color filter layer <NUM>, an upper insulation layer <NUM>, and an organic photoelectric device <NUM>.

The semiconductor substrate <NUM> may be a silicon substrate, and is integrated with the photo-sensing devices 50a and 50b, the transmission transistor (not shown), and the charge storage <NUM>. The photo-sensing devices 50a and 50b may be photodiodes.

The photo-sensing devices 50a and 50b, the transmission transistor, and/or the charge storage <NUM> may be integrated in each pixel, and as shown in the drawing, the photo-sensing devices 50a and 50b may be respectively included in a blue pixel and a red pixel and the charge storage <NUM> may be included in a green pixel.

The photo-sensing devices 50a and 50b sense light, the information sensed by the photo-sensing devices may be transferred by the transmission transistor, the charge storage <NUM> is electrically connected to the organic photoelectric device <NUM> that will be described later, and the information of the charge storage <NUM> may be transferred by the transmission transistor.

A metal wire (not shown) and a pad (not shown) are formed on the semiconductor substrate <NUM>. In order to decrease signal delay, the metal wire and pad may be made of a metal having low resistivity, for example, aluminum (Al), copper (Cu), silver (Ag), and alloys thereof, but are not limited thereto. Further, it is not limited to the structure, and the metal wire and pad may be disposed under the photo-sensing device 50a and 50b.

The lower insulation layer <NUM> is formed on the metal wire and the pad. The lower insulation layer <NUM> may be made of an inorganic insulating material such as a silicon oxide and/or a silicon nitride, or a low dielectric constant (low K) material such as SiC, SiCOH, SiCO, and SiOF. The lower insulation layer <NUM> has a trench exposing the charge storage <NUM>. The trench may be filled with fillers.

A color filter layer <NUM> is formed on the lower insulation layer <NUM>. The color filter layer <NUM> includes a blue filter 70a formed in a blue pixel and a red filter 70b in a red pixel. In the present embodiment, a green filter is not included, but a green filter may be further included.

The upper insulation layer <NUM> is formed on the color filter layer <NUM>. The upper insulation layer <NUM> eliminates a step caused by the color filter layer <NUM> and smoothens the surface. The upper insulation layer <NUM> and the lower insulation layer <NUM> may include a contact hole (not shown) exposing a pad, and a through-hole <NUM> exposing the charge storage <NUM> of the green pixel.

The aforementioned organic photoelectric device <NUM> is formed on the upper insulation layer <NUM>. The organic photoelectric device <NUM> includes the first electrode <NUM>, the organic layer <NUM>, and the second electrode <NUM> as described above. In the drawing, the first electrode <NUM>, the organic layer <NUM>, and the second electrode <NUM> are sequentially stacked, but this disclosure is not limited thereto, and for example they may be stacked in an order of the second electrode <NUM>, the organic layer <NUM>, and the first electrode <NUM>.

The first electrode <NUM> and the second electrode <NUM> may be all light-transmitting electrodes and the organic layer <NUM> is the same as described above. The organic layer <NUM> may for example selectively absorb light in a green wavelength region and may replace a color filter of a green pixel.

Light in a green wavelength region of light that enters from the second electrode <NUM> is mainly absorbed by the organic layer <NUM> and photoelectrically converted and light in a remaining wavelength region is transmitted through the first electrode <NUM> and is sensed by the photo-sensing devices 50a and 50b.

Focusing lens (not shown) may be further formed on the organic photoelectric device <NUM>. The focusing lens may control a direction of incident light and gather the light in one region. The focusing lens may have a shape of, for example, a cylinder or a hemisphere, but is not limited thereto.

As described above, the organic photoelectric device <NUM> has a stack structure thereby a size of an image sensor may be reduced to realize a down-sized image sensor.

In addition, the organic layer includes the fullerene derivative having optical absorption characteristics shifted toward a short wavelength as described above and thus may increase wavelength selectivity compared with the one including the unsubstituted C60 fullerene.

The organic photoelectric device selectively absorbing light in a green wavelength region is for example stacked but this disclosure is not limited thereto. For example, an organic photoelectric device selectively absorbing light in a blue wavelength region may be stacked and a green photo-sensing device and a red photo-sensing device may be integrated in the semiconductor substrate <NUM> or an organic photoelectric device selectively absorbing light in a red wavelength region may be stacked and a green photo-sensing device and a blue photo-sensing device may be integrated in the semiconductor substrate <NUM>.

<FIG> illustrates an embodiment including the organic photoelectric device <NUM> of <FIG>, but is not limited thereto, and the photoelectric device <NUM> of <FIG> may be applied thereto. <FIG> is a cross-sectional view illustrating a CMOS image sensor <NUM>' including the organic photoelectric device <NUM>.

<FIG> is a cross-sectional view showing another example of the organic CMOS image sensor.

The organic CMOS image sensor <NUM> according to the present embodiment like the above embodiment includes a semiconductor substrate <NUM> integrated with photo-sensing devices 50a and 50b, a transmission transistor (not shown), and a charge storage <NUM>, an upper insulation layer <NUM> having a through-hole <NUM>, and an organic photoelectric device <NUM>.

However, in the CMOS image sensor <NUM> according to the present embodiment unlike the above embodiment, the photo-sensing devices 50a and 50b are stacked in a vertical direction, but the color filter layer <NUM> is omitted. The photo-sensing devices 50a and 50b are electrically connected to charge storage (not shown) and may be transferred by the transmission transistor. The photo-sensing devices 50a and 50b may selectively absorb light in each wavelength region depending on a stacking depth.

As described above, the organic photoelectric device selectively absorbing light in a green wavelength region is stacked and the red photo-sensing device and the blue photo-sensing device are stacked, and thereby a size of an image sensor may be reduced to realize a down-sized image sensor.

In <FIG>, the organic photoelectric device selectively absorbing light in a green wavelength region is for example stacked, but this disclosure is not limited thereto. For example, an organic photoelectric device selectively absorbing light in a blue wavelength region may be stacked and a green photo-sensing device and a red photo-sensing device may be integrated in the semiconductor substrate <NUM> or an organic photoelectric device selectively absorbing light in a red wavelength region may be stacked and a green photo-sensing device and a blue photo-sensing device may be integrated in the semiconductor substrate <NUM>.

<FIG> is a schematic top plan view showing an organic CMOS image sensor according to another embodiment and <FIG> is a cross-sectional view of the organic CMOS image sensor according to another embodiment.

The organic CMOS image sensor <NUM> according to the present embodiment includes a green organic photoelectric device selectively absorbing light in a green wavelength region, a blue organic photoelectric device selectively absorbing light in a blue wavelength region, and a red organic photoelectric device selectively absorbing light in a red wavelength region that are stacked.

The organic CMOS image sensor <NUM> according to the present embodiment includes a semiconductor substrate <NUM>, a lower insulation layer <NUM>, an intermediate insulation layer <NUM>, an upper insulation layer <NUM>, a first organic photoelectric device 100a, a second organic photoelectric device 100b, and a third organic photoelectric device 100c.

The semiconductor substrate <NUM> may be a silicon substrate, and is integrated with the transmission transistor (not shown) and the charge storages 55a, 55b, and 55c.

A metal line (not shown) and pad (not shown) are formed on the semiconductor substrate <NUM> and a lower insulation layer <NUM> is formed on the metal line and pad.

The first organic photoelectric device 100a is formed on the lower insulation layer <NUM>.

The first organic photoelectric device 100a includes a first electrode 10a and a second electrode 20a facing each other and an organic layer 30a disposed between the first electrode 10a and the second electrode 20a. The first electrode 10a, the second electrode 20a, and the organic layer 30a are the same as described above and the organic layer 30a may selectively absorb light in one wavelength region of red, blue, and green. For example, the first organic photoelectric device 100a may be a red organic photoelectric device.

In the drawing, the first electrode 10a, the organic layer 30a, and the second electrode 20a are sequentially stacked, but this disclosure is not limited thereto, and for example they may be stacked in an order of the second electrode 20a, the organic layer 30a, and the first electrode 10a.

The intermediate insulation layer <NUM> is formed on the first organic photoelectric device 100a.

The second organic photoelectric device 100b is formed on the intermediate insulation layer <NUM>.

The second organic photoelectric device 100b includes a first electrode 10b and a second electrode 20b facing each other and an organic layer 30b disposed between the first electrode 10b and the second electrode 20b. The first electrode 10b, the second electrode 20b, and the organic layer 30b are the same as described above and the organic layer 30b may selectively absorb light in one wavelength region of red, blue and green. For example, the second photoelectric device 100b may be a blue organic photoelectric device.

In the drawing, the first electrode 10b, the organic layer 30b, and the second electrode 20b are sequentially stacked, but this disclosure is not limited thereto, and for example they may be stacked in an order of the second electrode 20b, the organic layer 30b, and the first electrode 10b.

The upper insulation layer <NUM> is formed on the second organic photoelectric device 100b. The lower insulation layer <NUM>, the intermediate insulation layer <NUM>, and the upper insulation layer <NUM> have a plurality of through-holes exposing the charge storages 55a, 55b, and 55c.

The third organic photoelectric device 100c is formed on the upper insulation layer <NUM>. The third organic photoelectric device 100c includes a first electrode 10c and a second electrode 20c facing each other and an organic layer 30c disposed between the first electrode 10c and the second electrode 20c. The first electrode 10c, the second electrode 20c, and the organic layer 30c are the same as described above and the organic layer 30c may selectively absorb light in one wavelength region of red, blue, and green. For example, the third organic photoelectric device 100c may be a green organic photoelectric device.

In the drawing, the first electrode 10c, the organic layer 30c, and the second electrode 20c are sequentially stacked, but this disclosure is not limited thereto, and for example they may be stacked in an order of the second electrode 20c, the organic layer 30c, and the first electrode 10c.

Focusing lens (not shown) may be further formed on the organic photoelectric device 100c. The focusing lens may control a direction of incident light and gather the light in one region. The focusing lens may have a shape of, for example, a cylinder or a hemisphere, but is not limited thereto.

In the drawing, the first organic photoelectric device 100a, the second organic photoelectric device 100b, and the third organic photoelectric device 100c are sequentially stacked, but the present disclosure is not limited thereto, and they may be stacked in various orders.

As described above, the first organic photoelectric device 100a, the second organic photoelectric device 100b, and the third organic photoelectric device 100c that absorb light in different wavelength regions are stacked, and thereby a size of an image sensor may be reduced to realize a down-sized image sensor.

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

<FIG> is a block diagram of a digital camera including an image sensor according to an embodiment.

Referring to <FIG>, a digital camera <NUM> includes a lens <NUM>, an image sensor <NUM>, a motor <NUM>, and an engine <NUM>. The image sensor <NUM> may be one of image sensors according to embodiments shown in <FIG>.

The lens <NUM> concentrates incident light on the image sensor <NUM>. The image sensor <NUM> generates RGB data for received light through the lens <NUM>.

In some embodiments, the image sensor <NUM> may interface with the engine <NUM>.

The motor <NUM> may adjust the focus of the lens <NUM> or perform shuttering in response to a control signal received from the engine <NUM>. The engine <NUM> may control the image sensor <NUM> and the motor <NUM>.

The engine <NUM> may be connected to a host/application <NUM>.

In example embodiments, the motor <NUM>, engine <NUM>, and host/application <NUM> may include processing circuitry such as hardware including logic circuits; a hardware/software combination such as a processor executing software; or a combination thereof. For example, the processing circuitry more specifically may 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-Chip (SoC), a programmable logic unit, a microprocessor, application-specific integrated circuit (ASIC), etc..

However, these examples are exemplary, and the scope of claims is not limited thereto.

A suspension including a <NUM>,<NUM>-dibromocorannulene derivative having dihydro-<NUM>,<NUM>-furandione (Compound (<NUM>), <NUM>, <NUM> mmol), isopropylamine (<NUM>, <NUM> mmol), and N-methylpyrrolidone (NMP, <NUM>) is prepared and put in a container of a microwave reactor. After reacting them at <NUM> for <NUM> minutes, a suspension in the container is mixed. Subsequently, NMP is removed under a vacuum distillation (less than or equal to <NUM> torr, greater than or equal to <NUM>). Then, chloroform is added to the residue and then, purified through silica gel column chromatography (an eluent: a mixture of chloroform and hexane in a volume ratio of <NUM>:<NUM>).

After evaporating the solvent from the obtained solution, a solid therefrom is dissolved in chloroform, and a product therefrom is separated by using Recycle HPLC (Buckyprep <NUM>φ X <NUM>; an eluent: chloroform). The solvent is evaporated from the solution to obtain an intermediate (Compound (<NUM>), <NUM>, <NUM> mmol, yield: <NUM>%).

The intermediate (Compound (<NUM>), <NUM>, <NUM> mmol), a catalyst of Pd(OAc)<NUM> (palladium (II) acetate, <NUM>, <NUM> mmol), a base of tBuONa (sodium tert-butoxide, <NUM>, <NUM> mmol), a toluene solution of P(tBu)<NUM> (tri-tert-butylphosphine, <NUM> wt%, <NUM>, <NUM> mmol), and m-xylene (<NUM>) are mixed in a flask and then, stirred by using an oil bath at <NUM> for <NUM> hours.

Subsequently, an evaporator (less than or equal to <NUM> mbar, greater than or equal to <NUM>) is used to remove the solvent. Then, chloroform is added to the residue and then, purified through silica gel column chromatography (an eluent: a mixture of chloroform and hexane in a volume ratio of <NUM>:<NUM>).

After evaporating the solvent from the solution, a solid therefrom is dissolved in chloroform, and a product therefrom is separated by using Recycle HPLC (Buckyprep <NUM>φ X <NUM>; an eluent: chloroform). The solvent is evaporated from the solution to obtain a compound represented by Chemical Formula A (Compound (<NUM>), <NUM>, <NUM> mmol, yield: <NUM>%). <NUM>H NMR (CDCl<NUM>): δ <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> to <NUM> (m. <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>).

The compound (<NUM>) in Synthesis Example <NUM> (<NUM>, <NUM> mmol), Pd(PPh<NUM>)<NUM> (tetrakis(triphenylphosphine)palladium (<NUM>), <NUM>, <NUM> mmol), Na<NUM>CO<NUM> (<NUM>, <NUM> mmol), phenyl boronic acid (PhB(OH)<NUM>, <NUM>, <NUM> mmol), and a mixed solvent (toluene (<NUM>), EtOH (<NUM>), and water (<NUM>)) are mixed and then, stirred by using an oil bath at <NUM> for <NUM> hours to obtain a compound represented by Chemical Formula B (<NUM>, <NUM> mmol, yield: <NUM>%). <NUM>H NMR (CDCl<NUM>): δ <NUM> (s, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> to <NUM> (m. <NUM>), <NUM> (s, <NUM>).

The compound (<NUM>) in Synthesis Example <NUM> (<NUM>, <NUM> mmol), Pd(PPh<NUM>)<NUM> (<NUM>, <NUM> mmol), Na<NUM>CO<NUM> (<NUM>, <NUM> mmol), phenyl boronic acid ester (<NUM>-tert-butylphenylboronic acid pinacol ester, <NUM>, <NUM> mmol), and a mixed solvent (toluene (<NUM>), EtOH (<NUM>), and water (<NUM>)) are mixed and then, stirred by using an oil bath at <NUM> for <NUM> hours to obtain a compound represented by Chemical Formula C (<NUM>, <NUM> mmol, yield: <NUM>%). <NUM>H NMR (CDCl<NUM>): δ <NUM> (s, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> (d. <NUM>), <NUM> to <NUM> (m. <NUM>), <NUM> (s, <NUM>).

An intermediate (Compound (<NUM>), <NUM>, <NUM> mmol, yield: <NUM>%) is synthesized according to the same method as Synthesis Example <NUM> except that phenyl amine (PhNH<NUM>) is used instead of the isopropylamine in the first step of Synthesis Example <NUM>.

The intermediate (Compound (<NUM>), <NUM>, <NUM> mmol), Pd(PPh<NUM>)<NUM> (<NUM>, <NUM> mmol), Na<NUM>CO<NUM> (<NUM>, <NUM> mmol), phenyl boronic acid ester (<NUM>-tert-butylphenylboronic acid pinacol ester, <NUM>, <NUM> mmol), and a mixed solvent (toluene (<NUM>), EtOH (<NUM>), and water (<NUM>)) are mixed and then, stirred by using an oil bath at <NUM> for <NUM> hours to obtain a compound represented by Chemical Formula D (Compound (<NUM>), <NUM>, <NUM> mmol, yield: <NUM>%). <NUM>H NMR (CDCl<NUM>): δ <NUM> to <NUM> (m, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> (S, <NUM>).

An intermediate (Compound (<NUM>), <NUM>, <NUM> mmol, yield: <NUM>%) is synthesized according to the same method as Synthesis Example <NUM> except that <NUM>,<NUM>-diisopropylphenylamine ((iPr)<NUM>C<NUM>H<NUM>NH<NUM>) is used instead of the isopropylamine in the first step of Synthesis Example <NUM>.

The intermediate (Compound (<NUM>), <NUM>, <NUM> mmol), Pd(PPh<NUM>)<NUM> (<NUM>, <NUM> mmol), Na<NUM>CO<NUM> (<NUM>, <NUM> mmol), phenyl boronic acid ester (<NUM>-isopropylphenylboronic acid pinacol ester, <NUM>, <NUM> mmol), and a mixed solvent (toluene (<NUM>), EtOH (<NUM>), and water (<NUM>)) are mixed and then, reacted by using a microwave reactor at <NUM> for <NUM> hour to obtain a compound represented by Chemical Formula E (Compound (<NUM>), <NUM>, <NUM> mmol, yield: <NUM>%). <NUM>H NMR (CDCl<NUM>): δ <NUM> to <NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>).

A compound represented by Chemical Formula F (<NUM>, <NUM> mmol, yield: <NUM>%) is synthesized according to the same method as that of Scheme <NUM> disclosed in an article of <NPL> except that benzo[d]thiazol-<NUM>-yl boronic acid (<NUM>, <NUM> mmol) is used instead of the <NUM>,<NUM>-dimethyl-fluorenyl-<NUM>-pinacolato boronic ester. <NUM>H NMR (CDCl<NUM>): δ <NUM> to <NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> (s, <NUM>).

A compound represented by Chemical Formula G (<NUM>, <NUM> mmol, yield: <NUM>%) is synthesized according to the same method as Synthesis Example <NUM> which is disclosed in a patent reference of <CIT>. <NUM>H NMR (DMSO- d <NUM>): δ <NUM> (d, <NUM>), <NUM> (s, <NUM>), <NUM> ( t , <NUM>), <NUM>-<NUM> (m, <NUM>).

A compound represented by Chemical Formula H (<NUM>, <NUM> mmol, yield: <NUM>%) is synthesized according to the same method as Preparation Example <NUM>, which is disclosed in a patent reference of <CIT>, except that <NUM>,<NUM>-dibromo-<NUM>-(trifluoromethyl)thiophene (<NUM>, <NUM> mmol) is used instead of <NUM>,<NUM>-dibromothiophene. <NUM>H NMR (C<NUM>D<NUM>CD<NUM>) d <NUM> (d. <NUM>), <NUM> (s, <NUM>).

The compound (<NUM>) in Synthesis Example <NUM> (<NUM>, <NUM> mmol), a catalyst of Pd(dba)<NUM> (bis(dibenzylideneacetone)palladium (<NUM>), <NUM>, <NUM> mmol), a base of Cs<NUM>CO<NUM> (<NUM>, <NUM> mmol), SPhos (<NUM>-dicyclohexylphosphino-<NUM>',<NUM>'-dimethoxybiphenyl, <NUM>, <NUM>µmol), m-xylene (<NUM>), and IPA (isopropyl alcohol, <NUM>) are mixed in a flask and then, stirred by using an oil bath at <NUM> for <NUM> hours. Subsequently, an evaporator (less than or equal to <NUM> mbar, greater than or equal to <NUM>) is used to remove the solvents. Then, chloroform is added to the residue and then, purified through silica gel column chromatography (an eluent: chloroform and hexane in a volume ratio of <NUM>:<NUM>).

After evaporating the solvent from the solution, a solid therefrom is dissolved in chloroform, and a product is separated therefrom by using Recycle HPLC (Buckyprep <NUM>φ X <NUM>; an eluent: chloroform). The solvent is evaporated from the solution to obtain a product (<NUM>, <NUM> mmol, yield: <NUM>%). <NUM>H NMR (CDCl<NUM>): δ <NUM> (d, <NUM>), <NUM> (d, <NUM>), <NUM> (d, <NUM>), <NUM> to <NUM> (m, <NUM>), <NUM> (s, <NUM>).

<CHM>
C60 fullerene (Nanom purple ST, Frontier Carbon Corp.

ITO is sputtered and deposited on a glass substrate to form an about <NUM>-thick anode, and an N-type semiconductor composition including a fullerene subunit derivative represented by Chemical Formula A according to Synthesis Example <NUM> (an N-type semiconductor compound) and C60 fullerene represented by Chemical Formula J and a compound represented by Chemical Formula X (a P-type semiconductor compound) are codeposited thereon to form a <NUM>-thick active layer. The N-type semiconductor composition and the P-type semiconductor compound are used in a volume ratio of <NUM>:<NUM>, and the N-type semiconductor composition includes the fullerene subunit derivative (the N-type semiconductor compound) and C60 fullerene represented by Chemical Formula J in a volume ratio of <NUM>:<NUM>. On the active layer, a <NUM>-thick molybdenum oxide (MoOx, <NUM><x≤<NUM>) thin film is formed as a charge auxiliary layer. Subsequently, on the molybdenum oxide thin film, ITO is deposited through sputtering to form a <NUM>-thick cathode, manufacturing an organic photoelectric device.

Organic photoelectric devices manufactured according to the same method as Example <NUM> except that the fullerene subunit derivatives according to Synthesis Examples <NUM> to <NUM> and Comparative Synthesis Example <NUM> are respectively used instead of the fullerene subunit derivative represented by Chemical Formula A according to Synthesis Example <NUM>.

An organic photoelectric device of Comparative Example <NUM> is manufactured according to the same method as Example <NUM> except that C60 fullerene and a P-type semiconductor compound are codeposited in a volume ration of <NUM>:<NUM> to form an active layer without using the fullerene derivative represented by Chemical Formula A according to Synthesis Example <NUM>.

The organic photoelectric devices according to Examples <NUM> to <NUM> and Comparative Examples <NUM> and <NUM> as an organic photoelectric device <NUM> for an image sensor <NUM> having a structure shown in <FIG> are respectively used to manufacture image sensors.

In order to evaluate thermal stability of the fullerene subunit derivatives according to Synthesis Examples <NUM> to <NUM>, deposition temperatures (Ts<NUM>) where <NUM> wt% is sublimated at <NUM> Pa and (Ts<NUM>) where <NUM> wt% is sublimated at <NUM> Pa are measured. In addition, the deposition temperatures of the compounds according to Comparative Synthesis Examples <NUM> to <NUM> are measured. Herein, specimens are all prepared by well drying powder purified up to high purity of greater than or equal to <NUM>%, and the deposition temperatures are measured in a thermal gravimetric analysis (TGA) method. The results of the compounds according to Synthesis Examples <NUM> to <NUM> and Comparative Synthesis Examples <NUM> to <NUM> and <NUM> are shown in Table <NUM>.

Referring to Table <NUM>, the fullerene subunit derivatives according to Synthesis Example <NUM> to <NUM> exhibit a lower deposition temperature than the compounds according to Comparative Synthesis Examples <NUM> to <NUM> and <NUM>. Accordingly, the fullerene subunit derivatives according to Synthesis Example <NUM> to <NUM> turn out to be compounds capable of being deposited through sublimation.

The fullerene subunit derivatives according to Synthesis Examples <NUM> to <NUM> are deposited to form thin films, and each thin film is measured with respect to HOMO and LUMO energy levels by using a B3LYP/<NUM>-<NUM>(d) level theory described in┌M. <NPL> in a method of Gaussian <NUM> program. The results of Synthesis Examples <NUM> to <NUM> and Comparative Synthesis Example <NUM> are shown in Table <NUM>. For reference, the HOMO and LUMO energy levels of the compounds represented by Chemical Formulae K and L as a P-type semiconductor compound are provided.

Chemical Formulae K and L shown in Table <NUM> have the following structures.

Referring to Table <NUM>, when the compounds according to Synthesis Examples <NUM> to <NUM> are measured with B3LYP/<NUM>-<NUM>(d) with reference to ┌<NPL>┘, HOMO levels thereof are equal to that of C60, and LUMO levels are not high enough to be usable as an N-type semiconductor. Compared with the HOMO and LUMO energy levels of the compounds of Chemical Formulae K and L as a P-type semiconductor compound, the compounds of Synthesis Examples <NUM> to <NUM> may be appropriately used as an N-type semiconductor compound.

A Nanomatch software is used to evaluate morphology of an active layer formed on a substrate by codepositing N-type and P-type semiconductors. Results of calculating average distances between the N-type and the P-type semiconductor (a compound represented by Chemical Formula X) in the active layer are shown in Table <NUM>. Virtually-formed blend morphology obtained by using the software is used to calculate the average distances, and the results are shown in Table <NUM>.

The structures of Chemical Formulae M to Q shown in Table <NUM> are as follows. <CHM>
<CHM>.

Referring to Table <NUM>, the compounds represented by Chemical Formulae A to E and M to Q include a bulky substituent X and an additional bulky substituent at the side and thus have shorter distances with the P-type semiconductor than the compound represented by Chemical Formula I having no bulky substituent. The reason is that since crystallization of each compound represented by Chemical Formulae A to E and M to Q (the N-type semiconductor) is further reduced or suppressed, compared with that of the compound represented by Chemical Formula I, the compounds are respectively well mixed with the P-type semiconductor and form the active layers. Accordingly, crystallinity of the compounds is not only sufficiently low, but also the compounds represented by Chemical Formulae A to E and M to Q are well mixed with the P-type semiconductor.

External quantum efficiency (EQE) of the organic photoelectric devices according to Examples <NUM> to <NUM> and Comparative Examples <NUM> and <NUM> is measured. The external quantum efficiency is measured by using an IPCE measurement system (McScience Inc, Korea). First, an Si photodiode (Hamamatsu Photonics K. , Japan) is used to calibrate the system, and the organic photoelectric devices according to Examples <NUM> to <NUM> and Comparative Examples <NUM> and <NUM> are respectively mounted thereon and measured with respect to the external quantum efficiency in a wavelength range of about <NUM> to <NUM>. The results of Examples <NUM> to <NUM> and Comparative Examples <NUM> and <NUM> are shown in Table <NUM>.

Referring to Table <NUM>, absorption of the organic photoelectric devices according to Examples <NUM> to <NUM> in a blue region is decreased by <NUM>% to <NUM>% or more, compared with that of Comparative Example <NUM>. Absorption of C60 in the blue region (<NUM>) is known due to aggregation of C60 (<NPL>). In other words, the absorption decrease of the organic photoelectric devices of Examples <NUM> to <NUM> in the blue region (<NUM>) means that the C60 aggregation decreases or disappears. Accordingly, abnormal light absorption properties of the organic photoelectric devices of Examples <NUM> to <NUM> in the blue region do not occur.

On the other hand, EQE of Comparative Example <NUM> in the blue region at room temperature is decreased before annealing like Examples <NUM> to <NUM>, but EQE performance thereof after the annealing is deteriorated in the entire visible light regions (Blue/Green/Red).

Although not bound by any theory, the reason that EQE performance of the organic photoelectric devices of Examples <NUM> to <NUM> is not deteriorated after the annealing is that the fullerene subunit derivative contains three bulky substituents in corannulene and thus is not crystallized at a high temperature. On the other hand, Comparative Example <NUM> including one bulky substituent X in the corannulene is crystallized due to the annealing. Accordingly, the fullerene subunit derivative having one bulky substituent exhibits low thermal stability.

The organic photoelectric devices of Examples <NUM> to <NUM> and Comparative Examples <NUM> and <NUM> are measured with respect to an absorption coefficient in the blue region (<NUM>). The results of Examples <NUM> to <NUM> and Comparative Example <NUM> are shown in Table <NUM>.

Referring to Table <NUM>, absorption of the organic photoelectric devices of Example <NUM> to <NUM> in the blue region is <NUM>% or more decreased compared with that of Comparative Example <NUM>.

Mobility of the organic photoelectric devices of Examples <NUM> to <NUM> and Comparative Examples <NUM> and <NUM> is measured. The mobility is measured in a Space-charge-limited current (SCLC) method disclosed in an article of <NPL>. The results of Examples <NUM> to <NUM> and Comparative Example <NUM> are shown in Table <NUM>.

Referring to Table <NUM>, the mobility of the organic photoelectric devices of Examples <NUM> to <NUM> is <NUM> times or more as high as that of the organic photoelectric device of Comparative Example <NUM>.

Since partial aggregation of C60 which is regarded to be present in a bulk hetero junction (BHJ) of the active layer is reduced or suppressed due to the fullerene subunit derivative, the mobility may be improved by suppressing a charge loss at aggregation points. In addition, the fullerene subunit derivative has N-type characteristics and thus may play a role of transporting charges and improve the mobility.

The image sensors of Examples <NUM> to <NUM> and Comparative Examples <NUM> to <NUM> respectively including the organic photoelectric devices of Examples <NUM> to <NUM> and Comparative Examples <NUM> and <NUM> are evaluated with respect to YSNR10. YSNR10 is measured by taking a photo of an <NUM>% gray patch of the Macbeth chart under a light source of D-<NUM>. Herein, lens has an F value of <NUM> and transmittance of <NUM>%, and interference-type lens are used for an infrared ray cut filter. A pixel size of the image sensors is <NUM>, and a frame rate of the image sensors is 15fps.

Herein, YSNR10 is used to evaluate sensitivity of the image sensors and measured in a <NPL>, but minimum illumination where a ratio of signal and noise becomes <NUM> is expressed as lux. The results of the image sensors including the organic photoelectric devices of Example <NUM> and Comparative Example <NUM> are shown in Table <NUM>.

Referring to Table <NUM>, the image sensor including the organic photoelectric device of Example <NUM> exhibits <NUM>% improved YSNR10 compared with the image sensor including the organic photoelectric device of Comparative Example <NUM>.

Claim 1:
An N-type semiconductor composition, comprising
fullerene or a fullerene derivative; and
a fullerene subunit derivative, characterized in that the fullerene subunit derivative is represented by Chemical Formula <NUM>:
<CHM>
wherein, in Chemical Formula <NUM>,
Cy is a cyclic group selected from a C3 to C20 alicyclic group and a C6 to C20 aromatic group, or a fused cyclic group of two or more cyclic groups,
wherein the cyclic group in Cy is a heterocyclic group including at least one functional group selected from -N=, -NR-, -O-, -S-, -Se-, -Te-, -C(=O)-, -C(=S)-, - C(=Se)-, -C(=Te)-, -C(=C(CN)<NUM>)-, and -C(=NR)- wherein R is a C1 to C10 alkyl group,
X is at least one bulky substituent selected from a substituted or unsubstituted C3 to C30 branched alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted C2 to C30 heteroaryl group,
R<NUM> and R<NUM> are a bulky substituent selected from a substituted or unsubstituted C3 to C20 branched alkyl group, a substituted or unsubstituted C3 to C20 branched alkoxy group, a substituted or unsubstituted C3 to C20 branched alkylsilyl group, a substituted or unsubstituted C3 to C20 branched heteroalkyl 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 C3 to C30 heterocycloalkyl group, and a combination thereof, and
R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, and R<NUM> are hydrogen, deuterium, a halogen, a cyano group, a C1 to C20 linear alkyl group, or a combination thereof.