Compounds, films, infrared sensors, combination sensors, and electronic devices

Abstract

The present invention relates to compounds, films, infrared sensors, combination sensors, and electronic devices. The compounds are represented by Chemical Formula 1. The compounds can be included in films, infrared sensors, combination sensors, and / or electronic devices. In Chemical Formula 1, X, Y 1 , Y 2 , Z 1 , Z 2 , Q, R 1 , and R 2 are the same as described in the detailed description.[Chemical Formula 1]

Description

[0001] Cross-reference to related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2020-0110629, filed on August 31, 2020, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Compounds, membranes, infrared sensors, combined sensors, and electronic devices (devices) are disclosed. Background Technology

[0004] Imaging devices are used in digital cameras and camcorders to capture images and store the captured images as electrical signals, and the imaging devices include sensors that separate incident light into individual components defined by individual wavelength spectra and convert each individual component into an electrical signal. Summary of the Invention

[0005] Some exemplary implementations provide compounds that exhibit good light absorption and electrical properties in the infrared wavelength spectrum.

[0006] Some exemplary implementations provide membranes comprising the compound.

[0007] Some exemplary embodiments provide infrared sensors comprising the said compound. Such infrared sensors can be configured to detect light in the infrared (IR) wavelength spectrum with improved sensitivity in low-light environments and / or can be configured to function as biometric or security devices.

[0008] Some exemplary implementations provide a combined sensor that includes the compound or the infrared sensor.

[0009] Some exemplary implementations provide electronic devices that include the compound, the infrared sensor, or the combined sensor.

[0010] According to some exemplary embodiments, compounds represented by chemical formula 1 are provided.

[0011] [Chemical Formula 1]

[0012]

[0013] In chemical formula 1,

[0014] X is O, S, Se, Te, SO, SO2, NR a CR b R c or SiR d R e ,

[0015] Y 1 and Y 2 Independent for CR f Or N,

[0016] Z 1 or Z 2 One of them is S and Z 1 or Z 2 The other is O, S, Se, Te, or NR. g ,

[0017] Q represents a substituted or unsubstituted C3-C30 quinone ring.

[0018] R 1 and R 2 Independently, it is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof.

[0019] R a -R g Independently, it is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, a cyano group, or a combination thereof.

[0020] R 1 and R 2 They can exist independently or be connected to each other to form a ring.

[0021] R b and R c They can exist independently or be connected to each other to form a ring.

[0022] R d and R e They exist independently or are connected to each other to form a ring, and

[0023] Adjacent R f They exist independently or are connected to each other to form a ring.

[0024] Q in Formula 1 may include at least one substituted or unsubstituted 5-membered quinone ring, at least one substituted or unsubstituted 6-membered quinone ring, or a fused ring thereof.

[0025] Q in chemical formula 1 can be one of the groups listed in group 1.

[0026] [Group 1]

[0027]

[0028]

[0029] In group 1,

[0030] W 1 Unlike X and being S, Se, or Te,

[0031] W 2 -W 13 Independently S, Se, or Te,

[0032] R 3 -R 46 Independently, it is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, a cyano group, or a combination thereof.

[0033] R 3 -R 46 Existing independently or R 3 -R 46 Two adjacent elements are connected to each other to provide a loop, and

[0034] * indicates the connection point with chemical formula 1.

[0035] X and Z of chemical formula 1 1 and Z 2 Each can be represented by an S.

[0036] The compound may be represented by one of the chemical formulas 1A to 1I.

[0037] [Chemical Formula 1A]

[0038]

[0039] [Chemical Formula 1B]

[0040]

[0041] [Chemical Formula 1C]

[0042]

[0043] [Chemical Formula 1D]

[0044]

[0045] [Chemical Formula 1E]

[0046]

[0047] [Chemical Formula 1F]

[0048]

[0049] [Chemical Formula 1G]

[0050]

[0051] [Chemical formula 1H]

[0052]

[0053] [Chemical Formula 1I]

[0054]

[0055] In chemical formulas 1A to 1I,

[0056] X is O, S, Se, Te, SO, SO2, NR a CR b R c or SiR d R e , where R a -R e Independently, it is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, a cyano group, or a combination thereof.

[0057] W 2 -W 9 W 12 and W 13 Independently S, Se, or Te,

[0058] R 1 and R 2 Independently being hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof, and

[0059] R 3 -R 6 R 9 -R 20 R 25 -R 30 R 43 -R 46 and R fIndependently, it is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, a cyano group, or a combination thereof.

[0060] The compound may be represented by one of the chemical formulas 1A-1 to 1I-1.

[0061] [Chemical Formula 1A-1]

[0062]

[0063] [Chemical Formula 1B-1]

[0064]

[0065] [Chemical formula 1C-1]

[0066]

[0067] [Chemical formula 1D-1]

[0068]

[0069] [Chemical Formula 1E-1]

[0070]

[0071] [Chemical formula 1F-1]

[0072]

[0073] [Chemical Formula 1G-1]

[0074]

[0075] [Chemical formula 1H-1]

[0076]

[0077] [Chemical formula 1I-1]

[0078]

[0079] In chemical formulas 1A-1 to 1I-1,

[0080] R 1 and R 2Independently being hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof, and

[0081] R 3 -R 6 R 9 -R 20 R 25 -R 30 R 43 -R 46 and R f Independently, it is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, a cyano group, or a combination thereof.

[0082] According to some exemplary embodiments, a membrane comprising the compound is provided.

[0083] The membrane has a peak absorption wavelength in the wavelength range of about 800 nm to about 3000 nm.

[0084] According to some exemplary embodiments, the infrared sensor includes: a first electrode and a second electrode facing each other, and an organic layer between the first electrode and the second electrode comprising a compound represented by chemical formula 1.

[0085] The wavelength at which the infrared sensor exhibits peak external quantum efficiency may fall within the wavelength range of approximately 800 nm to approximately 3000 nm, such that the infrared sensor exhibits peak EQE for incident light at the peak external quantum efficiency (EQE) wavelength within the wavelength range of approximately 800 nm to approximately 3000 nm.

[0086] The organic layer may include an infrared photoelectric conversion layer, which may include the compound and a counter material for forming a pn junction with the compound.

[0087] The infrared sensor may include an infrared photoelectric conversion layer and an auxiliary layer, wherein the auxiliary layer is located between the first electrode and the infrared photoelectric conversion layer or between the second electrode and the infrared photoelectric conversion layer.

[0088] The infrared photoelectric conversion layer may include the compound, and the auxiliary layer may include ytterbium (Yb), calcium (Ca), potassium (K), barium (Ba), magnesium (Mg), lithium fluoride (LiF), or alloys thereof.

[0089] The auxiliary layer may include the compound.

[0090] The infrared sensor may further include a semiconductor substrate.

[0091] According to some exemplary embodiments, the combined sensor includes: a first infrared sensor, which is the infrared sensor; and a second infrared sensor configured to detect incident light in an infrared wavelength spectrum in a wavelength spectrum shorter than or longer than that of the first infrared sensor, wherein the first infrared sensor and the second infrared sensor are stacked on top of each other in a depth direction perpendicular to the in-plane direction of the first infrared sensor.

[0092] According to some exemplary embodiments, the combined sensor includes the infrared sensor and the visible light sensor, the visible light sensor being configured to detect at least a portion of incident light in the visible light wavelength spectrum.

[0093] The combined sensor may further include a semiconductor substrate, and the infrared sensor may be arranged parallel to the visible light sensor along the in-plane direction of the semiconductor substrate, or may be stacked with the visible light sensor along the depth direction of the semiconductor substrate.

[0094] The visible light sensor may include: a blue sensor configured to sense light in the blue wavelength spectrum, a green sensor configured to sense light in the green wavelength spectrum, and a red sensor configured to sense light in the red wavelength spectrum, wherein each of the blue, green, and red sensors may be a photodiode integrated in a semiconductor substrate.

[0095] The visible light sensor may include: a blue sensor configured to sense light in the blue wavelength spectrum, a green sensor configured to sense light in the green wavelength spectrum, and a red sensor configured to sense light in the red wavelength spectrum, wherein two of the blue, green, or red sensors may be photodiodes integrated in a semiconductor substrate, and the other of the blue, green, or red sensors may be a visible light photoelectric conversion device stacked on the semiconductor substrate and in a depth direction perpendicular to the in-plane direction of the infrared sensor.

[0096] The visible light sensor may include: a blue sensor configured to sense light in the blue wavelength spectrum, a green sensor configured to sense light in the green wavelength spectrum, and a red sensor configured to sense light in the red wavelength spectrum, wherein each of the blue, green, and red sensors may be a visible light photoelectric conversion device stacked with the infrared sensor.

[0097] The infrared photoelectric conversion layer may include an intrinsic layer, which comprises the compound and the material in a volume ratio of about 1:9 to about 9:1.

[0098] The infrared photoelectric conversion layer may have a thickness of approximately 80 nm to approximately 300 nm.

[0099] The first infrared sensor is configured to sense a portion of incident light comprising at least a first wavelength in the infrared wavelength spectrum, the first wavelength being the peak absorption wavelength of the first infrared sensor. The second infrared sensor is configured to sense another portion of incident light comprising at least a second wavelength in the infrared wavelength spectrum, the second wavelength being the peak absorption wavelength of the second infrared sensor. The difference between the first wavelength and the second wavelength may be between approximately 70 nm and approximately 150 nm.

[0100] The membrane may have a thickness of approximately 1 nm to approximately 30 μm.

[0101] According to some exemplary embodiments, an infrared sensor may include: a first electrode and a second electrode facing each other, an infrared photoelectric conversion layer between the first electrode and the second electrode, and an auxiliary layer, the auxiliary layer being located between at least one of the first electrode and the infrared photoelectric conversion layer, or between the second electrode and the infrared photoelectric conversion layer, wherein at least one of the infrared photoelectric conversion layer or the auxiliary layer comprises a compound represented by chemical formula 1.

[0102] The compound may be one of compound A, compound B, or compound C:

[0103] [Compound A]

[0104]

[0105] [Compound B]

[0106]

[0107] [Compound C]

[0108]

[0109] The compound exhibits peak absorption wavelengths in a wavelength spectrum ranging from approximately 700 nm to approximately 1000 nm.

[0110] The infrared sensor can be configured to exhibit a peak EQE at the peak external quantum efficiency (EQE) wavelength of the infrared sensor, the peak EQE wavelength of the infrared sensor being between approximately 1000 nm and approximately 3000 nm.

[0111] According to some exemplary embodiments, electronic devices are provided that include the compound, membrane, infrared sensor, or combination of sensors.

[0112] The compound exhibits good light absorption and electrical properties in the infrared region, and therefore can be effectively applied to sensors. Attached Figure Description

[0113] Figure 1 To show a cross-sectional view of an example of an infrared sensor according to some exemplary embodiments,

[0114] Figure 2 To show a cross-sectional view of an example of a CMOS infrared sensor according to some exemplary embodiments,

[0115] Figure 3 To show a cross-sectional view of one example of a combined sensor according to some exemplary implementations,

[0116] Figure 4 To show a cross-sectional view of another example of a combined sensor according to some exemplary implementations,

[0117] Figure 5 To show a cross-sectional view of another example of a combined sensor according to some exemplary implementations,

[0118] Figure 6 To schematically show another example of a combined sensor according to some exemplary implementations, a cross-sectional view is provided.

[0119] Figure 7 To schematically show another example of a combined sensor according to some exemplary implementations, a cross-sectional view is provided.

[0120] Figure 8 A perspective view is provided to schematically illustrate another example of a combined sensor implemented according to some exemplary embodiments.

[0121] Figure 9 To illustrate along Figure 8 The line IX-IX' Figure 8 A cross-sectional view of an example of a combined sensor.

[0122] Figure 10 A perspective view is provided to schematically illustrate another example of a combined sensor implemented according to some exemplary embodiments.

[0123] Figure 11 For illustrative purposes only Figure 10 A cross-sectional view of an example of a combined sensor.

[0124] Figure 12 A schematic diagram of an electronic device according to some example embodiments, and

[0125] Figure 13 A graph showing the external quantum efficiency of the infrared sensors according to the embodiments and comparative examples based on wavelength. Detailed Implementation

[0126] The following description will detail exemplary implementations so that those skilled in the art can readily implement them. However, practical applications may utilize structures in many different forms, and are not limited to the exemplary implementations described herein.

[0127] In the accompanying drawings, the thickness of layers, films, panels, regions, etc., is magnified for clarity.

[0128] 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 may be directly on said other element or there may be intermediate elements present. Conversely, when an element is referred to as being "directly on" another element, there are no intermediate elements present. It will be further understood that when an element is referred to as being "on" another element, it may be above, below, or adjacent to (e.g., horizontally adjacent to) the other element.

[0129] It will be understood that elements and / or properties (e.g., structure, surface, orientation, etc.) that are described as "perpendicular", "parallel", "coplanar" with respect to other elements and / or their properties (e.g., structure, surface, orientation, etc.) may be "substantially perpendicular", "substantially parallel", or "substantially coplanar" with respect to other elements and / or their properties, respectively.

[0130] An element and / or its properties that are “substantially perpendicular” to another element and / or its properties (e.g., structure, surface, orientation, etc.) will be understood as being “perpendicular” to another element and / or its properties within manufacturing and / or material tolerances, and / or having a deviation of equal to or less than 10% in size and / or angle from being “perpendicular” to another element and / or its properties (e.g., ±10% tolerance).

[0131] Components and / or properties that are “substantially parallel” to other components and / or their properties (e.g., structure, surface, orientation, etc.) will be understood as being “parallel” to other components and / or their properties within manufacturing and / or material tolerances, and / or having a deviation of equal to or less than 10% in size and / or angle from being “parallel” to other components and / or their properties (e.g., ±10% tolerance).

[0132] Elements and / or properties that are “substantially coplanar” relative to other elements and / or their properties (e.g., structure, surface, orientation, etc.) will be understood as being “coplanar” relative to other elements and / or their properties within manufacturing and / or material tolerances, and / or having a deviation of equal to or less than 10% in size and / or angle from being “coplanar” relative to other elements and / or their properties (e.g., ±10% tolerance).

[0133] It will be understood that an element and / or its properties may be described herein as being "the same" or "equal" to another element, and it will be further understood that an element and / or its properties described herein as being "the same," "the same," or "equal" to another element may be "the same," "the same," or "equal," or "substantially the same," "substantially identical," or "substantially equivalent." Element and / or its properties being "substantially the same," "substantially identical," or "substantially equivalent" to another element and / or its properties will be understood to include elements and / or its properties being the same, the same, or equal to another element and / or its properties within manufacturing tolerances and / or material tolerances. Element and / or its properties being the same or substantially the same and / or the same or substantially the same may be structurally the same or substantially the same, functionally the same or substantially the same, and / or compositionally the same or substantially the same.

[0134] It will be understood that elements and / or properties described herein as “substantially” identical and / or the same include elements and / or properties having a relative difference in size equal to or less than 10%. Furthermore, regardless of whether an element and / or property is modified to “substantially”, it will be understood that such elements and / or properties should be interpreted to include manufacturing or operational tolerances (e.g., ±10%) surrounding the stated elements and / or properties.

[0135] When the terms “about” or “substantially” are used in this specification with respect to numerical values, it is intended that the relevant numerical values ​​include a tolerance of ±10% around the stated value. When a range is described, the range includes all values ​​therebetween, for example, increments of 0.1%.

[0136] As used herein, unless otherwise defined, “substituted” means that the hydrogen atom of a compound or group is replaced by a substituent selected from the following: halogen atom, hydroxyl, alkoxy, nitro, cyano, amino, azide, amido, hydrazine, hydrazone, carbonyl, carbamoyl, thiol group, ester group, carboxyl group or a salt thereof, sulfonic acid group or a salt thereof, phosphate group or a salt thereof, silyl, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C30 aryl, C7-C30 aralkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C20 heteroalkyl, C3-C20 heteroaryl, C3-C20 heteroaryl, C3-C30 cycloalkyl, C3-C15 cycloalkenyl, C6-C15 cycloalkynyl, C3-C30 heterocycloalkyl, and combinations thereof.

[0137] As used herein, unless otherwise defined, “heterogeneous” refers to a mixture of 1 to 4 heteroatoms selected from N, O, S, Se, Te, Si, and P.

[0138] As used herein, unless otherwise defined, "aromatic ring" refers to a functional group in which all atoms in the cyclic functional group have p orbitals, wherein these p orbitals are conjugated. For example, an aromatic ring can be C6-C30 aryl or C2-C30 heteroaryl.

[0139] As used herein, unless otherwise defined, "aryl" refers to a group comprising at least one hydrocarbon aromatic moiety. All elements of the hydrocarbon aromatic moiety have conjugated p orbitals, such as phenyl, naphthyl, etc., and two or more hydrocarbon aromatic moieties may be linked by σ bonds and may be, for example, biphenyl, terphenyl, tetraphenyl, etc., and two or more hydrocarbon aromatic moieties may be directly or indirectly fused to provide a non-aromatic fused ring, such as fluorene. Aryl groups may include monocyclic, polycyclic, or fused polycyclic (i.e., rings sharing adjacent carbon pairs) functional groups.

[0140] As used herein, unless otherwise defined, "heterocyclic" or "heterocyclic group" is a broader concept that includes "heteroaryl" and may include at least one heteroatom selected from N, O, S, Se, Te, P, and Si in place of carbon (C). When the heterocycle is a fused ring, the heterocycle may have at least one heteroatom, and each ring may have heteroatoms.

[0141] As used herein, unless otherwise defined, "ring" refers to an aromatic ring, a non-aromatic ring, a heteroaromatic ring, a non-aromatic heterocyclic ring, a fused ring, and / or a combination thereof. The aromatic ring may be C6-C30 aryl or C2-C30 heteroaromatic, and the non-aromatic ring may be C3-C30 cycloalkyl, C3-C30 cycloalkenyl, C3-C30 cycloynyl, C3-C30 heterocycloalkyl, C3-C30 heterocycloalkenyl, or C3-C30 heterocycloynyl.

[0142] In the following text, the work function, HOMO level, or LUMO level are referred to as absolute values ​​relative to the vacuum level. Furthermore, when the work function, HOMO level, or LUMO level is referred to as deep, high, or large, it may have a large absolute value based on the vacuum level "0 eV," while when the work function, HOMO level, or LUMO level is referred to as shallow, low, or small, it may have a small absolute value based on the vacuum level "0 eV."

[0143] In the following text, band gap refers to the absolute value of the difference between the HOMO and LUMO energy levels. A wide band gap means that the absolute value of the difference between the HOMO and LUMO energy levels is large.

[0144] In the following text, the term "metal" includes both metals and semi-metals.

[0145] The following describes compounds according to some exemplary embodiments. In some exemplary embodiments, the composition may include the compounds.

[0146] The compounds according to some exemplary embodiments may be light-absorbing materials, and may be infrared light-absorbing materials configured to absorb light in the infrared wavelength spectrum. The compounds according to some exemplary embodiments may be light-absorbing semiconductors or infrared photoelectric conversion materials configured to absorb light in the infrared wavelength spectrum and convert the absorbed light into electrical signals.

[0147] The compounds described in some examples may be represented by chemical formula 1.

[0148] [Chemical Formula 1]

[0149]

[0150] In chemical formula 1,

[0151] X is O, S, Se, Te, SO, SO2, NR a CR b R c or SiR d R e ,

[0152] Y 1 and Y 2 Independent for CR f Or N,

[0153] Z 1 or Z 2 One of them is S and Z 1 or Z 2 The other is O, S, Se, Te, or NR. g ,

[0154] Q represents a substituted or unsubstituted C3-C30 quinone ring.

[0155] R 1 and R 2 Independently, it is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof.

[0156] R a -R g Independently, it is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, a cyano group, or a combination thereof.

[0157] R 1 and R 2 They exist independently (e.g., not connected to each other to provide a loop) or are connected to each other to provide (e.g., form) a loop.

[0158] R b and R c They exist independently or are connected to each other to form a ring.

[0159] R d and R e They exist independently or are connected to each other to provide a ring, and

[0160] Adjacent R f They exist independently or are connected to each other to provide a ring.

[0161] The compound represented by Formula 1 has heterocyclic groups containing chalcogenides and malononitrile at both ends, and therefore can form a very large dipole moment due to its strong electron-donating and electron-accepting properties. Furthermore, the length and planarity of the molecule can be effectively tuned by the two quinone rings between the two ends. In this document, the quinone rings are cyclic structures derived from the oxidation of aromatic rings, heteroaromatic rings, or their fused rings. Therefore, the compound can be efficiently configured to absorb light in the infrared wavelength spectrum and exhibit satisfactory photoelectric conversion properties.

[0162] For example, X can be O, S, Se, Te, or NR. a For example, O, S, Se, or Te, for example, S, Se, or Te, for example, S or Se, for example, S.

[0163] For example, Y 1 and Y 2Each can be independently classified as CR f For example, CH.

[0164] For example, Z 1 or Z 2 One of them can be S and Z 1 or Z 2 The other can be S, Se, or Te, for example Z. 1 or Z 2 One of them can be S and Z 1 or Z 2 The other can be S or Se, and for example Z. 1 and Z 2 Each can be independently represented as S.

[0165] For example, X, Z 1 and Z 2 Each can be independently S or Se, and can be, for example, S.

[0166] For example, Q may comprise at least one substituted or unsubstituted 5-membered quinone ring, at least one substituted or unsubstituted 6-membered quinone ring, or a fused ring thereof. For example, Q may be one, two, or three substituted or unsubstituted 5-membered quinone rings; a fused ring of one, two, or three substituted or unsubstituted 5-membered quinone rings; a fused ring of one, two, or three substituted or unsubstituted 6-membered quinone rings; a fused ring of one or two substituted or unsubstituted 5-membered quinone rings and one or two substituted or unsubstituted 6-membered quinone rings; or combinations thereof. However, when Q is a substituted or unsubstituted 5-membered quinone ring, Q may differ from adjacent rings (including X, Y). 1 and Y 2 (a 5-membered quinone ring).

[0167] For example, Q can be one of the groups listed in Group 1, but is not limited to this.

[0168] [Group 1]

[0169]

[0170] In group 1,

[0171] W 1 It may be different from X, and may be S, Se, or Te.

[0172] W 2 -W 13 It can be independently S, Se, or Te.

[0173] R 3 -R 46It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, a cyano group, or a combination thereof.

[0174] R 3 -R 46 It can exist independently or R 3 -R 46 Two adjacent elements can be connected to each other to provide a loop, and

[0175] *This can be a connection point with chemical formula 1.

[0176] For example, when X is S, W 1 It can be Se or Te.

[0177] For example, when X is Se, W 1 It can be S or Te.

[0178] For example, W 2 -W 11 It can be independently S or Se, and for example, it can be independently S.

[0179] For example, a compound represented by chemical formula 1 may be represented by one of chemical formulas 1A to 1I, but is not limited thereto.

[0180] [Chemical Formula 1A]

[0181]

[0182] [Chemical Formula 1B]

[0183]

[0184] [Chemical Formula 1C]

[0185]

[0186] [Chemical Formula 1D]

[0187]

[0188] [Chemical Formula 1E]

[0189]

[0190] [Chemical Formula 1F]

[0191]

[0192] [Chemical Formula 1G]

[0193]

[0194] [Chemical formula 1H]

[0195]

[0196] [Chemical Formula 1I]

[0197]

[0198] In chemical formulas 1A to 1I, X and W 2 -W 9 W 12 W 13 R 1 -R 6 R 9 -R 20 R 25 -R 30 R 43 -R 46 and R f Same as described above.

[0199] For example, a compound represented by chemical formula 1 may be represented by one of chemical formulas 1A-1 to 1I-1, but is not limited thereto.

[0200] [Chemical Formula 1A-1]

[0201]

[0202] [Chemical Formula 1B-1]

[0203]

[0204] [Chemical formula 1C-1]

[0205]

[0206] [Chemical formula 1D-1]

[0207]

[0208] [Chemical Formula 1E-1]

[0209]

[0210] [Chemical formula 1F-1]

[0211]

[0212] [Chemical Formula 1G-1]

[0213]

[0214] [Chemical formula 1H-1]

[0215]

[0216] [Chemical formula 1I-1]

[0217]

[0218] In chemical formulas 1A-1 to 1I-1, R 1 -R 6 R 9 -R 20 R 25 -R 30 R 43 -R 46 and R f Same as described above.

[0219] The main absorption spectrum of the compound can be in the infrared absorption wavelength spectrum, wherein the infrared absorption wavelength spectrum can be, for example, greater than or equal to about 750 nm, greater than or equal to about 780 nm, greater than or equal to about 790 nm, greater than or equal to about 800 nm, greater than or equal to about 810 nm, greater than or equal to about 820 nm, greater than or equal to about 830 nm, greater than or equal to about 850 nm, greater than or equal to about 870 nm, greater than or equal to about 890 nm, greater than or equal to about 900 nm, greater than or equal to about 920 nm, greater than or equal to about 940 nm, greater than or equal to about 960 nm, greater than or equal to about 980 nm, greater than or equal to about 1000 nm, greater than or equal to about 1050 nm, or greater than or equal to about 1100 nm. For example, the peak absorption wavelength of the compound may be in the following wavelength spectrum: about 750 nm to about 3000 nm, within the range of about 800 nm to about 3000 nm, for example, about 750 nm to about 2500 nm, for example, about 780 nm to about 2200 nm, for example, about 790 nm to about 2100 nm, for example, about 800 nm to about 2000 nm, for example, about 810 nm to about 2000 nm, for example, about 820 nm to about 2000 nm, for example, about 830 nm to about 2000 nm, for example, about 8 50nm to approximately 2000nm, for example, approximately 870nm to approximately 2000nm, for example, approximately 890nm to approximately 2000nm, for example, approximately 900nm to approximately 2000nm, for example, approximately 920nm to approximately 2000nm, for example, approximately 940nm to approximately 2000nm, for example, approximately 960nm to approximately 2000nm, for example, approximately 980nm to approximately 2000nm, for example, approximately 1000nm to approximately 2000nm, for example, approximately 1050nm to approximately 2000nm, or for example, approximately 1100nm to approximately 2000nm.

[0220] The compound exhibits good photoelectric conversion properties and is therefore effectively used as a photoelectric conversion material for infrared sensors. For example, the band gap of the compound can be, for example, about 0.5 eV to about 1.5 eV, and within the range of about 0.6 eV to about 1.4 eV, about 0.7 eV to about 1.3 eV, or about 0.8 eV to about 1.2 eV. For example, the HOMO level of the compound can be, for example, about 4.0 eV to about 5.5 eV, and within the range of about 4.2 eV to about 5.3 eV, about 4.4 eV to about 5.1 eV, or about 4.5 eV to about 5.0 eV.

[0221] On the other hand, the compound exhibits good heat resistance, thus preventing or reducing thermal decomposition during deposition, and therefore can be deposited repeatedly. The compound can be deposited thermally or under vacuum, and can be deposited, for example, by sublimation. For example, deposition by sublimation can be confirmed by thermogravimetric analysis (TGA), and at a pressure less than or equal to about 10 Pa, the temperature at which 10% weight loss relative to the initial weight is less than or equal to about 450°C, and the temperature at which 50% weight loss relative to the initial weight is less than or equal to about 500°C. For example, at a pressure less than or equal to about 10 Pa, the temperature at which 10% weight loss relative to the initial weight of the compound is, for example, about 230°C to about 450°C, and the temperature at which 50% weight loss relative to the initial weight is about 300°C to about 500°C.

[0222] The compound can be deposited to prepare a film. Therefore, in some exemplary embodiments, a film comprising the aforementioned compound can be provided. The film may have similar or identical properties to those described herein with respect to the compound. For example, a film comprising the compound may have a peak absorption wavelength in a wavelength spectrum of 800 nm to about 3000 nm. The film may have dimensions in the in-plane direction (e.g., the xy direction) (i.e., the width and length of the film) that are much larger than its dimensions in the depth direction (e.g., the z-direction) (i.e., the thickness of the film). For example, the thickness of the film may be about 1 nm to about 100 μm, about 1 nm to about 80 μm, about 1 nm to about 50 μm, about 1 nm to about 40 μm, about 1 nm to about 30 μm, about 1 nm to about 20 μm, or about 1 nm to about 10 μm.

[0223] The membrane can be applied to a variety of fields that require light absorption properties in the infrared wavelength spectrum, such as infrared absorbing / blocking membranes.

[0224] The compound possesses both infrared wavelength absorption properties and photoelectric properties, and can be effectively used as a photoelectric conversion material for infrared sensors.

[0225] The infrared sensor can be configured to sense at least some light (e.g., incident light) in an infrared wavelength spectrum, for example, selectively absorbing at least a portion of the infrared wavelength spectrum of the incident light, and thus converting it (e.g., photoelectric conversion of the selectively absorbed incident light) into an electrical signal. The infrared sensor can exhibit an absorption spectrum having peak absorption wavelengths in the infrared wavelength spectrum, wherein the infrared wavelength spectrum is the same as described above. Each infrared sensor can independently include a photosensitive device such as a photodiode or a photoelectric conversion device, and can be, for example, a photoelectric conversion device.

[0226] Figure 1 A cross-sectional view showing an example of an infrared sensor according to some exemplary embodiments.

[0227] refer to Figure 1 According to some exemplary embodiments, the infrared sensor 100 may be an infrared photoelectric conversion device, and includes a first electrode 10 and a second electrode 20 facing each other, and an organic layer 30 between the first electrode 10 and the second electrode 20. The organic layer 30 may include the aforementioned compound.

[0228] A substrate (not shown) may be disposed on the first electrode 10 or the second electrode 20, and may be in direct contact with at least one of the first electrode 10 or the second electrode 20. The substrate may be made of, for example, an inorganic material such as glass, an organic material such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyethersulfone, or combinations thereof, or a silicon wafer. The substrate may be a semiconductor substrate. The substrate may be omitted.

[0229] One of the first electrode 10 or the second electrode 20 is an anode and the other is a cathode. For example, the first electrode 10 may be an anode and the second electrode 20 may be a cathode.

[0230] At least one of the first electrode 10 or the second electrode 20 may be a (semi) light transmission electrode, and the (semi) light transmission electrode may be made of: a conductive oxide such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO2), aluminum tin oxide (AlTO), and fluorine-doped tin oxide (FTO), or a thin single layer or multiple layers of a metal film, including silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), magnesium-silver (Mg-Ag), magnesium-aluminum (Mg-Al), or combinations thereof.

[0231] For example, both the first electrode 10 and the second electrode 20 can be (semi)light-transmitting electrodes. For example, the second electrode 20 can be a light-receiving electrode disposed on the side receiving light (e.g., incident light).

[0232] As an example, one of the first electrode 10 or the second electrode 20 may be a (semi-)transmissive electrode and the other may be a reflective electrode. The reflective electrode may include a reflective layer comprising an optically opaque material. The reflective layer may have a light transmittance of less than about 10%, less than or equal to about 8%, less than or equal to about 7%, less than or equal to about 5%, less than or equal to about 3%, or less than or equal to about 1%. The light transmittance of the reflective layer may be equal to or greater than 0%, equal to or greater than about 0.1%, equal to or greater than about 0.5%, equal to or greater than about 1%, or equal to or greater than about 5%. The reflective layer may have a reflectance of greater than or equal to about 10%, greater than or equal to about 20%, greater than or equal to about 30%, greater than or equal to about 50%, or greater than or equal to about 70%. The reflectance of the reflective layer may be equal to or less than 100%, equal to or less than about 99%, equal to or less than about 95%, equal to or less than about 90%, or equal to or less than about 80%. The optically opaque material may include metals, metal nitrides, or combinations thereof, such as silver (Ag), copper (Cu), aluminum (Al), gold (Au), titanium (Ti), chromium (Cr), nickel (Ni), their alloys, their nitrides (e.g., TiN), or combinations thereof, but is not limited thereto. The reflective layer may be one layer or two or more layers.

[0233] The organic layer 30 includes an infrared photoelectric conversion layer 31 and auxiliary layers 32 and 33 disposed on and / or below the infrared photoelectric conversion layer 31.

[0234] The infrared photoelectric conversion layer 31 is configured to absorb light in the infrared wavelength spectrum (e.g., incident light) and photoelectrically convert the absorbed light into an electrical signal, and may include the aforementioned compound. Such absorption and photoelectric conversion of light in the infrared wavelength spectrum may be referred to herein as “sensing” and / or “detecting” the light in the infrared wavelength spectrum. The infrared photoelectric conversion layer 31 may include p-type and n-type semiconductors forming a pn junction, and generates excitons by receiving light from the outside (e.g., the surrounding environment outside the infrared sensor 100), and then separates the generated excitons into holes and electrons.

[0235] The p-type semiconductor and / or the n-type semiconductor may be light-absorbing materials configured to absorb light in at least a portion of the wavelength spectrum. For example, the aforementioned compound may be used (e.g., included) in the infrared photoelectric conversion layer 31 as a p-type semiconductor or an n-type semiconductor in the infrared photoelectric conversion layer 31, and the infrared photoelectric conversion layer 31 may further include a pairing material (also referred to herein as a pair material) forming a pn junction with the compound. The pair material may be, for example, a light-absorbing material or a non-light-absorbing material. For example, the aforementioned compound may be used as a p-type semiconductor, and the infrared photoelectric conversion layer 31 may further include an n-type semiconductor forming a pn junction with the compound. The n-type semiconductor may include a fullerene or a fullerene derivative. For example, the aforementioned compound may be used as an n-type semiconductor, and the infrared photoelectric conversion layer 31 may further include a p-type semiconductor forming a pn junction with the compound.

[0236] For example, the infrared photoelectric conversion layer 31 may include an intrinsic layer (I layer) 31i in which a p-type semiconductor and an n-type semiconductor are co-deposited, wherein one of the p-type semiconductor or the n-type semiconductor includes the aforementioned compound represented by chemical formula 1, and the other of the p-type semiconductor or the n-type semiconductor includes the aforementioned pair of materials. The intrinsic layer 31i may be a blend layer in which the p-type semiconductor and the n-type semiconductor are blended in the form of a bulk heterojunction.

[0237] For example, a volume ratio (thickness ratio) of about 1:9 to about 9:1, or within the range of about 2:8 to about 8:2, about 3:7 to about 7:3, about 4:6 to about 6:4, or about 5:5, may include the p-type semiconductor and the n-type semiconductor (e.g., the aforementioned compound and the aforementioned material) in the intrinsic layer.

[0238] For example, the p-type semiconductor (which may include one of the compound or the paired materials) in intrinsic layer 31i may be included in fewer quantities than the n-type semiconductor (which may include the other of the compound or the paired materials). For example, the composition ratio (volume ratio or thickness ratio) of the p-type semiconductor to the n-type semiconductor in intrinsic layer 31i may be about 0.10 to about 0.90. The composition ratio of the p-type semiconductor to the n-type semiconductor may be, for example, about 0.10 to about 0.80, about 0.10 to about 0.70, about 0.10 to about 0.50, or about 0.10 to about 0.30.

[0239] In addition to the intrinsic layer 31i, the infrared photoelectric conversion layer 31 may further include a p-type layer 31p and / or an n-type layer 31n. However, exemplary embodiments are not limited thereto. For example, in some exemplary embodiments, the p-type layer 31p and the n-type layer 31n are absent, such that the intrinsic layer 31i constitutes the entire infrared photoelectric conversion layer 31. In some exemplary embodiments, the infrared photoelectric conversion layer 31 includes a single layer (e.g., a single layer comprising a material or a combination of materials) and does not include any additional layers. The p-type layer 31p may include the aforementioned p-type semiconductor (which may include one of the compounds or the paired materials), and the n-type layer 31n may include the aforementioned n-type semiconductor (which may include the other of the compounds or the paired materials). For example, it (e.g., the infrared photoelectric conversion layer 31) may include various combinations such as p-type layer / I-layer, I-layer / n-type layer, and p-type layer / I-layer / n-type layer.

[0240] The main absorption spectrum of the compound may be in an infrared absorption wavelength spectrum, wherein the infrared absorption wavelength spectrum may be, for example, greater than or equal to about 800 nm, greater than or equal to about 810 nm, greater than or equal to about 820 nm, greater than or equal to about 830 nm, greater than or equal to about 850 nm, greater than or equal to about 870 nm, greater than or equal to about 890 nm, greater than or equal to about 900 nm, greater than or equal to about 920 nm, greater than or equal to about 940 nm, greater than or equal to about 960 nm, greater than or equal to about 980 nm, greater than or equal to about 1000 nm, greater than or equal to about 1050 nm, or greater than or equal to about 1100 nm. For example, the infrared photoelectric conversion layer 31, and therefore the infrared sensor 100, may have peak absorption wavelengths belonging to the following wavelength spectrum: about 800 nm to about 3000 nm, within the range of, for example, about 810 nm to about 2500 nm, for example, about 820 nm to about 2200 nm, for example, about 830 nm to about 2100 nm, for example, about 840 nm to about 2000 nm, for example, about 850 nm to about 2000 nm, for example, about 860 nm to about 2000 nm, for example, about 870 nm to about 2000 nm, for example, about 880nm to approximately 2000nm, for example, approximately 890nm to approximately 2000nm, for example, approximately 900nm to approximately 2000nm, for example, approximately 920nm to approximately 2000nm, for example, approximately 940nm to approximately 2000nm, for example, approximately 960nm to approximately 2000nm, for example, approximately 980nm to approximately 2000nm, for example, approximately 990nm to approximately 2000nm, for example, approximately 1000nm to approximately 2000nm, for example, approximately 1050nm to approximately 2000nm, or for example, approximately 1100nm to approximately 2000nm.

[0241] The infrared photoelectric conversion layer 31 may have the following thicknesses: approximately 30 nm to approximately 500 nm, approximately 50 nm to approximately 400 nm within the above range, approximately 80 nm to approximately 300 nm, approximately 100 nm to approximately 200 nm, or approximately 140 nm to approximately 160 nm.

[0242] The organic layer 30 may further include auxiliary layers 32 and 33. Auxiliary layers 32 and 33 may be located between the first electrode 10 and the infrared photoelectric conversion layer 31, and / or between the second electrode 20 and the infrared photoelectric conversion layer 31, respectively. In some exemplary embodiments, one or both of auxiliary layers 32 and / or 33 may be omitted. Therefore, it will be understood that the infrared sensor 100 may include auxiliary layers (e.g., 32 and / or 33) located at least one of the following: between the first electrode 10 and the infrared photoelectric conversion layer 31, or between the second electrode 20 and the infrared photoelectric conversion layer 31.

[0243] For example, auxiliary layers 32 and 33 may be charge-assisted layers used to improve the transfer of holes and electrons separated from the infrared photoelectric conversion layer 31 to improve the efficiency of the infrared sensor 100. Auxiliary layers 32 and 33 may include at least one selected from: a hole injection layer (HIL) that promotes hole injection, a hole transport layer (HTL) that promotes hole transport, an electron blocking layer (EBL) that blocks electron movement, an electron injection layer (EIL) that promotes electron injection, an electron transport layer (ETL) that promotes electron transport, and a hole blocking layer (HBL) that blocks hole movement.

[0244] As an example, auxiliary layers 32 and 33 may be light-absorbing auxiliary layers and may be disposed on and / or below the infrared photoelectric conversion layer 31 to increase the amount of light absorbed by the infrared photoelectric conversion layer 31 and thereby improve the light absorption properties. For example, one of auxiliary layers 32 or 33 may include the aforementioned compounds. For example, one of auxiliary layers 32 or 33 may include fullerenes or fullerene derivatives.

[0245] The auxiliary layers 32 and 33 may include, for example, organic materials, inorganic materials, or organic-inorganic materials.

[0246] For example, at least one of the auxiliary layers 32 or 33 may include a low molecular weight compound, such as the aforementioned compound.

[0247] For example, at least one of the auxiliary layers 32 or 33 may include a low molecular weight compound, such as a compound containing carbazole.

[0248] For example, at least one of the auxiliary layers 32 or 33 may include a polymer.

[0249] For example, one of the auxiliary layers 32 or 33 may include inorganic materials, such as lanthanides such as ytterbium (Yb); calcium (Ca); potassium (K); barium (Ba); magnesium (Mg); lithium fluoride (LiF); or alloys thereof.

[0250] For example, at least one of the auxiliary layers 32 or 33 may include a fullerene or a fullerene derivative.

[0251] For example, one of the auxiliary layers 32 or 33 may include an inorganic material and may include metal oxides such as molybdenum oxide, tungsten oxide, or nickel oxide.

[0252] For example, at least one of the auxiliary layers 32 or 33 may include the aforementioned compound represented by chemical formula 1.

[0253] In some embodiments, the infrared sensor 100 may include at least one auxiliary layer 32 or 33 and an infrared photoelectric conversion layer 31, wherein at least one of the auxiliary layers 32 or 33 or at least one of the infrared photoelectric conversion layers 31 includes the aforementioned compound represented by chemical formula 1. For example, in some embodiments, at least one of the auxiliary layers 32 or 33 may include the aforementioned compound represented by chemical formula 1, while the infrared photoelectric conversion layer 31 may not include the aforementioned compound represented by chemical formula 1.

[0254] The auxiliary layers 32 and 33 may each have an independent thickness of approximately 1 nm to approximately 200 nm, approximately 5 nm to approximately 200 nm within the range, approximately 5 nm to approximately 180 nm, or approximately 5 nm to approximately 150 nm.

[0255] At least one of the auxiliary layers 32 or 33 may be omitted.

[0256] The infrared sensor 100 may further include an anti-reflective layer (not shown) on the first electrode 10 or below the second electrode 20. The anti-reflective layer may be disposed on the side where light is incident to reduce the reflectivity of the incident light, thereby further improving light absorption. For example, when light is incident on the first electrode 10, the anti-reflective layer may be below the first electrode 10, and when light is incident on the second electrode 20, the anti-reflective layer may be disposed on the second electrode 20.

[0257] The antireflective layer may include, for example, a material having a refractive index of about 1.6 to about 2.5, and may include at least one of a metal oxide, metal sulfide, or organic material having a refractive index within the said range. The antireflective layer may include, for example, metal oxides such as oxides containing aluminum, oxides containing molybdenum, oxides containing tungsten, oxides containing vanadium, oxides containing rhenium, oxides containing niobium, oxides containing tantalum, oxides containing titanium, oxides containing nickel, oxides containing copper, oxides containing cobalt, oxides containing manganese, oxides containing chromium, oxides containing tellurium, or combinations thereof; metal sulfides such as zinc sulfide; or organic materials such as amine derivatives, but are not limited thereto.

[0258] The infrared sensor 100 may further include an encapsulation film (not shown) below the first electrode 10 or on the second electrode 20 (e.g., in direct contact with at least one of the first electrode 10 or the second electrode 20).

[0259] The infrared sensor 100 may further include an optical auxiliary layer (not shown) below the first electrode 10 or on the second electrode 20 (e.g., in direct contact with at least one of the first electrode 10 or the second electrode 20). The optical auxiliary layer may be configured to selectively transmit light in a specific (or, alternatively, predetermined) wavelength spectrum within the incident light, and may be configured to reflect and / or absorb light in a wavelength spectrum different from the specific (or, alternatively, predetermined) wavelength spectrum. That is, the optical auxiliary layer may be a selectively transmissive layer, for example, a semi-transmissive layer.

[0260] The optical auxiliary layer may include, for example, a first optical auxiliary layer and a second optical auxiliary layer with different refractive indices. The first optical auxiliary layer may be, for example, a high refractive index layer, and the second optical auxiliary layer may be, for example, a low refractive index layer. The refractive index of the high refractive index layer (e.g., in the range of about 800 nm to about 1200 nm) may be, for example, greater than or equal to about 1.55, or about 1.55 to about 1.90, and the refractive index of the low refractive index layer (e.g., in the range of about 800 nm to about 1200 nm) may be, for example, less than about 1.55, or greater than or equal to about 1.20 and less than about 1.55. For example, the first optical auxiliary layer may be alumina, an organic buffer material, an inorganic buffer material, or a combination thereof, and the second optical auxiliary layer may be silicon oxide, silicon nitride, silicon oxynitride, or a combination thereof, but is limited thereto.

[0261] In the infrared sensor 100, when light is incident from one side of the first electrode 10 or the second electrode 20 and absorbed by the infrared photoelectric conversion layer 31 in the infrared wavelength spectrum, excitons are generated therein. In the infrared photoelectric conversion layer 31, the generated excitons separate into holes and electrons. The separated holes can move toward the anode, which is one of the first electrode 10 or the second electrode 20, and the separated electrons can move toward the cathode, which is the other of the first electrode 10 or the second electrode 20, thus generating an electrical signal.

[0262] For example, when the infrared sensor 100 includes a reflective electrode and a (semi)transmitting electrode as a first electrode 10 and a second electrode 20, a microcavity structure can be formed. Due to the microcavity structure, incident light can be repeatedly reflected between the reflective electrode and the (semi)transmitting electrode, which are separated by a specific (or, alternatively, predetermined) optical path length to enhance light having a specific (or, alternatively, predetermined) wavelength spectrum. For example, light having a specific (or, alternatively, predetermined) wavelength spectrum in the incident light can be adjusted by repeated reflection between the reflective electrode and the (semi)transmitting electrode, and in the adjusted light, light of a wavelength spectrum corresponding to the resonant wavelength of the microcavity can be enhanced to exhibit photoelectric conversion characteristics amplified in a narrow wavelength spectrum.

[0263] Due to this microcavity structure, in addition to the aforementioned main absorption spectrum, the absorption spectrum of the infrared photoelectric conversion layer 31 may further include a secondary absorption spectrum. The secondary absorption spectrum may be located in a wavelength spectrum longer than the main absorption spectrum, and the peak wavelength of the secondary absorption spectrum may, for example, be greater than or equal to about 1000 nm, greater than or equal to about 1050 nm, greater than or equal to about 1100 nm, greater than or equal to about 1150 nm, greater than or equal to about 1200 nm, for example, about 1000 nm to about 3000 nm, about 1050 nm to about 3000 nm, about 1100 nm to about 3000 nm, about 1150 nm to about 3000 nm, or about 1200 nm to about 3000 nm.

[0264] The infrared sensor 100 can be applied in various fields to sense light in the infrared wavelength spectrum. For example, it can be used in image sensors to improve sensitivity in low-light environments, in sensors to enhance the detection capability of 3D images by broadening the dynamic range for detailed black and white contrast, in security sensors, in vehicle sensors, and in biometric sensors. The biometric sensor can be, for example, an iris sensor; a distance sensor; a fingerprint sensor; a biosignal sensor such as a PPG sensor; or a biological imaging sensor such as a vascular imaging sensor, but is not limited thereto. The infrared sensor can be applied to, for example, a CMOS infrared sensor or a CMOS image sensor.

[0265] The CMOS infrared sensor may include a plurality of pixels, and at least some of the plurality of pixels may include the aforementioned infrared sensor 100. The CMOS infrared sensor may include a plurality of infrared sensors 100 arranged in an array along rows and / or columns on a semiconductor substrate, or a single infrared sensor 100. Therefore, the image sensor may include… Figure 1 The infrared sensor 100 may further include a semiconductor substrate, wherein the infrared sensor 100 is on the semiconductor substrate (e.g., the first electrode 10 or the second electrode 20 may be in direct contact with the semiconductor substrate).

[0266] Figure 2 A cross-sectional view showing an example of a CMOS infrared sensor according to some exemplary embodiments.

[0267] According to some exemplary embodiments, a CMOS infrared sensor 300 includes a semiconductor substrate 40, an insulating layer 80, and an infrared sensor 100.

[0268] The semiconductor substrate 40 may be a silicon substrate and integrates a transfer transistor (not shown) and a charge memory 55. The charge memory 55 may be integrated in each pixel. The charge memory 55 is electrically connected to the infrared sensor 100, and the information in the charge memory 55 can be transmitted through the transfer transistor.

[0269] Metal lines (not shown) and pads (not shown) are formed on the semiconductor substrate 40. To reduce signal delay, the metal lines and pads may be made of metals with low resistivity, such as aluminum (Al), copper (Cu), silver (Ag), and alloys thereof, but are not limited thereto. However, the structure is not limited to this, and the metal lines and pads may be disposed under the semiconductor substrate 40.

[0270] An insulating layer 80 is formed on the metal wire and the pad. The insulating layer 80 may be made of inorganic insulating materials such as silicon oxide and / or silicon nitride, or low dielectric constant (low K) materials such as SiC, SiCOH, SiCO, and SiOF. The insulating layer 80 has trenches 85 that expose the charge storage device 55. The trenches may be filled with filler.

[0271] The aforementioned infrared sensor 100 is formed on the insulating layer 80. The infrared sensor 100 may include the first electrode 10, the second electrode 20, the infrared photoelectric conversion layer 31, and optionally auxiliary layers 32 and 33 as described above.

[0272] Both the first electrode 10 and the second electrode 20 can be transparent electrodes, and the descriptions of the first electrode 10, the second electrode 20, the infrared photoelectric conversion layer 31, and the auxiliary layers 32 and 33 are the same as those described above. Light incident from the second electrode 20 side in the infrared wavelength spectrum can be effectively absorbed by the infrared photoelectric conversion layer 31 for photoelectric conversion.

[0273] A focusing lens (not shown) may be further formed on the infrared sensor 100. The focusing lens can control the direction of the incident light and focus the light into a region. The focusing lens may have, for example, a cylindrical or hemispherical shape, but is not limited thereto.

[0274] Infrared sensor 100 or CMOS infrared sensor 300 may be included in a combined sensor, which includes multiple sensors with different functions.

[0275] At least one of the multiple sensors with different functions may be a biometric sensor. The biometric sensor may be, for example, an iris sensor, a depth sensor, a fingerprint sensor, or a vascular distribution sensor, but is not limited thereto. For example, one of the multiple sensors with different functions may be an iris sensor and another may be a depth sensor.

[0276] For example, multiple sensors with different functions may include a first infrared sensor configured to sense light in the infrared region having a first wavelength (λ1) and a second infrared sensor configured to sense infrared light having a second wavelength (λ2) in the infrared wavelength spectrum.

[0277] Within the infrared wavelength spectrum, the first wavelength (λ1) and the second wavelength (λ2) may be different from each other. For example, the difference between the first wavelength (λ1) and the second wavelength (λ2) may be greater than or equal to about 30 nm, greater than or equal to about 50 nm, greater than or equal to about 70 nm, greater than or equal to about 80 nm, or greater than or equal to about 90 nm. The difference may be equal to or less than about 500 nm, equal to or less than about 400 nm, equal to or less than about 300 nm, equal to or less than about 200 nm, equal to or less than about 150 nm, equal to or less than about 100 nm, or equal to or less than about 95 nm.

[0278] For example, one of the first wavelength (λ1) or the second wavelength (λ2) may be in the wavelength spectrum of about 750 nm to about 1000 nm, and the other of the first wavelength (λ1) or the second wavelength (λ2) may be in the wavelength spectrum of about 800 nm to about 1500 nm.

[0279] Figure 3 A cross-sectional view is shown to illustrate one example of a combined sensor implemented according to some exemplary embodiments.

[0280] According to some exemplary embodiments, the combined sensor 400 includes: a filter 250; an infrared sensor 100; an insulating layer 80; and a semiconductor substrate 40 in which a photodiode 180 and a charge memory 55 are integrated. The infrared sensor 100 and the photodiode 180 are stacked along the depth direction (e.g., the z-direction) of the semiconductor substrate 40. To reiterate, the infrared sensor 100 and the photodiode 180 can be understood as being stacked together in a depth direction (e.g., the z-direction) perpendicular to the plane in which the infrared sensor 100 extends and / or the in-plane directions of the infrared sensor 100 (e.g., the x and y directions), and / or perpendicular to the upper surface of the semiconductor substrate 40 opposite to the surfaces 100s, 180s of the infrared sensor 100 and the photodiode 180, and further perpendicular to the opposite surface 31s of at least the infrared photoelectric conversion layer 31 of the infrared sensor 100, the opposite surface of the first electrode 10, and the opposite surface of the second electrode 20.

[0281] The filter 250 may be disposed on the front side (front side) of the combined sensor 400 and may be configured to selectively transmit light in the infrared wavelength spectrum including the first wavelength (λ1) and light in the infrared wavelength spectrum including the second wavelength (λ2), and may be configured to block and / or absorb other light. Here, the other light may also include ultraviolet and visible light.

[0282] Infrared sensor 100 may be a first infrared sensor, and is described in the same detail as above.

[0283] The photodiode 180 may be a second infrared sensor and may be integrated in the semiconductor substrate 40. The semiconductor substrate 40 may be, for example, a silicon substrate, and the photodiode 180, charge memory 55, and transfer transistor (not shown) are integrated therein.

[0284] Infrared sensor 100 can be configured to detect (e.g., absorb and / or photoelectric convert) incident light comprising a first wavelength (λ1) of the infrared wavelength spectrum in a first wavelength spectrum of the infrared wavelength spectrum. Photodiode 180 can be configured to detect (e.g., absorb and / or photoelectric convert) incident light comprising a second wavelength (λ2) of the infrared wavelength spectrum in a second wavelength spectrum of the infrared wavelength spectrum. The second wavelength spectrum can be a wavelength spectrum shorter or longer than the first wavelength spectrum. To reiterate, the wavelength in the second wavelength spectrum (e.g., the second wavelength (λ2) of the infrared wavelength spectrum) can be a wavelength shorter or longer than the wavelength in the first wavelength spectrum (e.g., the first wavelength (λ1) of the infrared wavelength spectrum). The first and second wavelength spectra can partially overlap or can be completely non-overlapping. In some exemplary embodiments, the difference between the closest wavelengths of the non-overlapping first and second wavelength spectra can be greater than or equal to about 30 nm, greater than or equal to about 50 nm within the range, greater than or equal to about 70 nm, greater than or equal to about 80 nm, or greater than or equal to about 90 nm. The difference may be equal to or less than about 500 nm, equal to or less than about 400 nm, equal to or less than about 300 nm, equal to or less than about 200 nm, equal to or less than about 150 nm, equal to or less than about 100 nm, or equal to or less than about 95 nm.

[0285] The light entering the photodiode 180 is light that has already passed through the filter 250 and the infrared sensor 100, and may be light in a specific (or, alternatively predetermined) region of the infrared wavelength spectrum including the second wavelength (λ2). Infrared light in the specific (or, alternatively predetermined) region including the first wavelength (λ1) may be substantially entirely absorbed in the infrared photoelectric conversion layer 31 of the infrared sensor 100 and therefore does not reach the photodiode 180. Therefore, a separate filter (filter) for wavelength selectivity of the light entering the photodiode 180 is not required. However, in cases where light in the specific (or, alternatively predetermined) region of the infrared wavelength spectrum including the first wavelength (λ1) is not entirely absorbed in the infrared photoelectric conversion layer 31, a separate color filter (not shown) may be provided between the infrared sensor 100 and the photodiode 180. The first wavelength (λ1) may be the peak absorption wavelength of the first infrared sensor (e.g., infrared sensor 100) (e.g., presented by it), and the second wavelength (λ2) may be the peak absorption wavelength of the second infrared sensor (e.g., photodiode).

[0286] According to some exemplary embodiments, the combined sensor 400 can not only operate as a combined sensor by including two infrared sensors that perform two different functions, but also greatly improve sensitivity by stacking the two sensors that perform different functions in each pixel to double the number of active pixels of each infrared sensor while maintaining the same size.

[0287] Figure 4 A cross-sectional view is shown to illustrate another example of a combined sensor implemented according to some exemplary embodiments.

[0288] refer to Figure 4 According to some example embodiments, the combined sensor 400 includes an infrared sensor 100, a visible light sensor 200, and a filter 250.

[0289] As described above, the infrared sensor 100 includes a first electrode 10, a second electrode 20, an infrared photoelectric conversion layer 31, and optionally auxiliary layers 32 and 33. The details are the same as described above.

[0290] Visible light sensor 200 is configured to sense (e.g., detect) at least a portion of incident light in the visible light wavelength spectrum and may be a photodiode integrated in semiconductor substrate 40. Visible light sensor 200 may be integrated in semiconductor substrate 40 and may include a blue sensor 200a configured to sense light in the blue wavelength spectrum, a green sensor 200b configured to sense light in the green wavelength spectrum, and a red sensor 200c configured to sense light in the red wavelength spectrum. Figure 4 As shown, the blue sensor 200a, green sensor 200b, and red sensor 200c can be photodiodes integrated into the semiconductor substrate 40 such that they are located within a volume space defined by the outer surface of the semiconductor substrate 40 and can be partially or completely enclosed within the semiconductor substrate 40. The blue sensor 200a can be integrated into a blue pixel, the green sensor 200b into a green pixel, and the red sensor 200c into a red pixel.

[0291] The semiconductor substrate 40 may be, for example, a silicon substrate, and a visible light sensor 200, a charge memory 55, and a transfer transistor (not shown) are integrated therein. The visible light sensor 200 is configured to sense light in the visible light wavelength spectrum that has passed through the filter 250, the infrared sensor 100, and the color filter layer 70, and the sensed information can be transmitted via the transfer transistor. The charge memory 55 is electrically connected to the infrared sensor 100.

[0292] Metal lines (not shown) and pads (not shown) are formed on the semiconductor substrate 40. To reduce signal delay, the metal lines and pads may be made of metals with low resistivity, such as aluminum (Al), copper (Cu), silver (Ag), and alloys thereof, but are not limited thereto. However, the structure is not limited to this, and the metal lines and pads may be disposed below the blue sensor 200a, the green sensor 200b, and the red sensor 200c.

[0293] A lower insulating layer 60 is formed on the semiconductor substrate 40. The lower insulating layer 60 may be made of inorganic insulating materials such as silicon oxide and / or silicon nitride, or low dielectric constant (low K) materials such as SiC, SiCOH, SiCO, and SiOF.

[0294] A color filter layer 70 is formed on the insulating layer 60. The color filter layer 70 may include a blue filter 70a configured to selectively transmit light in the blue wavelength spectrum, a green filter 70b configured to selectively transmit light in the green wavelength spectrum, and a red filter 70c configured to selectively transmit light in the red wavelength spectrum. The blue filter 70a, green filter 70b, and red filter 70c each overlap with the blue sensor 200a, green sensor 200b, and red sensor 200c in the depth direction (e.g., the z-direction). The blue filter 70a may be configured to selectively transmit light in the blue wavelength spectrum, the green filter 70b may be configured to selectively transmit light in the green wavelength spectrum, and the red filter 70c may be configured to selectively transmit light in the red wavelength spectrum. The transmitted blue wavelength light may flow into the blue sensor 200a, the transmitted green wavelength light may flow into the green sensor 200b, and the transmitted red wavelength light may flow into the red sensor 200c. However, this disclosure is not limited to this, and at least one of the blue filter 70a, green filter 70b, or red filter 70c can be replaced by a yellow filter, cyan filter, or magenta filter. Here, the color filter layer 70 is disposed between the infrared sensor 100 and the visible light sensor 200, but is not limited to this, and can be disposed on the infrared sensor 100. For example, the upper insulating layer 80 and the color filter layer 70 can be disposed between the infrared sensor 100 and the filter 250.

[0295] An upper insulating layer 80 (also referred to herein as insulating layer 80) is formed on the color filter layer 70. The upper insulating layer 80 may be, for example, a planarization layer. The lower insulating layer 60 and the upper insulating layer 80 may have trenches 85 exposing the charge storage device 55. The trenches 85 may be filled with filler. At least one of the lower insulating layer 60 or the upper insulating layer 80 may be omitted.

[0296] A filter 250 is disposed on the visible light sensor 200 and the infrared sensor 100, and specifically, on the entire surface of the visible light sensor 200 and the infrared sensor 100. The filter 250 can be configured to selectively transmit light of wavelengths sensed in the visible light sensor 200 and light of wavelengths sensed in the infrared sensor 100, but reflect or absorb and thus block light of other wavelengths.

[0297] A focusing lens (not shown) may be further formed on the upper or lower surface of the filter 250. The focusing lens can control the direction of the incident light and focus the light into a region. The focusing lens may have, for example, a cylindrical or hemispherical shape, but is not limited thereto.

[0298] Figure 5 A cross-sectional view is shown to illustrate another example of a combined sensor implemented according to some exemplary embodiments.

[0299] According to some exemplary embodiments, the combined sensor 400 includes a semiconductor substrate 40, a color filter layer 70, an infrared sensor 100, a visible light sensor 200, and a filter 250, as in [the context of] including [other components]. Figure 4 The example implementation shown is the same as some of the example implementations.

[0300] The infrared sensor 100 includes a first electrode 10, a second electrode 20, an infrared photoelectric conversion layer 31, and optionally auxiliary layers 32 and 33, the details of which are the same as described above.

[0301] The visible light sensor 200 may be a combination of a photodiode integrated in the semiconductor substrate 40 and a visible light photoelectric conversion device disposed on the semiconductor substrate 40.

[0302] In the semiconductor substrate 40, a blue sensor 200a, a red sensor 200c, charge memories 55 and 240, and a transfer transistor (not shown) are integrated. The blue sensor 200a and the red sensor 200c are photodiodes and are arranged to be spaced apart (e.g., isolated from each other and not in direct contact) in the planar direction (e.g., the xy direction) (also referred to herein as the in-plane direction). The blue sensor 200a is integrated in a blue pixel and the red sensor 200c is integrated in a red pixel.

[0303] A lower insulating layer 60 and a color filter layer 70 are formed on a semiconductor substrate 40. The color filter layer 70 includes a blue filter 70a that overlaps with the blue sensor 200a and a red filter 70c that overlaps with the red sensor 200c.

[0304] An intermediate insulating layer 65 is formed on the color filter layer 70. The lower insulating layer 60 and the intermediate insulating layer 65 may have trenches 85 and 87 that expose the charge storage devices 55 and 240. The trenches 85 and 87 may be filled with a filler material. At least one of the lower insulating layer 60 or the intermediate insulating layer 65 may be omitted.

[0305] A green sensor 200b is formed on an intermediate insulating layer 65. The green sensor 200b can be a visible light photoelectric conversion device and is formed on the entire surface of the semiconductor substrate 40. The green sensor 200b includes a lower electrode 210b and an upper electrode 220b facing each other, and a green photoelectric conversion layer 230b disposed between the lower electrode 210b and the upper electrode 220b. Either the lower electrode 210b or the upper electrode 220b is an anode, and the other is a cathode.

[0306] Both the lower electrode 210b and the upper electrode 220b can be light-transmitting electrodes. The light-transmitting electrodes can be made of transparent conductors such as indium tin oxide (ITO) or indium zinc oxide (IZO), or they can be a single layer or multiple layers of a metal thin film with a thickness of a few nanometers to tens of nanometers, or a metal thin film with a thickness of a few nanometers to tens of nanometers and doped with metal oxides.

[0307] The green photoelectric conversion layer 230b can be configured to selectively absorb light in the green wavelength spectrum and allow light from wavelengths different from the green wavelength spectrum, namely the blue and red wavelength spectra, to pass through. The green photoelectric conversion layer 230b can be formed on the entire surface of the combined sensor 400. As a result, it can be configured to selectively absorb light in the green wavelength spectrum from the entire surface of the combined sensor 400 and increase the light area, thereby achieving high absorption efficiency.

[0308] The green photoelectric conversion layer 230b selectively absorbs light in the green wavelength spectrum to form excitons, and then separates these excitons into holes and electrons. The separated holes move toward the anode, which is either the lower electrode 210b or the upper electrode 220b, while the separated electrons move toward the cathode, which is the other electrode, thus achieving a photoelectric conversion effect. The separated electrons and / or holes can be collected in the charge storage 240.

[0309] An auxiliary layer (not shown) may be further included between the lower electrode 210b and the green photoelectric conversion layer 230b and / or between the upper electrode 220b and the green photoelectric conversion layer 230b. The auxiliary layer may be a charge-assisted layer, a light-absorbing auxiliary layer, or a combination thereof, but is not limited thereto.

[0310] Here, an example structure is described in which the blue sensor 200a and the red sensor 200c are photodiodes and the green sensor 200b is a photoelectric conversion device, but it is not limited thereto. The blue sensor 200a and the green sensor 200b may be photodiodes and the red sensor 200c may be a photoelectric conversion device, or the green sensor 200b and the red sensor 200c may be photodiodes and the blue sensor 200a may be a photoelectric conversion device. Therefore, two of the blue sensor 200a, the green sensor 200b, or the red sensor 200c may be integrated in the semiconductor substrate 40, and the other of the blue sensor 200a, the green sensor 200b, or the red sensor 200c may be a visible light photoelectric conversion device stacked on the semiconductor substrate 40 and in the depth direction (e.g., the z-direction) perpendicular to the in-plane direction (e.g., the x and y directions) of the infrared sensor 100 and / or perpendicular to the upper surface 40s of the semiconductor substrate 40.

[0311] An upper insulating layer 80 is formed on the green sensor 200b, and an infrared sensor 100 and a filter 250 are disposed on the upper insulating layer 80. The infrared sensor 100 and the filter 250 are the same as described above.

[0312] exist Figure 5 The diagram shows a structure in which the infrared sensor 100 is disposed on the green sensor 200b, which is one of the visible light photoelectric conversion devices, but is not limited thereto, and the green sensor 200b may be disposed on the infrared sensor 100.

[0313] exist Figure 5In this embodiment, the color filter layer 70 and the intermediate insulating layer 65 are located between the photoelectric conversion device (e.g., green sensor 200b) and the photodiode (e.g., blue and red sensors 200a and 200c) of the visible light sensor 200. However, the exemplary embodiments are not limited to this. For example, in some exemplary embodiments, the photoelectric conversion device (e.g., green sensor 200b) of the visible light sensor 200 may be located between the color filter layer 70 and the photodiode (e.g., blue and red sensors 200a and 200c) of the visible light sensor 200, wherein the color filters of the color filter layer 70 are each configured to selectively transmit a mixture of wavelength spectra absorbed by the photodiode and photoelectric conversion device overlapping with the color filter. For example, sensors 200a-200c may be configured to sense individual (separate) colors of red-green-blue (RGB), and color filters 70a, 70c may be configured to selectively transmit individual (separate) colors of cyan-magenta-yellow (CMY). For example, when the green sensor 200b is between the color filter layer 70 and the blue and red sensors 200a and 200c, the blue filter 70a overlapping with the blue sensor 200a in the depth direction can be replaced by a cyan filter, and the red filter 70c overlapping with the red sensor 200c in the depth direction can be replaced by a yellow filter. The color filter layer 70, alone or together with the intermediate insulating layer 65, can be located in the depth direction between the infrared sensor 100 and the photoelectric conversion device (e.g., the green sensor 200b) (e.g., replacing the insulating layer 80). The color filter layer 70, alone or together with the intermediate insulating layer 65, can be located in the depth direction between the infrared sensor 100 and the filter 250.

[0314] According to some exemplary embodiments, the combined sensor 400 may include an infrared sensor 100 and a visible light sensor 200 stacked along the depth direction (e.g., the z-direction) of a semiconductor substrate 40, and the visible light sensor 200 also has a structure in which a photodiode and a visible light photoelectric conversion device are stacked, thereby further reducing the area of ​​the combined sensor and thus achieving miniaturization of the combined sensor.

[0315] Figure 6 A cross-sectional view is shown schematically to illustrate another example of a combined sensor implemented according to some exemplary embodiments.

[0316] refer to Figure 6 According to some exemplary embodiments, the combined sensor 400 includes a semiconductor substrate 40, an infrared sensor 100, a visible light sensor 200, and a filter 250, as in a configuration including at least Figure 4 The example implementation shown is the same as some of the example implementations.

[0317] The infrared sensor 100 includes a first electrode 10, a second electrode 20, an infrared photoelectric conversion layer 31, and optionally auxiliary layers 32 and 33, with the same details as described above.

[0318] The visible light sensor 200 includes a blue sensor 200a and a red sensor 200c integrated in a semiconductor substrate 40, and a green sensor 200b disposed on the semiconductor substrate 40. The blue sensor 200a and the red sensor 200c may be photodiodes, and the green sensor 200b may be a visible light photoelectric conversion device. The green sensor 200b includes a lower electrode 210b, a green photoelectric conversion layer 230b, and an upper electrode 220b.

[0319] However, in the combined sensor 400 according to some exemplary embodiments, a blue sensor 200a and a red sensor 200c integrated in a semiconductor substrate 40 are stacked along the depth direction (e.g., the z-direction) of the semiconductor substrate 40. The blue sensor 200a and the red sensor 200c can be configured to selectively absorb and sense light in their respective wavelength spectra along the stacking depth from the surface 40s of the semiconductor substrate 40. In other words, the red sensor 200c, configured to absorb red light in the long wavelength spectrum, can be positioned deeper from the surface of the semiconductor substrate 40 than the blue sensor 200a, configured to absorb blue light in the short wavelength spectrum. Thus, since the absorbed wavelengths are separated along the stacking depth from the surface 40s of the semiconductor substrate 40, the color filter layer 70 for separating the absorbed wavelengths can be omitted.

[0320] Here, the blue sensor 200a and the red sensor 200c are each shown as photodiodes, for example, while the green sensor 200b is shown as a photoelectric conversion device. However, the inventive concept is not limited thereto, and the blue sensor 200a and the green sensor 200b may be photodiodes while the red sensor 200c may be a photoelectric conversion device, or the green sensor 200b and the red sensor 200c may be photodiodes while the blue sensor 200a may be a photoelectric conversion device.

[0321] Figure 6 The present invention presents a structure in which the infrared sensor 100 is disposed on one of the visible light photoelectric conversion devices, namely the green sensor 200b, but the inventive concept is not limited thereto, and the green sensor 200b may be disposed on the infrared sensor 100.

[0322] According to some exemplary embodiments, the combined sensor 400 is a combined sensor equipped with an infrared sensor 100 and a visible light sensor 200 stacked on top of each other. The visible light sensor 200 is also equipped with photodiodes and visible light photoelectric conversion devices stacked on top of each other, and the photodiodes also have a stacked structure, resulting in a reduction in the area of ​​the combined sensor and thus miniaturization of the combined sensor. In addition, according to some exemplary embodiments, the combined sensor 400 may not include a separate color filter layer, thereby simplifying the structure and process.

[0323] Figure 7 A cross-sectional view is shown schematically to illustrate another example of a combined sensor implemented according to some exemplary embodiments.

[0324] refer to Figure 7 According to some exemplary embodiments, the combined sensor 400, such as those including at least Figure 4 As in some of the example embodiments shown, it includes a semiconductor substrate 40, an infrared sensor 100, a visible light sensor 200, and a filter 250.

[0325] The infrared sensor 100, as described above, includes a first electrode 10, a second electrode 20, an infrared photoelectric conversion layer 31, and optionally auxiliary layers 32 and 33, and its details are the same as those described above.

[0326] The visible light sensor 200 includes a blue sensor 200a, a green sensor 200b, and a red sensor 200c integrated in a semiconductor substrate 40. The blue sensor 200a, green sensor 200b, and red sensor 200c are stacked in the semiconductor substrate 40 along its depth direction (e.g., the z-direction). The blue sensor 200a, green sensor 200b, and red sensor 200c can separate absorption wavelengths along the stack depth, and therefore, the color filter layer 70 can be omitted. An insulating layer 80 with trenches 85 may be formed between the semiconductor substrate 40 and the infrared sensor 100. The semiconductor substrate 40 includes a charge memory 55 connected to the infrared sensor 100.

[0327] Figure 8 A perspective view illustrating another example of a combined sensor according to some exemplary implementations, and Figure 9 To illustrate along Figure 8 The line IX-IX' Figure 8 A cross-sectional view of an example of a combined sensor.

[0328] refer to Figure 8 and 9 According to some exemplary embodiments, the combined sensor 400, such as those including at least Figure 4 As in some of the exemplary embodiments shown, it includes a semiconductor substrate 40; an infrared sensor 100; a visible light sensor 200; an insulating layer 80; and a filter 250. The visible light sensor 200 includes a blue sensor 200a, a green sensor 200b, and a red sensor 200c.

[0329] Infrared sensor 100, blue sensor 200a, green sensor 200b, and red sensor 200c may be arranged side by side along the planar direction (e.g., the xy direction) of semiconductor substrate 40 and connected to charge storage devices 55, 240a, 240b, and 240c integrated in semiconductor substrate 40 via corresponding trenches 85, respectively.

[0330] The blue sensor 200a, green sensor 200b, and red sensor 200c can each be a visible light photoelectric conversion device.

[0331] The infrared sensor 100 includes a first electrode 10, a second electrode 20, an infrared photoelectric conversion layer 31, and optionally an auxiliary layer (not shown), and the details are the same as described above.

[0332] The blue sensor 200a includes a lower electrode 210a, a blue photoelectric conversion layer 230a, and an upper electrode 220a. The green sensor 200b includes a lower electrode 210b, a green photoelectric conversion layer 230b, and an upper electrode 220b. The red sensor 200c includes a lower electrode 210c, a red photoelectric conversion layer 230c, and an upper electrode 220c. The blue photoelectric conversion layer 230a is configured to absorb light in the blue wavelength spectrum and photoelectricly convert the absorbed light; the green photoelectric conversion layer 230b is configured to absorb light in the green wavelength spectrum and photoelectricly convert the absorbed light; and the red photoelectric conversion layer 230c is configured to absorb light in the red wavelength spectrum and photoelectricly convert the absorbed light.

[0333] Figure 10 A perspective view is provided to schematically illustrate another example of a combined sensor according to some exemplary embodiments, and Figure 11 For illustrative purposes only Figure 10 A cross-sectional view of an example of a combined sensor.

[0334] refer to Figure 10 and 11 According to some exemplary embodiments, the combined sensor 400 includes a semiconductor substrate 40; an infrared sensor 100; a visible light sensor 200; and a filter 250. The visible light sensor 200 includes a blue sensor 200a, a green sensor 200b, and a red sensor 200c.

[0335] Infrared sensor 100, blue sensor 200a, green sensor 200b, and red sensor 200c may be stacked along the depth direction (e.g., z direction) of semiconductor substrate 40 and electrically connected via corresponding trenches 85 to respective charge memories 55, 240a, 240b, and 240c integrated in semiconductor substrate 40.

[0336] The infrared sensor 100 includes a first electrode 10, a second electrode 20, an infrared photoelectric conversion layer 31, and optionally an auxiliary layer (not shown), and the details are the same as described above.

[0337] The blue sensor 200a includes a lower electrode 210a, a blue photoelectric conversion layer 230a, and an upper electrode 220a. The green sensor 200b includes a lower electrode 210b, a green photoelectric conversion layer 230b, and an upper electrode 220b. The red sensor 200c includes a lower electrode 210c, a red photoelectric conversion layer 230c, and an upper electrode 220c.

[0338] Each insulating layer 80a, 80b, 80c, and 80d may be located between the semiconductor substrate 40 and the blue sensor 200a, between the blue sensor 200a and the green sensor 200b, between the green sensor 200b and the red sensor 200c, and between the red sensor 200c and the infrared sensor 100.

[0339] Some exemplary embodiments illustrate a structure in which infrared sensor 100, blue sensor 200a, green sensor 200b, and red sensor 200c are stacked sequentially, but this is not a limitation, and the stacking order can be varied without restriction. Therefore, blue sensor 200a, green sensor 200b, and red sensor 200c can each be a visible light photoelectric conversion device stacked with infrared sensor 100 in a depth direction (e.g., z direction) perpendicular to the in-plane direction (e.g., x and y directions) and / or perpendicular to the upper surface 40s of semiconductor substrate 40.

[0340] Overall reference Figure 4-11 The combined sensor 400 may include an infrared sensor 100, a visible light sensor 200, and a semiconductor substrate 40. For example, in at least... Figure 8-9 As shown, the infrared sensor 100 may be arranged parallel to the visible light sensor 200 along an in-plane direction (e.g., the xy plane), and both the infrared sensor 100 and the visible light sensor 200 extend in the in-plane direction (e.g., the xy plane). As in at least Figure 4-7 and Figure 10-11As shown, the infrared sensor 100 may be stacked with the visible light sensor along the depth direction of the semiconductor substrate 40. The depth direction can be understood as perpendicular to the upper surface 40s of the semiconductor substrate 40. The depth direction can also be understood as perpendicular to the in-plane direction, such as the x and y directions, in which the infrared sensor 100 extends.

[0341] The aforementioned infrared sensor 100, CMOS infrared sensor 300, or combined sensor 400 can be applied to, for example, various electronic devices, such as mobile phones, digital cameras, biometric devices, security devices, automotive electronic components, etc., but not limited thereto.

[0342] Figure 12 This is a schematic diagram of an electronic device according to some example implementations.

[0343] refer to Figure 12 The electronic device 1300 includes a processor 1320, a memory 1330, a sensor 1340, and a display device 1350 (e.g., an OLED display device) electrically connected via a bus 1310. The sensor 1340 may be the aforementioned infrared sensor 100, CMOS infrared sensor 300, or combined sensor 400 according to any embodiment, and may include the aforementioned film and / or compound. The processor 1320 may execute a stored program and thus at least one function. The processor 1320 may additionally execute a stored program and thus display an image on the display device 1350. The processor 1320 may generate output.

[0344] Processor 1320 may include processing circuitry systems, such as hardware including logic circuitry; hardware / software combinations, such as a processor executing software; or combinations thereof. For example, the processing circuitry systems may more specifically include, but are not limited to, central processing units (CPUs), arithmetic logic units (ALUs), digital signal processors, microcomputers, field-programmable gate arrays (FPGAs), system-on-a-chip (SoCs), programmable logic units, microprocessors, application-specific integrated circuits (ASICs), etc. Processor 1320 may be configured to generate output based on such processing (e.g., an image to be displayed on a display interface).

[0345] One or more of the processor 1320, memory 1330, sensor 1340, or display device 1350 may be included in, include, and / or implement one or more of the processing circuitry system, such as hardware including logic circuitry, hardware / software combinations such as a processor executing software, or combinations thereof. In some exemplary embodiments, one or more of the processing circuitry system may include, but is not limited to, a central processing unit (CPU), application processor (AP), arithmetic logic unit (ALU), graphics processing unit (GPU), digital signal processor, microcomputer, field-programmable gate array (FPGA), system-on-a-chip (SoC), programmable logic unit, microprocessor, or application-specific integrated circuit (ASIC), etc. In some exemplary embodiments, any of the memory, storage unit, etc., as described herein may include a non-transitory computer-readable storage device for storing instruction programs, such as a solid-state drive (SSD), and one or more of the processing circuitry system may be configured to execute instruction programs to implement some or all of the functions of the electronic device 1300, processor 1320, memory 1330, sensor 1340, and display 1350 according to any exemplary embodiment described herein.

[0346] In the following description, some exemplary embodiments are illustrated in more detail with reference to examples. However, the scope of the present invention is not limited to these embodiments.

[0347] Compound Synthesis

[0348] Synthesis Example 1

[0349] [Compound A]

[0350]

[0351] [Reaction Scheme 1]

[0352]

[0353] (1) Synthesis of compound I-1

[0354] 1-Bromo-4-iodobenzene (33.8 g, 120 mmol), 2-thiopheneboronic acid (15.3 g, 120 mmol), potassium carbonate (21.5 g, 155 mmol), and tetrakis(triphenylphosphine)palladium (0) (1 mol%) were dissolved in 150 mL of 1,4-dioxane and 40 mL of H₂O, and then stirred at 80 °C for 24 hours. When the reaction was complete, the product was extracted with H₂O / chloroform, and then separated and purified by silica gel column chromatography (n-hexane only) to obtain 26.2 g of compound I-1. The yield was 92%.

[0355] NMR (500MHz, CD2Cl2): 7.53 (s, 4H), 7.36 (d, 1H), 7.35 (d, 1H), 7.12 (t, 1H).

[0356] (2) Synthesis of compound I-2

[0357] NaH (60% in mineral oil, 4.5 g, 113 mmol) was dispersed in 130 mL of THF (tetrahydrofuran) at 0 °C, and then stirred while slowly adding a solution prepared by dissolving malononitrile (5.6 g, 85 mmol) in 10 mL of THF. After 2 hours, tetra(triphenylphosphine)palladium (0) (2 mol%), 1,1'-bis(diphenylphosphine)ferrocene (DPPF, 4 mol%), and compound I-1 (13.5 g, 56 mmol) were added sequentially, and the mixture was stirred at 80 °C for 24 hours. When the reaction was complete, the product was cooled to 0 °C and 100 mL of H2O was slowly added. Subsequently, all the THF was evaporated, and 100 mL of 1N HCl was slowly added to precipitate the material. The obtained product was extracted with H2O / chloroform and separated and purified by silica gel column chromatography (chloroform only), thus yielding 10.9 g of compound I-2. The yield was 86%.

[0358] LC-MS: Molecular weight 225.07 m / z.

[0359] (3) Synthesis of compound A

[0360] 1,3-Dithiacyclopentadien-2-thione (7.2 g, 53 mmol) and dimethyl sulfate (7.4 g, 58 mmol) were dissolved in 100 mL of acetic acid and stirred at 90 °C for 2 hours. Subsequently, compound I-2 (10.9 g, 49 mmol) was dissolved in a mixed solvent of 100 mL of acetic acid and 50 mL of triethylamine, and this solution was added to the first reactant, followed by stirring at 90 °C for 12 hours. When the reaction was complete, the result was poured into 500 mL of acetone and filtered. The product was purified by three further reprecipitations in acetone and finally by sublimation to obtain compound A.

[0361] NMR (500MHz, DMSO-d6): 8.32 (s, 2H), 8.32 (d, 1H), 7.63 (d, 1H), 7.66 (d, 2H), 6.85 (d, 2H).

[0362] Synthesis Example 2

[0363] [Compound B]

[0364]

[0365] [Reaction Scheme 2]

[0366]

[0367] (1) Synthesis of compound I-3

[0368] 2,5-Dibromothieno[3,2-b]thiophene (8.9 g, 30 mmol), 2-thienoboronic acid (3.8 g, 30 mmol), potassium carbonate (5.3 g, 39 mmol), and tetra(triphenylphosphine)palladium (0) (1 mol%) were dissolved in 80 mL of 1,4-dioxane and 20 mL of H₂O, and then stirred at 100 °C for 24 hours. When the reaction was complete, the product was extracted with H₂O / chloroform, and then separated and purified by silica gel column chromatography (n-hexane only) to obtain 2.6 g of compound I-3. The yield was 29%.

[0369] The molecular weight of LC-MS is 300.04 m / z.

[0370] (2) Synthesis of compound I-4

[0371] NaH (60% in mineral oil, 0.8 g, 20 mmol) was dispersed in 40 mL of THF at 0 °C, and the mixture was stirred while a solution obtained by adding malononitrile (0.9 g, 13 mmol) to 10 mL of THF was slowly added. After 2 hours, tetrakis(triphenylphosphine)palladium (0) (2 mol%), DPPF (4 mol%), and compound I-3 (2.6 g, 9 mmol) were added sequentially, and the mixture was stirred at 80 °C for 24 hours. When the reaction was complete, the product was cooled to 0 °C and 50 mL of H2O was slowly added. Subsequently, the THF was evaporated, and 20 mL of 1N HCl was slowly added to precipitate the material. The obtained product was extracted with H2O / chloroform, and then separated and purified by silica gel column chromatography (chloroform only) to obtain 2.1 g of compound I-4. The yield was 85%.

[0372] LC-MS: Molecular weight 287.01 m / z.

[0373] (3) Synthesis of compound B

[0374] 1,3-Dithiacyclopentadien-2-thione (1.0 g, 7.7 mmol) and dimethyl sulfate (1.1 g, 8.4 mmol) were dissolved in 16 mL of acetic acid and stirred at 90 °C for 2 hours. Subsequently, compound I-4 (2.0 g, 7.0 mmol) was dissolved in a mixed solvent of 16 mL of acetic acid and 8 mL of triethylamine, and this solution was added to the first reactant, followed by stirring at 90 °C for 12 hours. When the reaction was complete, 300 mL of acetone was added, and the mixture was filtered. The obtained product was purified by three further reprecipitations in acetone and finally by sublimation to obtain compound B.

[0375] NMR (500MHz, DMSO-d6): 8.07 (d, 1H), 8.06 (s, 1H), 7.98 (s, 2H), 7.53 (d, 1H), 6.73 (s, 1H).

[0376] Synthesis Example 3

[0377] [Compound C]

[0378]

[0379] [Reaction Scheme 3]

[0380]

[0381] (1) Synthesis of compound I-5

[0382] 6-Bromo-2-iodobenzo[b]thiophene (8.0 g, 23 mmol), 2-thiopheneboronic acid (3.0 g, 23 mmol), potassium carbonate (4.2 g, 30 mmol), and tetrakis(triphenylphosphine)palladium (0) (1 mol%) were dissolved in 80 mL of 1,4-dioxane and 20 mL of H₂O, and then stirred at 100 °C for 24 hours. When the reaction was complete, the product was extracted with H₂O / chloroform, and then separated and purified by silica gel column chromatography (n-hexane only) to obtain 6.1 g of compound I-5. The yield was 88%.

[0383] NMR (500MHz, CDCl3): 7.92 (s, 1H), 7.59 (d, 1H), 7.46 (d, 1H), 7.35 (s, 1H), 7.33 (d, 1H), 7.31 (d, 1H), 7.08 (t, 1H).

[0384] (2) Synthesis of compound I-6

[0385] NaH (60% in mineral oil, 2.0 g, 49 mmol) was dispersed in 100 mL THF at 0 °C, and the mixture was stirred while a solution obtained by dissolving malononitrile (2.3 g, 35 mmol) in 10 mL THF was slowly added. After 2 hours, tetrakis(triphenylphosphine)palladium (0) (2 mol%), DPPF (4 mol%), and compound I-5 (6.1 g, 21 mmol) were added sequentially, and the mixture was stirred at 80 °C for 24 hours. When the reaction was complete, the product was cooled to 0 °C and 100 mL H₂O was slowly added. Subsequently, the THF was evaporated, and 50 mL of 1 N HCl was slowly added to precipitate the material. The obtained product was extracted with H₂O / chloroform, and then separated and purified by silica gel column chromatography (chloroform alone) to obtain 4.9 g of compound I-6. The yield was 85%.

[0386] NMR (500MHz, CDCl3): 7.94 (s, 1H), 7.84 (d, 1H), 7.45 (d, 1H), 7.44 (s, 1H), 7.37 (d, 1H), 7.36 (d, 1H), 7.11 (t, 1H), 5.18 (s, 1H).

[0387] (3) Synthesis of compound C

[0388] 1,3-Dithiacyclopentadien-2-thione (1.0 g, 7.7 mmol) and dimethyl sulfate (1.1 g, 8.4 mmol) were dissolved in 16 mL of acetic acid and stirred at 90 °C for 2 hours. Subsequently, compound I-6 (2.0 g, 7.1 mmol) was dissolved in a mixed solvent of 16 mL of acetic acid and 8 mL of triethylamine, and this solution was added to the first reactant, followed by stirring at 90 °C for 12 hours. When the reaction was complete, the result was poured into 300 mL of acetone and filtered. The obtained product was purified by three reprecipitations in acetone and finally by sublimation to obtain compound C.

[0389] MALDI-TOF-MS: Molecular weight 380.81 m / z.

[0390] Synthesis Example 4

[0391] [Compound D]

[0392]

[0393] [Reaction Scheme 4]

[0394]

[0395] (1) Synthesis of compound I-7

[0396] NaH (60% in mineral oil, 2.0 g, 49 mmol) was dispersed in 100 mL of THF at 0 °C, and then stirred while a solution prepared by dissolving malononitrile (2.3 g, 35 mmol) in 10 mL of THF was slowly added. After 2 hours, tetrakis(triphenylphosphine)palladium (0) (2 mol%), DPPF (4 mol%), and 2-(4-bromophenyl)-3-hexylthiophene (5.5 g, 17 mmol) were added sequentially, followed by stirring at 80 °C for 24 hours. When the reaction was complete, the product was cooled to 0 °C and 100 mL of H2O was slowly added. Subsequently, the THF was evaporated, and 50 mL of 1 N HCl was slowly added to precipitate the material. The obtained product was extracted with H2O / chloroform, and then separated and purified by silica gel column chromatography (chloroform only) to obtain 4.7 g of compound I-7. The yield was 90%.

[0397] NMR (500MHz, CDCl3): 7.56 (s, 4H), 7.30 (d, 1H), 7.02 (d, 1H), 5.11 (s, 1H), 2.65 (t, 2H), 1.61 (m, 2H), 1.33-1.24 (m, 6H), 0.89 (t, 3H).

[0398] (2) Synthesis of compound D

[0399] 1,3-Dithiacyclopentadien-2-thione (0.24 g, 1.8 mmol) and dimethyl sulfate (0.25 g, 1.9 mmol) were dissolved in 4 mL of acetic acid and stirred at 90 °C for 2 hours. Subsequently, compound I-7 (0.50 g, 1.6 mmol) was dissolved in a mixed solvent of 4 mL of acetic acid and 2 mL of triethylamine, and this solution was added to the first reactant, followed by stirring at 90 °C for 12 hours. When the reaction was complete, the product was poured into 100 mL of H₂O and filtered. The resulting product was purified by silica gel column chromatography (tetrahydrofuran:chloroform = 2:1 v / v) to obtain compound D.

[0400] NMR (500MHz, CDCl3): 7.37 (s, 2H), 7.34 (s, 1H), 7.30 (d, 2H), 6.99 (d, 2H), 2.75 (t, 2H), 1.69 (m, 2H), 1.45 (t, 2H), 1.37 (m, 4H), 0.93 (t, 3H).

[0401] Synthesis Example 5

[0402] [Compound E]

[0403]

[0404] [Reaction Scheme 5]

[0405]

[0406] (1) Synthesis of compound I-8

[0407] 5-(4-bromo-2,5-dihexylphenyl)thiophene-2-carboxaldehyde (3.1 g, 7.1 mmol), benzene-1,2-dithiol (0.9 g, 6.4 mmol), and p-toluenesulfonic acid monohydrate (0.7 g, 3.6 mmol) were dissolved in 100 mL of toluene and stirred at 120 °C for 5 hours. When the reaction was complete, 100 mL of saturated NaHCO3 (aqueous solution) was added, and the result was extracted with H2O / chloroform. The product was purified by silica gel column chromatography (chloroform:n-hexane = 1:4 v / v) to give 1.9 g of compound I-8. The yield was 48%.

[0408] LC-MS: Molecular weight 559.15 m / z.

[0409] (2) Synthesis of compound E

[0410] NaH (60% in mineral oil, 0.41 g, 10.2 mmol) was dispersed in 30 mL of THF at 0 °C, and the mixture was stirred while a solution prepared by dissolving malononitrile (0.45 g, 6.8 mmol) in 10 mL of THF was slowly added. After 2 hours, tetrakis(triphenylphosphine)palladium (0) (2 mol%), DPPF (4 mol%), and compound I-8 (1.9 g, 3.4 mmol) were added sequentially, and the mixture was stirred at 80 °C for 24 hours. When the reaction was complete, the product was cooled to 0 °C and 100 mL of H₂O was slowly added. Subsequently, the THF was evaporated, and 10 mL of 1N HCl was slowly added to precipitate the material. The obtained product was then dissolved in 50 mL of chloroform, and a saturated solution of p-chloroquinone was added to the product for oxidation. The product was then separated and purified by silica gel column chromatography (tetrahydrofuran:chloroform = 1:10 v / v) to obtain compound E.

[0411] NMR (500MHz, CDCl3): 7.60-7.57(m, 2H), 7.46(d, 1H), 7.43-7.41(m, 2H), 7.38(d, 1H), 7.26(s, 1H), 7.10(s, 1H), 2.86(t, 2H), 2.81(t, 2H), 1.63(m, 4H), 1.50-1.43(m, 4H), 1.37-1.34(m, 8H), 0.92(t, 3H), 0.89(t, 3H).

[0412] Synthetic Comparative Example

[0413] [Compound F]

[0414]

[0415] Compound F was synthesized according to the method described in Synthetic Metals 1997, 84 1-3, 395-396.

[0416] NMR (500MHz, DMSO-d6): 7.93 (d, 1H), 7.89 (d, 1H), 7.70 (s, 2H), 7.48 (d, 1H), 6.75 (d, 1H).

[0417] Evaluation I

[0418] The compounds obtained in the synthetic examples and synthetic comparative examples will be divided into 1×10 -5 The concentration of M was dissolved in dimethyl sulfoxide (DMSO) to prepare a solution, and the light absorption properties of the compound in the solution were evaluated.

[0419] The peak absorption wavelength (λ) was measured using a UV-Vis-NIR spectrometer (UV-3600Plus, Shimadzu Corp.). 峰值,A1 To evaluate the light absorption properties.

[0420] The results are shown in Table 1.

[0421] Table 1

[0422] Synthesis Example 1 776 Synthesis Example 2 915 Synthesis Example 3 850 Synthesis Example 4 753 Synthesis Example 5 868 Synthetic Comparative Example 822

[0423] Referring to Table 1, the compounds according to the synthesis examples and comparative examples, in solution state, exhibit peak absorption wavelengths (λ) in the wavelength spectrum from approximately 700 nm to approximately 1000 nm. 峰值,A1 ).

[0424] Manufacturing of infrared sensors

[0425] Example 1

[0426] On a glass substrate, ITO is sputtered to form a 150 nm thick anode. Subsequently, on the anode, the compound of Synthesis Example 1 and C60 are co-deposited at a 1:1 volume ratio to form a 150 nm thick photoelectric conversion layer. On the photoelectric conversion layer, C60 is deposited to form an auxiliary layer. On the auxiliary layer, ITO is sputtered to form a 7 nm thick cathode. Subsequently, alumina (Al2O3) is deposited on the cathode to form a 50 nm thick antireflective layer, and then sealed with a glass plate to fabricate an infrared sensor.

[0427] Example 2

[0428] The infrared sensor was manufactured according to the same method as in Example 1, except that the compound of Synthetic Example 2 was used instead of the compound of Synthetic Example 1.

[0429] Comparative Example

[0430] The infrared sensor was manufactured according to the same method as in Example 1, except that the compound of the comparative synthesis was used instead of the compound of Example 1.

[0431] Evaluation II

[0432] The peak external quantum efficiency (EQE) of the infrared sensors according to the embodiments and comparative examples was evaluated. 峰值 The peak EQE wavelength (λ) 峰值,EQE ).

[0433] External quantum efficiency (EQE) was measured using an IPCE measurement system (TNE Tech Co., Ltd., South Korea). First, the system was calibrated using a Si photodiode (Hamamatsu Photonics KK, Japan). Then, the photoelectric conversion device was mounted on it to measure the EQE in the wavelength spectrum from approximately 400 nm to approximately 1400 nm. The peak EQE was then measured. 峰值 The peak EQE wavelength (λ) 峰值,EQE ).

[0434] The results are shown in Table 2 and Figure 13 middle.

[0435] Figure 13 A graph showing the external quantum efficiency of the infrared sensors according to the embodiments and comparative examples based on wavelength.

[0436] Table 2

[0437]

[0438]

[0439] Refer to Table 2 and Figure 13When the external quantum efficiency (EQE) of the infrared sensor is measured to study the light absorption properties of the deposited thin film, compared to the thin film including the compound of the synthetic comparative example, the thin film including the compound of the synthetic example exhibits a shift in the wavelength at which the peak EQE is displayed towards a longer wavelength spectrum. Here, the wavelength at which the peak EQE is displayed (e.g., the wavelength of the incident light at which the infrared sensor displays the peak EQE) corresponds to the peak absorption wavelength of the deposited thin film. As described herein, the infrared sensor can be located at the peak EQE wavelength (λ) of the infrared sensor. 峰值,EQE (For example, for λ) 峰值,EQE The peak external quantum efficiency (EQE) is observed at the wavelength of the incident light. 峰值 As described in this paper, infrared sensors exhibit peak external quantum efficiency (EQE). 峰值 The peak EQE wavelength (λ) 峰值,EQE This corresponds to the peak absorption wavelength of the infrared sensor. Referring to Tables 1 and 2, compared to the compounds of the synthetic comparative examples, the absorption wavelength spectra of the compounds of the synthetic examples shift towards longer wavelengths due to improved molecular arrangement and crystallinity during deposition. As shown in Tables 2 and... Figure 13 As shown, an infrared sensor including the compound can exhibit a peak EQE wavelength (λ) between about 1000 nm and about 3000 nm (e.g., about 1000 nm and about 2000 nm, about 1050 nm and about 1070 nm, etc.). 峰值,EQE Peak external quantum efficiency (EQE) at ) 峰值 ).

[0440] Although this disclosure has been described with respect to exemplary embodiments which are now considered to be practical, it will be understood that the inventive concept is not limited to the described exemplary embodiments, but rather is intended to cover a variety of variations and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A compound, represented by chemical formula 1: [Chemical Formula 1] in, In chemical formula 1, X is O, S, Se, or Te. Y 1 and Y 2 Independent for CR f , Z 1 or Z 2 One of them is S and Z 1 or Z 2 The other is O, S, Se, or Te. Q is a substituted or unsubstituted C3-C30 quinone ring, and Q is different from X and Y. 1 and Y 2 The 5-membered quinone ring, R 1 and R 2 Independently hydrogen, substituted or unsubstituted C1 alkyl, halogen, or a combination thereof, R f It is hydrogen, substituted or unsubstituted C1-C30 alkyl, halogen, or a combination thereof. Q is one of the groups listed in Group 1: [Group 1] 、 、 In group 1, W 2 -W 4 Independently S, Se, or Te, R 3 -R 6 and R 9 -R 14 Independently hydrogen, substituted or unsubstituted C1-C30 alkyl, halogen, or a combination thereof, R 3 -R 6 and R 9 -R 14 Existing independently, and For the connection point with chemical formula 1, In this context, "substitution" refers to the replacement of hydrogen atoms in a group by substituents selected from the following: halogen atoms.

2. The compound of claim 1, wherein X and Z of chemical formula 1 1 and Z 2 Each is represented by an S.

3. The compound of claim 1, wherein the compound is represented by one of chemical formulas 1A to 1D: [Chemical Formula 1A] [Chemical Formula 1B] [Chemical Formula 1C] [Chemical Formula 1D] in, In chemical formulas 1A to 1D, X is O, S, Se, or Te. W 2 -W 4 Independently S, Se, or Te, R 1 and R 2 Independently hydrogen, substituted or unsubstituted C1 alkyl, halogen, or combinations thereof, and R 3 -R 6 R 9 -R 14 and R f Independently hydrogen, substituted or unsubstituted C1-C30 alkyl, halogen, or a combination thereof, In this context, "substitution" refers to the replacement of hydrogen atoms in a group by substituents selected from the following: halogen atoms.

4. The compound of claim 1, wherein the compound is represented by one of chemical formulas 1A-1 to 1D-1: [Chemical Formula 1A-1] [Chemical Formula 1B-1] [Chemical formula 1C-1] [Chemical formula 1D-1] in, In chemical formulas 1A-1 to 1D-1, R 1 and R 2 Independently hydrogen, substituted or unsubstituted C1 alkyl, halogen, or combinations thereof, and R 3 -R 6 R 9 -R 14 and R f Independently hydrogen, substituted or unsubstituted C1-C30 alkyl, halogen, or a combination thereof, In this context, "substitution" refers to the replacement of hydrogen atoms in a group by substituents selected from the following: halogen atoms.

5. A membrane, comprising the compound as described in any one of claims 1-4.

6. The membrane of claim 5, wherein the membrane has a peak absorption wavelength in the wavelength spectrum of 800 nm to 3000 nm.

7. Infrared sensor, including: The first and second electrodes facing each other, and An organic layer between the first electrode and the second electrode, the organic layer comprising a compound as described in any one of claims 1-4.

8. The infrared sensor of claim 7, wherein the infrared sensor exhibits peak external quantum efficiency for incident light at a wavelength belonging to the wavelength range of 800 nm to 3000 nm.

9. The infrared sensor of claim 7, wherein the organic layer comprises an infrared photoelectric conversion layer, and the infrared photoelectric conversion layer comprises the compound and a pn junction material formed with the compound.

10. The infrared sensor of claim 7, wherein the organic layer comprises: Infrared photoelectric conversion layer, and An auxiliary layer, wherein the auxiliary layer is located in at least one of the following: Between the first electrode and the infrared photoelectric conversion layer, or Between the second electrode and the infrared photoelectric conversion layer.

11. The infrared sensor of claim 10, wherein the auxiliary layer comprises the compound.

12. The infrared sensor of claim 10, wherein the infrared photoelectric conversion layer comprises the compound, and the auxiliary layer comprises ytterbium (Yb), calcium (Ca), potassium (K), barium (Ba), magnesium (Mg), lithium fluoride (LiF), or alloys thereof.

13. The infrared sensor of claim 7, further comprising a semiconductor substrate.

14. A combined sensor, including: The first infrared sensor is the infrared sensor as described in any one of claims 7-13, and A second infrared sensor is configured to detect incident light in the infrared wavelength spectrum that is either shorter or longer than that of the first infrared sensor. The first infrared sensor and the second infrared sensor are stacked on top of each other in a depth direction perpendicular to the in-plane direction of the first infrared sensor.

15. A combined sensor, including: The first infrared sensor is the infrared sensor as described in any one of claims 7-13, and A visible light sensor configured to detect at least a portion of incident light in the visible light wavelength spectrum.

16. The combined sensor of claim 15, further comprising: Semiconductor substrate, The infrared sensor mentioned above Arranged parallel to the visible light sensor along the in-plane direction of the semiconductor substrate, or The visible light sensor is stacked along the depth direction of the semiconductor substrate.

17. The combined sensor of claim 15, wherein The visible light sensor includes a blue sensor configured to sense light in the blue wavelength spectrum, a green sensor configured to sense light in the green wavelength spectrum, and a red sensor configured to sense light in the red wavelength spectrum. The blue, green, and red sensors are each photodiodes integrated into a semiconductor substrate.

18. The combined sensor of claim 15, wherein The visible light sensor includes a blue sensor configured to sense light in the blue wavelength spectrum, a green sensor configured to sense light in the green wavelength spectrum, and a red sensor configured to sense light in the red wavelength spectrum. The two components of the blue, green, or red sensor are photodiodes integrated into a semiconductor substrate. Another of the blue, green, or red sensors is a visible light photoelectric conversion device stacked on the semiconductor substrate and in a depth direction perpendicular to the in-plane direction of the infrared sensor.

19. The combined sensor of claim 15, wherein The visible light sensor includes a blue sensor configured to sense light in the blue wavelength spectrum, a green sensor configured to sense light in the green wavelength spectrum, and a red sensor configured to sense light in the red wavelength spectrum. The blue, green, and red sensors are each visible light photoelectric conversion devices stacked with the infrared sensor.

20. An electronic device comprising the membrane as claimed in claim 5 or 6, the infrared sensor as claimed in any one of claims 7-13, or the combined sensor as claimed in any one of claims 14-19.

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