Photoelectric conversion devices, sensors and electronic devices

Abstract

The present invention relates to a photoelectric conversion device, a sensor, and an electronic device. The photoelectric conversion device includes a first electrode, a second electrode, and a photoelectric conversion layer between the first and second electrodes. The photoelectric conversion layer includes: a first material and a second material, the first and second materials being configured to form a pn junction; and a third material different from the first and second materials. The third material includes an electron-withdrawing group.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to and the benefit of Korean Patent Application Nos. 10-2019-0140290 and 10-2020-0146152, filed on November 5, 2019, and November 4, 2020, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Disclosed are a photoelectric conversion device, a sensor, and an electronic device. Background Art

[0004] Photoelectric conversion devices convert light into electrical signals using the photoelectric effect. Photoelectric conversion devices include photodiodes and phototransistors, and can be applied to sensors or photodetectors (for example, included in sensors or photodetectors).

[0005] Sensors are increasingly demanding higher resolution, leading to smaller pixel sizes. Currently, silicon photodiodes are widely used, but they can suffer from degraded sensitivity because they have a smaller absorption area due to their small pixels. Therefore, organic materials that can replace silicon have been researched.

[0006] Organic materials may have a high extinction coefficient and be configured to selectively absorb light within a specific wavelength spectrum depending on the molecular structure, and thus may replace both photodiodes and color filters, and as a result, improve sensitivity and contribute to high integration.

[0007] However, the organic material may differ from silicon due to its high binding energy and recombination behavior, and it may be difficult to accurately predict the characteristics of the organic material, which may make it difficult to easily control properties required for a photoelectric conversion device. Summary of the Invention

[0008] Some example embodiments provide a photoelectric conversion device capable of reducing residual charge carriers and improving charge carrier extraction characteristics.

[0009] Some example embodiments provide a sensor including the photoelectric conversion device.

[0010] Some example embodiments provide electronic devices including the photoelectric conversion device or the sensor.

[0011] According to some example embodiments, a photoelectric conversion device includes: a first electrode and a second electrode; and a photoelectric conversion layer between the first electrode and the second electrode, wherein the photoelectric conversion layer includes a first material and a second material that together define a pn junction, and a third material, the third material being different from the first material and the second material and including an electron-withdrawing group.

[0012] In some example embodiments, the third material may be an organic material including an electron donating portion, an electron accepting portion, and a π-conjugated linking portion connecting the electron donating portion and the electron accepting portion, wherein at least one of the electron donating portion, the electron accepting portion, or the π-conjugated linking portion may include the electron withdrawing group.

[0013] In some example embodiments, the electron-withdrawing group may include halogen; cyano; nitro; C1-C30 alkyl substituted with halogen, cyano, nitro, or a combination thereof; C1-C30 alkoxy substituted with halogen, cyano, nitro, or a combination thereof; C3-C30 cycloalkyl substituted with halogen, cyano, nitro, or a combination thereof; C6-C30 aryl substituted with halogen, cyano, nitro, or a combination thereof; or C3-C30 heteroaryl substituted with halogen, cyano, nitro, or a combination thereof.

[0014] In some example embodiments, the electron withdrawing group may include fluorine, cyano, or a combination thereof.

[0015] In some example embodiments, the electron-donating moiety may include the electron-withdrawing group, and the electron-withdrawing group may include halogen; cyano; nitro; C1-C30 alkyl substituted with halogen, cyano, nitro, or a combination thereof; C1-C30 alkoxy substituted with halogen, cyano, nitro, or a combination thereof; C3-C30 cycloalkyl substituted with halogen, cyano, nitro, or a combination thereof; C6-C30 aryl substituted with halogen, cyano, nitro, or a combination thereof; or C3-C30 heteroaryl substituted with halogen, cyano, nitro, or a combination thereof.

[0016] In some example embodiments, the electron withdrawing group may include fluorine, cyano, or a combination thereof.

[0017] In some example embodiments, the third material may be represented by Chemical Formula 1-1.

[0018] [Chemical Formula 1-1]

[0019]

[0020] In Chemical Formula 1-1,

[0021] X 1 For O, S, Se, Te, SO, SO2, CO, CR'R", NR'", SiR a R b , or GeR c R d ,

[0022] EDM3 is the electron-donating part,

[0023] EAM3 is the electron-accepting part,

[0024] R 1 、R 2 , R', R", R'", and R a 、R b 、R c , and R d are independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and R 1 and R 2 , R' and R", R a and R b , and R c and R d exist independently or are connected to each other to form a ring,

[0025] X 1 、EDM3、R 1 、R 2 , and EAM3 exist independently or two adjacent ones are connected to each other to form a ring, and

[0026] EDM3, EAM3, R 1 、R 2 , R', R", R'", R a 、R b 、R c , or R d At least one of the molecules comprises an electron-withdrawing group.

[0027] In some example embodiments, the third material may be represented by one of Chemical Formulas 1-2 to 1-4.

[0028]

[0029] In Chemical Formulas 1-2 to 1-4,

[0030] X 1 For O, S, Se, Te, SO, SO2, CO, CR'R", NR'", SiR a R b , or GeR c R d , EAM3 is the electron-accepting part,

[0031] Ar in Chemical Formula 1-2 1 and Ar 2are independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl,

[0032] Ar in Chemical Formula 1-2 1 or Ar 2 At least one of the groups is a C1-C30 alkyl group substituted by halogen, cyano, nitro, or a combination thereof; a C1-C30 alkoxy group substituted by halogen, cyano, nitro, or a combination thereof; a C3-C30 cycloalkyl group substituted by halogen, cyano, nitro, or a combination thereof; a C6-C30 aryl group substituted by halogen, cyano, nitro, or a combination thereof; or a C3-C30 heteroaryl group substituted by halogen, cyano, nitro, or a combination thereof,

[0033] Ar in chemical formulas 1-3 1 and Ar 2 are independently substituted or unsubstituted C1-C30 alkylene, substituted or unsubstituted C3-C30 cycloalkylene, substituted or unsubstituted C6-C30 arylene, or substituted or unsubstituted C3-C30 heteroarylene,

[0034] Ar in chemical formulas 1-3 1 or Ar 2 At least one of the groups is a C1-C30 alkylene group substituted by halogen, cyano, nitro, or a combination thereof; a C3-C30 cycloalkylene group substituted by halogen, cyano, nitro, or a combination thereof; a C6-C30 arylene group substituted by halogen, cyano, nitro, or a combination thereof; or a C3-C30 heteroarylene group substituted by halogen, cyano, nitro, or a combination thereof,

[0035] Ar 3 is a nitrogen-containing cyclic group substituted by halogen, cyano, nitro, or a combination thereof,

[0036] G is a single bond, -O-, -S-, -Se-, -Te-, -N=, or -NR e -、-(CR f R g ) n2 -(n2 is 1 or 2), -SiR h R i -、-GeR j R k -、-(C(R l )=C(R m ))-, or SnR n R o ,as well as

[0037] R 1 、R2 , R', R", R'", R a 、R b 、R c 、R d 、R e 、R f 、R g 、R h 、R i 、R j 、R k 、R l 、R m 、R n , and R o are independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and R 1 and R 2 , R' and R", R a and R b 、R c and R d 、R f and R g 、R h and R i 、R j and R k 、R l and R m , and R n and R o They may exist independently or be linked to each other to form a ring.

[0038] In some example embodiments, Ar of Chemical Formula 1-2 1 or Ar 2At least one of the alkyl radicals may be phenyl substituted by halogen, cyano, nitro, or a combination thereof; naphthyl substituted by halogen, cyano, nitro, or a combination thereof; anthracenyl substituted by halogen, cyano, nitro, or a combination thereof; phenanthrenyl substituted by halogen, cyano, nitro, or a combination thereof; pyridinyl substituted by halogen, cyano, nitro, or a combination thereof; pyridazinyl substituted by halogen, cyano, nitro, or a combination thereof; pyrimidinyl substituted by halogen, cyano, nitro, or a combination thereof; pyrazinyl substituted by halogen, cyano, nitro, or a combination thereof; quinolyl substituted by halogen, cyano, nitro, or a combination thereof; or a combination thereof; isoquinolinyl substituted by halogen, cyano, nitro, or a combination thereof; naphthyridinyl substituted by halogen, cyano, nitro, or a combination thereof; cinnolinyl substituted by halogen, cyano, nitro, or a combination thereof; quinazolinyl substituted by halogen, cyano, nitro, or a combination thereof; phthalazinyl substituted by halogen, cyano, nitro, or a combination thereof; benzotriazinyl substituted by halogen, cyano, nitro, or a combination thereof; pyridopyrazinyl substituted by halogen, cyano, nitro, or a combination thereof; pyridopyrimidinyl substituted by halogen, cyano, nitro, or a combination thereof; or pyridopyridazinyl substituted by halogen, cyano, nitro, or a combination thereof, and Ar of Chemical Formulas 1-3 1 or Ar 2 At least one of them is a phenylene substituted by halogen, cyano, nitro, or a combination thereof; a naphthylene substituted by halogen, cyano, nitro, or a combination thereof; an anthrylene substituted by halogen, cyano, nitro, or a combination thereof; a phenanthrenyl substituted by halogen, cyano, nitro, or a combination thereof; a pyridinyl substituted by halogen, cyano, nitro, or a combination thereof; a pyridazinyl substituted by halogen, cyano, nitro, or a combination thereof; a pyrimidinyl substituted by halogen, cyano, nitro, or a combination thereof; a pyrazinyl substituted by halogen, cyano, nitro, or a combination thereof; a quinolyl substituted by halogen, cyano, nitro, or a combination thereof; , nitro, or a combination thereof; isoquinolinylene substituted by halogen, cyano, nitro, or a combination thereof; naphthyridinylene substituted by halogen, cyano, nitro, or a combination thereof; cinnolinylene substituted by halogen, cyano, nitro, or a combination thereof; quinazolinylene substituted by halogen, cyano, nitro, or a combination thereof; phthalazinylene substituted by halogen, cyano, nitro, or a combination thereof; benzotriazinylene substituted by halogen, cyano, nitro, or a combination thereof; pyridopyrazinylene substituted by halogen, cyano, nitro, or a combination thereof; pyridopyrimidinylene substituted by halogen, cyano, nitro, or a combination thereof; or pyridopyridazinylene substituted by halogen, cyano, nitro, or a combination thereof.

[0039] In some example embodiments, Ar of Chemical Formula 1-2 1 or Ar 2At least one of may be fluorine-substituted phenyl, fluorine-substituted naphthyl, fluorine-substituted anthracenyl, fluorine-substituted phenanthrenyl, fluorine-substituted pyridinyl, fluorine-substituted pyridazinyl, fluorine-substituted pyrimidinyl, fluorine-substituted pyrazinyl, fluorine-substituted quinolyl, fluorine-substituted isoquinolyl, fluorine-substituted naphthyridinyl, fluorine-substituted cinnolinyl, fluorine-substituted quinazolinyl, fluorine-substituted phthalazinyl, fluorine-substituted benzotriazinyl, fluorine-substituted pyridopyrazinyl, fluorine-substituted pyridopyrimidinyl, or fluorine-substituted pyridopyridazinyl, and Ar of Chemical Formula 1-3 1 or Ar 2 At least one of the fluorine-substituted phenylene, fluorine-substituted naphthylene, fluorine-substituted anthrylene, fluorine-substituted phenanthrenylene, fluorine-substituted pyridinylene, fluorine-substituted pyridazinylene, fluorine-substituted pyrimidinylene, fluorine-substituted pyrazinylene, fluorine-substituted quinolylene, fluorine-substituted isoquinolylene, fluorine-substituted naphthyridinylene, fluorine-substituted cinnolinylene, fluorine-substituted quinazolinylene, fluorine-substituted phthalazinylene, fluorine-substituted benzotriazinylene, fluorine-substituted pyridopyrazinylene, fluorine-substituted pyridopyrimidinylene, or fluorine-substituted pyridopyridazinylene.

[0040] In some example embodiments, the third material may be represented by Chemical Formula 1-2a or 1-3a.

[0041]

[0042]

[0043] In Chemical Formula 1-2a or 1-3a,

[0044] X 1 For O, S, Se, Te, SO, SO2, CO, CR'R", NR'", SiR a R b , or GeR c R d , EAM3 is the electron-accepting part,

[0045] G is a single bond, -O-, -S-, -Se-, -Te-, -N=, or -NR e -、-(CR f R g ) n2 -(n2 is 1 or 2), -SiR h R i -、-GeR j R k -、-(C(R l )=C(R m ))-, or SnR n R o ,

[0046] R1 、R 2 , R', R", R'", R a 、R b 、R c 、R d 、R e 、R f 、R g 、R h 、R i 、R j 、R k 、R l 、R m 、R n 、R o 、R 7f 、R 7g 、R 7h 、R 7i 、R 7j 、R 8f 、R 8g 、R 8h 、R 8i , or R 8j are independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro,

[0047] R 7f 、R 7g 、R 7h 、R 7i , and R 7j exist independently or two adjacent thereof are connected to each other to form a fused ring,

[0048] R 8f 、R 8g 、R 8h 、R 8i , and R 8j exist independently or two adjacent thereof are connected to each other to form a fused ring, and

[0049] R 7f 、R 7g 、R 7h 、R 7i 、R 7j 、R 8f 、R 8g 、R 8h 、R 8i , or R 8jAt least one of the electron-withdrawing groups includes halogen; cyano; nitro; C1-C30 alkyl substituted by halogen, cyano, nitro, or a combination thereof; C1-C30 alkoxy substituted by halogen, cyano, nitro, or a combination thereof; C3-C30 cycloalkyl substituted by halogen, cyano, nitro, or a combination thereof; C6-C30 aryl substituted by halogen, cyano, nitro, or a combination thereof; or C3-C30 heteroaryl substituted by halogen, cyano, nitro, or a combination thereof.

[0050] In some example embodiments, EAM3 may be one of the group of groups listed in Group 1.

[0051] [Group 1]

[0052]

[0053] In Group 1,

[0054] Y 1 、Y 2 , and Y 3 are independently O, S, Se, Te, or C(R p )(CN)(where R p is hydrogen, cyano, or C1-C10 alkyl),

[0055] Ar 4 is a substituted or unsubstituted C6-C30 aromatic ring, a substituted or unsubstituted C3-C30 heteroaromatic ring, or a condensed ring of two or more substituted or unsubstituted C6-C30 aromatic rings and substituted or unsubstituted C3-C30 heteroaromatic rings,

[0056] R 3 、R 4 、R 5 , and R 6 are independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and

[0057] * indicates the connection point.

[0058] In some example embodiments, at least one of the first material or the second material may be an organic material.

[0059] In some example embodiments, the first material may be an organic material that does not include an electron withdrawing group.

[0060] In some example embodiments, the first material may be an organic material that does not include any fluorine.

[0061] In some example embodiments, the HOMO energy level of the third material may be between the HOMO energy level of the first material and the HOMO energy level of the second material.

[0062] In some example embodiments, the HOMO energy level of the first material may be about 5.0 eV to about 5.8 eV, the HOMO energy level of the second material may be about 6.2 eV to about 7.2 eV, and the HOMO energy level of the third material may be about 5.1 eV to about 6.5 eV.

[0063] In some example embodiments, the photoelectric conversion layer may include a mixture of the first material, the second material, and the third material.

[0064] In some example embodiments, the photoelectric conversion layer may include a first thin film layer including the first material and the third material; and a second thin film layer including the second material and the third material.

[0065] In some example embodiments, the third material may be included in an amount less than or equal to about 50 volume % based on the total volume of the first material and the third material.

[0066] In some example embodiments, the absorption spectrum of the photoelectric conversion layer may have a maximum absorption wavelength within a first wavelength spectrum that is one of a blue wavelength spectrum, a green wavelength spectrum, a red wavelength spectrum, or an infrared wavelength spectrum, and the first material and the third material may each be a light absorbing material having a maximum absorption wavelength within the first wavelength spectrum.

[0067] In some example embodiments, a full width at half maximum (FWHM) of an absorption spectrum of the photoelectric conversion layer may be smaller than the FWHM of an absorption spectrum of a thin film formed of the first material and the second material.

[0068] In some example embodiments, the photoelectric conversion layer may be a ternary system consisting of the first material, the second material, and the third material.

[0069] According to some example embodiments, there is provided a sensor including the photoelectric conversion device.

[0070] According to some example embodiments, the sensor may be an image sensor, and the image sensor may further include a semiconductor substrate stacked on the photoelectric conversion device.

[0071] According to some example embodiments, there is provided an electronic device including the photoelectric conversion device or the sensor.

[0072] Charge carrier extraction characteristics may be improved by increasing the wavelength selectivity of the photoelectric conversion device and reducing residual charge carriers.

[0073] According to some example embodiments, a photoelectric conversion device may include a first material and a second material configured to collectively define a pn junction. The photoelectric conversion device may further include a third material different from the first material and the second material, the third material including an electron-withdrawing group.

[0074] The photoelectric conversion device may further include a first thin film layer, the first thin film layer including one of the first material, the second material, or the third material and excluding the other of the first material, the second material, or the third material. The photoelectric conversion device may further include a second thin film layer on the first thin film layer, the second thin film layer including the other of the first material, the second material, or the third material and excluding the first material, the second material, or the third material.

[0075] The one material may be the first material, and the other material may be the second material.Both the first film layer and the second film layer may include the third material.

[0076] The first film layer may include both the first material and the second material and exclude the third material, and the second film layer may include the third material and exclude the first material and the second material.

[0077] The second film layer may be in direct contact with the first film layer.

[0078] The photoelectric conversion device may further include separate first, second, and third thin film layers, each of the first, second, and third thin film layers including a different material of the first material, the second material, or the third material. BRIEF DESCRIPTION OF THE DRAWINGS

[0079] Figure 1A is a cross-sectional view showing an example of a photoelectric conversion device according to some example embodiments,

[0080] Figure 1B According to some example embodiments Figure 1A An enlarged view of area A,

[0081] Figure 1C According to some example embodiments Figure 1A An enlarged view of area A,

[0082] Figure 2is a cross-sectional view showing an example of a photoelectric conversion device according to some example embodiments,

[0083] Figure 3 is a cross-sectional view showing an example of an image sensor according to some example embodiments,

[0084] Figure 4 is a plan view showing an example of an image sensor according to some example embodiments,

[0085] Figure 5 To display Figure 4 A cross-sectional view of an example of an image sensor,

[0086] Figure 6 To display Figure 4 A cross-sectional view of an example of an image sensor,

[0087] Figure 7 is a plan view showing an example of an image sensor according to some example embodiments,

[0088] Figure 8 To display Figure 7 A cross-sectional view of an example of an image sensor,

[0089] Figure 9 is a plan view showing another example of an image sensor according to some example embodiments,

[0090] Figure 10 To display Figure 9 A cross-sectional view of an example of an image sensor,

[0091] Figure 11 is a cross-sectional view showing an example of an image sensor according to some example embodiments,

[0092] Figure 12 is a cross-sectional view showing another example of an image sensor according to some example embodiments, and

[0093] Figure 13 is a schematic diagram showing an electronic device according to some example embodiments. DETAILED DESCRIPTION

[0094] Example embodiments will be described in detail below and can be readily implemented by those skilled in the relevant art. However, the present disclosure may be embodied in many different forms and should not be construed as limited to the example embodiments set forth herein.

[0095] In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity.

[0096] It will be understood that when an element such as a layer, film, region, or substrate is referred to as being “on” another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.

[0097] Hereinafter, as used herein, when no definition is otherwise provided, “substituted” means that a hydrogen of a compound or group is replaced by a substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazine group, a hydrazone group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a silyl group, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C30 aryl group, a C7-C30 aralkyl group, a C1-C30 alkoxy group, a C1-C20 heteroalkyl group, a C3-C20 heteroaryl group, a C3-C20 heteroaralkyl group, a C3-C30 cycloalkyl group, a C3-C15 cycloalkenyl group, a C6-C15 cycloalkynyl group, a C3-C30 heterocycloalkyl group, and combinations thereof.

[0098] As used herein, when a specific definition is not otherwise provided, "hetero" means including 1 to 4 heteroatoms selected from N, O, S, Se, Te, Si, and P.

[0099] Hereinafter, "combination" refers to a mixture or stacked structure of two or more.

[0100] As used herein, when a specific definition is not otherwise provided, energy levels refer to the highest occupied molecular orbital (HOMO) energy level and the lowest unoccupied molecular orbital (LUMO) energy level.

[0101] Hereinafter, the work function or energy level is expressed as an absolute value from the vacuum energy level. In addition, when the work function or energy level is referred to as deep, high, or large, it may have a large absolute value based on the vacuum energy level of "0 eV", and when the work function or energy level is referred to as shallow, low, or small, it may have a small absolute value based on the vacuum energy level of "0 eV".

[0102] Hereinafter, a photoelectric conversion device according to some example embodiments is described with reference to the accompanying drawings.

[0103] Figure 1A is a cross-sectional view showing an example of a photoelectric conversion device according to some example embodiments, and Figure 1B and 1C According to some example embodiments Figure 1A Magnified view of area A.

[0104] Reference Figure 1AAccording to some example embodiments, a photoelectric conversion device 100 includes a first electrode 10, a second electrode 20, and a photoelectric conversion layer 30 between the first electrode 10 and the second electrode 20. In some example embodiments, the first and second electrodes 10 and 20 may not be present in the photoelectric conversion device. For example, in some example embodiments, the photoelectric conversion device may include only the photoelectric conversion layer 30, only the photoelectric conversion layer and one or more auxiliary layers 40 and / or 50, etc.

[0105] A substrate (not shown) may be provided on one side of the first electrode 10 or the second electrode 20 (e.g., in contact with the surface of the first electrode 10 or the second electrode 20). The substrate may be, for example, a glass plate, an inorganic substrate such as a silicon wafer, or an organic substrate made of (e.g., at least partially including) an organic material such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyethersulfone, or a combination thereof. The substrate may be omitted.

[0106] One of the first electrode 10 or the second electrode 20 is an anode and the other is a cathode. In some example embodiments, the first electrode 10 may be an anode and the second electrode 20 may be a cathode. In some example embodiments, the first electrode 10 may be a cathode and the second electrode 20 may be an anode.

[0107] At least one of the first electrode 10 or the second electrode 20 may be a transparent electrode. Here, the transparent electrode may have a high light transmittance of greater than or equal to about 80%. The transparent electrode may include, for example, at least one of an oxide conductor, a carbon conductor, and a metal thin film. The oxide conductor may include, for example, at least one of indium tin oxide (ITO), indium zinc oxide (IZO), zinc tin oxide (ZTO), aluminum tin oxide (AlTO), or aluminum zinc oxide (AZO). The carbon conductor may include at least one of graphene or carbon nanostructures. The metal thin film may be a very thin film including aluminum (Al), magnesium (Mg), silver (Ag), gold (Au), alloys thereof, or combinations thereof.

[0108] One of the first electrode 10 or the second electrode 20 may be a reflective electrode. In some exemplary embodiments, the reflective electrode may have a light transmittance of less than about 10% or a high reflectivity of about 5% or greater. The reflective electrode may include a reflective conductor such as a metal, and may include, for example, aluminum (Al), silver (Ag), gold (Au), or alloys thereof.

[0109] In some example embodiments, each of the first electrode 10 and the second electrode 20 may be a transparent electrode, and one of the first electrode 10 and the second electrode 20 may be a light receiving electrode disposed at a light receiving side.

[0110] In some example embodiments, the first electrode 10 may be a transparent electrode (e.g., having a transmittance greater than or equal to about 80%), the second electrode 20 may be a reflective electrode (e.g., having a transmittance less than about 10%), and the first electrode 10 may be a light receiving electrode.

[0111] When the term "about" or "substantially" is used in conjunction with a numerical value in this specification, it means that the relevant numerical value includes a tolerance of ±10% around the numerical value. When a range is stated, the range includes all values ​​therebetween, for example, increments of 0.1%.

[0112] In some example embodiments, the first electrode 10 may be a reflective electrode, the second electrode 20 may be a transparent electrode, and the second electrode 20 may be a light receiving electrode.

[0113] The photoelectric conversion layer 30 may be disposed (eg, located) between the first electrode 10 and the second electrode 20 .

[0114] The photoelectric conversion layer 30 may be configured to absorb light in at least a portion of a wavelength spectrum and may be configured to convert the absorbed light into an electrical signal. In some example embodiments, the photoelectric conversion layer 30 may be configured to convert a portion of light in the blue wavelength spectrum (hereinafter referred to as "blue light"), light in the green wavelength spectrum (hereinafter referred to as "green light"), light in the red wavelength spectrum (hereinafter referred to as "red light"), or light in the infrared wavelength spectrum (hereinafter referred to as "infrared light") into an electrical signal. To reiterate, the absorption spectrum of the photoelectric conversion layer 30 may have a maximum absorption wavelength in a first wavelength spectrum that is one of the blue wavelength spectrum, the green wavelength spectrum, the red wavelength spectrum, or the infrared wavelength spectrum.

[0115] In some example embodiments, the photoelectric conversion layer 30 may be configured to selectively absorb at least one of blue light, green light, red light, or infrared light and convert the selectively absorbed light into an electrical signal. Here, selective absorption of at least one of blue light, green light, red light, or infrared light means that the absorption spectrum has a maximum absorption wavelength (λ) within one of greater than or equal to about 380 nm and less than about 500 nm, about 500 nm to about 600 nm, greater than about 600 nm and less than or equal to about 700 nm, or greater than about 700 nm and less than or equal to about 3000 nm. 最大 ), and the absorption spectrum in the corresponding wavelength spectrum is significantly higher than those in other wavelength spectrums. Herein, "significantly higher" means that about 70% to about 100%, about 75% to about 100%, about 80% to about 100%, about 85% to about 100%, about 90% to about 100%, or about 95% to about 100% of the total area relative to the absorption spectrum may belong to the corresponding wavelength spectrum.

[0116] Reference Figure 1BThe photoelectric conversion layer 30 may include a first material 30p and a second material 30n that together form (e.g., define, establish, etc.) a pn junction 31, and the first material 30p and the second material 30n may be configured to absorb incident light to generate excitons. The generated excitons may be separated into holes and electrons. The first material 30p and the second material 30n may each be a semiconductor, and in some example embodiments, the first material 30p may be a p-type semiconductor and the second material 30n may be an n-type semiconductor.

[0117] In some example embodiments, the first material 30p and the second material 30n may each independently be a light absorbing material that absorbs light within a specific (or alternatively, predetermined) wavelength spectrum, and in some example embodiments, at least one of the first material 30p or the second material 30n may be an organic light absorbing material. In some example embodiments, at least one of the first material 30p or the second material 30n may be a light absorbing material having wavelength selectivity, which is configured to selectively absorb light within a specific (or alternatively, predetermined) wavelength spectrum. In some example embodiments, at least one of the first material 30p or the second material 30n may be an organic light absorbing material having wavelength selectivity. The absorption spectra of the first material 30p and the second material 30n may have maximum absorption wavelengths (λ) within the same or different wavelength spectra. 最大 ).

[0118] In some example embodiments, the absorption spectra of the first material 30p and the second material 30n may independently be within one of blue light, green light, red light, or infrared light. The maximum absorption wavelength (λ) of the absorption spectra of the first material 30p and the second material 30n 最大 ) may exist within one of greater than or equal to about 380 nm and less than about 500 nm, about 500 nm to about 600 nm, greater than about 600 nm and less than or equal to about 700 nm, or greater than about 700 nm and less than or equal to about 3000 nm.

[0119] In some example embodiments, at least one of the first material 30 p and / or the second material 30 n may be an organic material.

[0120] In some example embodiments, the first material 30 p and / or the second material 30 n may be small molecules (low molecular weight compounds).

[0121] In some example embodiments, the first material 30 p and / or the second material 30 n may be a depositable compound.

[0122] In some example embodiments, the first material 30p may be an organic material having a core structure including an electron donating moiety (EDM), a π-conjugated linking moiety (LM), and an electron accepting moiety (EMA). The first material 30p may be an organic material that does not include an electron withdrawing group (e.g., does not include any electron withdrawing group, excludes any electron withdrawing group, etc.).

[0123] The first material 30 p may be represented by, for example, Chemical Formula A, but is not limited thereto.

[0124] [Chemical Formula A]

[0125] EDM1-LM1-EAM1

[0126] In chemical formula A,

[0127] EDM1 can be the electronic part,

[0128] EAM1 may be an electron accepting moiety, and

[0129] LM1 may be a π-conjugated linking portion connecting the electron-donating portion and the electron-accepting portion.

[0130] In some example embodiments, the first material 30 p represented by Chemical Formula A may be represented by Chemical Formula A-1, but is not limited thereto.

[0131] [Chemical Formula A-1]

[0132]

[0133] In Chemical Formula A-1,

[0134] EDM1 can be the electronic part,

[0135] EAM1 can be an electron-accepting part,

[0136] X a Can be O, S, Se, Te, SO, SO2, SiR a1 R b1 , or GeR c1 R d1 ,as well as

[0137] R 1a 、R 2a , and R a1 、R b1 、R c1 , and R d1 may independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and R1a and R 2a 、R a1 and R b1 , and R c1 and R d1 They may exist independently or may be linked to each other to form a ring.

[0138] In some example embodiments, the first material 30 p represented by Chemical Formula A-1 may be represented, for example, by one of Formulas A-2 to A-4, but is not limited thereto.

[0139]

[0140] In Chemical Formulas A-2 to A-4,

[0141] X a 、R 1a 、R 2a , and EAM1 are the same as described above,

[0142] Ar in Chemical Formula A-2 1a and Ar 2a may independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl,

[0143] Ar in Chemical Formula A-3 1a and Ar 2a are independently substituted or unsubstituted C1-C30 alkylene, substituted or unsubstituted C3-C30 cycloalkylene, substituted or unsubstituted C6-C30 arylene, or substituted or unsubstituted C3-C30 heteroarylene,

[0144] Ar 3a It may be a nitrogen-containing cyclic group,

[0145] W can be a single bond, -O-, -S-, -Se-, -Te-, -N=, -NR e1 -、-(CR f1 R g1 ) n1 -(n1 is 1 or 2), -SiR h1 R i1 -、-GeR j1 R k1 -、-(C(R l1 )=C(R m1 ))-, or SnR n1 R o1 ,and

[0146] R e1-R o1 may independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and R f1 and R g1 、R h1 and R i1 、R j1 and R k1 、R l1 and R m1 , and R n1 and R o1 They may exist independently or may be linked to each other to form a ring.

[0147] In some example embodiments, Ar in Formula A-2 1a and Ar 2a and may independently be one of the following: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted cinnolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted phthalazinyl, substituted or unsubstituted benzotriazinyl, substituted or unsubstituted pyridopyrazinyl, substituted or unsubstituted pyridopyrimidinyl, or substituted or unsubstituted pyridopyridazinyl.

[0148] In some example embodiments, Ar in Formula A-3 1a and Ar 2a and may independently be one of the following: substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrenylene, substituted or unsubstituted pyridinylene, substituted or unsubstituted pyridazinylene, substituted or unsubstituted pyrimidinylene, substituted or unsubstituted pyrazinylene, substituted or unsubstituted quinolylene, substituted or unsubstituted isoquinolylene, substituted or unsubstituted naphthyridinylene, substituted or unsubstituted cinnolinylene, substituted or unsubstituted quinazolinylene, substituted or unsubstituted phthalazinylene, substituted or unsubstituted benzotriazinylene, substituted or unsubstituted pyridopyrazinylene, substituted or unsubstituted pyridopyrimidinylene, or substituted or unsubstituted pyridopyridazinylene.

[0149] In some example embodiments, the first material 30p represented by Chemical Formula A-2 may be represented by Chemical Formula A-2a, and the first material 30p represented by Chemical Formula A-3 may be represented by Chemical Formula A-3a, but they are not limited thereto.

[0150]

[0151] In Chemical Formula A-2a or A-3a,

[0152] EAM1, X a , W, R 1a , and R 2a Same as described above,

[0153] R 7a -R 7e and R 8a -R 8e may independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro,

[0154] R 7a -R 7e may exist independently or two adjacent thereof may be linked to each other to form a condensed ring, and

[0155] R 8a -R 8e may exist independently or two adjacent thereof may be linked to each other to form a condensed ring.

[0156] In some example embodiments, EAM1 may be one of the groups in Group A, but is not limited thereto.

[0157] [Group A]

[0158]

[0159] In Group A,

[0160] Y 1a 、Y 2a , and Y 3a can be independently O, S, Se, Te, or C(R p1 )(CN)(where R p1 is hydrogen, cyano, or C1-C10 alkyl),

[0161] Ar 4a It may be a substituted or unsubstituted C6-C30 aromatic ring, a substituted or unsubstituted C3-C30 heteroaromatic ring, or a condensed ring of two or more thereof (e.g., two or more of a substituted or unsubstituted C6-C30 aromatic ring and a substituted or unsubstituted C3-C30 heteroaromatic ring),

[0162] R 3a 、R 4a 、R 5a , and R6a may independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and

[0163] * indicates the connection point.

[0164] In some example embodiments, Y of Group A 1a -Y 3a Both of can be O.

[0165] In some example embodiments, Y of Group A 1a and Y 2a Each can be O.

[0166] In some example embodiments, Y of Group A 1a and Y 2a Each can be O and Y 3a Can be S.

[0167] In some example embodiments, Y of Group A 2a and Y 3a Each can be O.

[0168] In some example embodiments, Ar of Group A 4a It may be a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted thiophene ring, a substituted or unsubstituted selenophene ring, a substituted or unsubstituted tellurophene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrimidine ring, or a fused ring of two or more of the foregoing.

[0169] In some example embodiments, R of Group A 3a It can be hydrogen, deuterium, or methyl.

[0170] In some example embodiments, the first material 30p may not include (e.g., may exclude) electron-withdrawing groups such as halogen, cyano, and / or nitro groups, and in some example embodiments, may not include (e.g., may exclude) any electron-withdrawing groups. In some example embodiments, the first material 30p may not include fluorine (e.g., may not include any fluorine).

[0171] In some example embodiments, the first material may be one selected from the compounds listed in Group A1:

[0172] [Group A1]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182] In group A1, R 1a 、R 1b 、R 11 and R 12 may independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and R 1a and R 1b In some example embodiments, the second material 30n may include an organic material, an inorganic material, and / or an organic / inorganic material, and in some example embodiments, may be thiophene or a thiophene derivative, fullerene, or a fullerene derivative, but is not limited thereto.

[0183] In addition to the aforementioned first and second materials 30p and 30n, the photoelectric conversion layer 30 further includes a third material 30v. The third material 30v may be a material different from the first and second materials 30p and 30n, and may be, for example, a dopant capable of changing physical properties of the photoelectric conversion layer 30.

[0184] The third material 30v may be an organic material such as a small molecule (low molecular weight compound), for example, a depositable organic compound. In some example embodiments, the photoelectric conversion layer 30 may be a co-deposited thin film of the first material 30p, the second material 30n, and the third material 30v (e.g., a single layer including a mixture of the first to third materials 30p, 30n, and 30v).

[0185] In some example embodiments, the third material 30v may be a light absorbing material, and in some example embodiments, may be a light absorbing material configured to selectively absorb light in one of the blue, green, red, or infrared wavelength spectrums.

[0186] In some example embodiments, the absorption spectra of the first material 30p and the third material 30v may each have a maximum absorption wavelength (λ) that commonly belongs to one of the blue wavelength spectrum, the green wavelength spectrum, the red wavelength spectrum, or the infrared wavelength spectrum. 最大 In some example embodiments, the absorption spectra of the first material 30p and the third material 30v may each have a maximum absorption wavelength (λ) within a blue wavelength spectrum greater than or equal to about 380 nm and less than about 500 nm. 最大 In some example embodiments, the absorption spectra of the first material 30p and the third material 30v may each have a maximum absorption wavelength (λ) within a green wavelength spectrum of about 500 nm to about 600 nm. 最大 In some example embodiments, the absorption spectra of the first material 30p and the third material 30v may each have a maximum absorption wavelength (λ) within a red wavelength spectrum greater than approximately 600 nm and less than or equal to approximately 700 nm. 最大 In some example embodiments, the absorption spectra of the first material 30p and the third material 30v may each have a maximum absorption wavelength (λ) within an infrared wavelength spectrum greater than about 700 nm and less than or equal to about 3000 nm. 最大 In some example embodiments, when the absorption spectrum of the photoelectric conversion layer 30 has a maximum absorption wavelength within a first wavelength spectrum that is one of a blue wavelength spectrum, a green wavelength spectrum, a red wavelength spectrum, or an infrared wavelength spectrum, each of the first material 30 p and the third material 30 v may be a light absorbing material having a maximum absorption wavelength within the first wavelength spectrum.

[0187] The third material 30v may be a small molecule (low molecular weight compound) including an electron-withdrawing group, for example, a small molecule (low molecular weight compound) including a halogen (F, Cl, Br, and / or I), a cyano group, and / or a nitro group. The electron-withdrawing group may be an atom or group that attracts electron density from adjacent atoms toward itself, for example, based on resonance or inductive effects. In some example embodiments, the third material 30v may be a small molecule (low molecular weight compound) including fluorine and / or a cyano group, and in some example embodiments, may be a small molecule (low molecular weight compound) including fluorine.

[0188] In this article, the electron-withdrawing group may include halogen; cyano; nitro; and / or a monovalent functional group substituted with halogen, cyano, nitro, or a combination thereof, such as halogen; cyano; nitro; C1-C30 alkyl substituted with halogen, cyano, nitro, or a combination thereof; C1-C30 alkoxy substituted with halogen, cyano, nitro, or a combination thereof; C3-C30 cycloalkyl substituted with halogen, cyano, nitro, or a combination thereof; C6-C30 aryl substituted with halogen, cyano, nitro, or a combination thereof; or C3-C30 heteroaryl substituted with halogen, cyano, nitro, or a combination thereof. The electron-withdrawing group may include fluorine, cyano, or a combination thereof.

[0189] In some example embodiments, the third material 30v may be a small molecule (low molecular weight compound) including fluorine, a monovalent functional group substituted with fluorine, a cyano group, a monovalent functional group substituted with a cyano group, or a combination thereof.

[0190] In some example embodiments, the third material 30v may be an organic material including an electron donating portion, an electron accepting portion, and a π-conjugated connecting portion connecting the electron donating portion and the electron accepting portion, and according to any example embodiment, at least one of the electron donating portion, the electron accepting portion, or the π-conjugated connecting portion may include an electron withdrawing group. In some example embodiments, at least one of the electron donating moiety, the electron accepting moiety, or the π-conjugated linking moiety may include halogen; cyano; nitro; and / or a monovalent functional group substituted with halogen, cyano, nitro, or a combination thereof, such as halogen; cyano; nitro; C1-C30 alkyl substituted with halogen, cyano, nitro, or a combination thereof; C1-C30 alkoxy substituted with halogen, cyano, nitro, or a combination thereof; C3-C30 cycloalkyl substituted with halogen, cyano, nitro, or a combination thereof; C6-C30 aryl substituted with halogen, cyano, nitro, or a combination thereof; or C3-C30 heteroaryl substituted with halogen, cyano, nitro, or a combination thereof.

[0191] In some example embodiments, at least one of the electron donating moiety, the electron accepting moiety, or the π-conjugated linking moiety may include fluorine; a monovalent functional group substituted with fluorine; a cyano group; a monovalent functional group substituted with a cyano group; or a combination thereof.

[0192] In some example embodiments, the electron donating moiety may include fluorine or a monovalent functional group substituted with fluorine.

[0193] In some example embodiments, the electron accepting moiety may include fluorine or a monovalent functional group substituted with fluorine.

[0194] In some example embodiments, the π-conjugated linking portion may include fluorine or a monovalent functional group substituted with fluorine.

[0195] In some example embodiments, the electron donating moiety, the electron accepting moiety, and the π-conjugated linking moiety may include 1 to 5 fluorine atoms (eg, fluorine atoms).

[0196] In some example embodiments, the fluorine-substituted monovalent functional group may include a fluorine-substituted C1-C30 alkyl group, a fluorine-substituted C1-C30 alkoxy group, a fluorine-substituted C3-C30 cycloalkyl group, a fluorine-substituted C6-C30 aryl group, and / or a fluorine-substituted C3-C30 heteroaryl group, but is not limited thereto.

[0197] In some example embodiments, the electron donating moiety may include a cyano group or a monovalent functional group substituted with a cyano group.

[0198] In some example embodiments, the electron accepting moiety may include a cyano group or a monovalent functional group substituted with a cyano group.

[0199] In some example embodiments, the π-conjugated linking portion may include a cyano group or a monovalent functional group substituted with a cyano group.

[0200] In some example embodiments, the electron donating moiety, the electron accepting moiety, and the π-conjugated linking moiety may include 1 to 5 cyano groups.

[0201] In some example embodiments, the monovalent functional group substituted with a cyano group may include a cyano-substituted C1-C30 alkyl group, a cyano-substituted C1-C30 alkoxy group, a cyano-substituted C3-C30 cycloalkyl group, a cyano-substituted C6-C30 aryl group, and / or a cyano-substituted C3-C30 heteroaryl group, but is not limited thereto.

[0202] In some example embodiments, the third material 30v may be represented by Chemical Formula 1.

[0203] [Chemical Formula 1]

[0204] EDM3-LM3-EAM3

[0205] In Chemical Formula 1,

[0206] EDM3 can be the electronic part,

[0207] EAM3 can be the electron acceptor part,

[0208] LM3 may be a π-conjugated linking portion connecting the electron-donating portion and the electron-accepting portion, and

[0209] At least one of EDM3, EAM3, or LM3 may include an electron withdrawing group.

[0210] In some example embodiments, the third material 30v represented by Chemical Formula 1 may be represented by Chemical Formula 1-1, but is not limited thereto.

[0211] [Chemical Formula 1-1]

[0212]

[0213] In Chemical Formula 1-1,

[0214] X 1 Can be O, S, Se, Te, SO, SO2, CO, CR'R", NR"', SiR a R b , or GeR c R d ,

[0215] EDM3 can be the electronic part,

[0216] EAM3 can be the electron acceptor part,

[0217] R 1 、R 2 , R', R", R'", R a 、R b 、R c , and R d may independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and R 1 and R 2 , R' and R", R a and R b , and R c and R d may exist independently or may be linked to each other to form a ring,

[0218] X 1 、EDM3、R 1 、R 2 , and EAM3 may exist independently or two adjacent thereof may be connected to each other to form a ring, and

[0219] EDM3, EAM3, R 1 、R 2 , R', R", R'", R a 、R b 、R c , or R d At least one of may include an electron withdrawing group.

[0220] In some example embodiments, in Chemical Formula 1-1, EDM3 may include an electron withdrawing group. In some example embodiments, the third material 30v represented by Chemical Formula 1-1 may be represented by, for example, one of Chemical Formulas 1-2 to 1-4.

[0221]

[0222] In Chemical Formulas 1-2 to 1-4,

[0223] X 1 、R 1 、R 2 , and EAM3 are the same as described above,

[0224] Ar in Chemical Formula 1-2 1 and Ar 2 may independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl,

[0225] Ar in Chemical Formula 1-2 1 or Ar 2 At least one of the groups may be a C1-C30 alkyl group substituted by halogen, cyano, nitro, or a combination thereof; a C1-C30 alkoxy group substituted by halogen, cyano, nitro, or a combination thereof; a C3-C30 cycloalkyl group substituted by halogen, cyano, nitro, or a combination thereof; a C6-C30 aryl group substituted by halogen, cyano, nitro, or a combination thereof; or a C3-C30 heteroaryl group substituted by halogen, cyano, nitro, or a combination thereof,

[0226] Ar in chemical formulas 1-3 1 and Ar 2 may independently be a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group,

[0227] Ar in chemical formulas 1-3 1 or Ar 2 At least one of the groups may be a C1-C30 alkylene group substituted by halogen, cyano, nitro, or a combination thereof; a C3-C30 cycloalkylene group substituted by halogen, cyano, nitro, or a combination thereof; a C6-C30 arylene group substituted by halogen, cyano, nitro, or a combination thereof; or a C3-C30 heteroarylene group substituted by halogen, cyano, nitro, or a combination thereof,

[0228] Ar 3It may be a nitrogen-containing cyclic group substituted by halogen, cyano, nitro, or a combination thereof,

[0229] G is a single bond, -O-, -S-, -Se-, -Te-, -N=, or -NR e -、-(CR f R g ) n2 -(n2 is 1 or 2), -SiR h R i -、-GeR j R k -、-(C(R l )=C(R m ))-, or SnR n R o ,as well as

[0230] R 1 、R 2 , R', R", R'", R a 、R b 、R c 、R c 、R d 、R e 、R f 、R g 、R h 、R i 、R j 、R k 、R l 、R m 、R n , and R o may independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and R f and R g 、R h and R i 、R j and R k 、R l and R m , and R n and R o They may exist independently or may be linked to each other to form a ring.

[0231] In some example embodiments, Ar in Formula 1-2 1 or Ar 2At least one of the C6-C30 aryl groups substituted by halogen, cyano, nitro, or a combination thereof, or a C3-C30 heteroaryl group substituted by halogen, cyano, nitro, or a combination thereof, such as a phenyl group substituted by halogen, cyano, nitro, or a combination thereof; a naphthyl group substituted by halogen, cyano, nitro, or a combination thereof; an anthracenyl group substituted by halogen, cyano, nitro, or a combination thereof; a phenanthrenyl group substituted by halogen, cyano, nitro, or a combination thereof; a pyridinyl group substituted by halogen, cyano, nitro, or a combination thereof; a pyridazinyl group substituted by halogen, cyano, nitro, or a combination thereof; a pyrimidinyl group substituted by halogen, cyano, nitro, or a combination thereof; a pyrazinyl group substituted by halogen, cyano, nitro, or a combination thereof substituted by halogen, cyano, nitro, or a combination thereof; benzotriazinyl substituted by halogen, cyano, nitro, or a combination thereof; pyridopyrazinyl substituted by halogen, cyano, nitro, or a combination thereof; pyridopyrimidinyl substituted by halogen, cyano, nitro, or a combination thereof; or pyridopyridazinyl substituted by halogen, cyano, nitro, or a combination thereof.

[0232] In some example embodiments, Ar in Formula 1-2 1 or Ar 2 At least one of the groups may be a fluorine-substituted C6-C30 aryl group or a fluorine-substituted C3-C30 heteroaryl group, such as a fluorine-substituted phenyl group, a fluorine-substituted naphthyl group, a fluorine-substituted anthracenyl group, a fluorine-substituted phenanthrenyl group, a fluorine-substituted pyridinyl group, a fluorine-substituted pyridazinyl group, a fluorine-substituted pyrimidinyl group, a fluorine-substituted pyrazinyl group, a fluorine-substituted quinolyl group, a fluorine-substituted isoquinolyl group, a fluorine-substituted naphthyridinyl group, a fluorine-substituted cinnolinyl group, a fluorine-substituted quinazolinyl group, a fluorine-substituted phthalazinyl group, a fluorine-substituted benzotriazinyl group, a fluorine-substituted pyridopyrazinyl group, a fluorine-substituted pyridopyrimidinyl group, or a fluorine-substituted pyridopyridazinyl group.

[0233] In some example embodiments, Ar in Formulas 1-3 1 or Ar 2At least one of the C6-C30 arylene groups substituted by halogen, cyano, nitro, or a combination thereof, or a C3-C30 heteroarylene group substituted by halogen, cyano, nitro, or a combination thereof, such as a phenylene group substituted by halogen, cyano, nitro, or a combination thereof; a naphthylene group substituted by halogen, cyano, nitro, or a combination thereof; an anthrylene group substituted by halogen, cyano, nitro, or a combination thereof; a phenanthrenyl group substituted by halogen, cyano, nitro, or a combination thereof; a pyridinyl group substituted by halogen, cyano, nitro, or a combination thereof; a pyridazinyl group substituted by halogen, cyano, nitro, or a combination thereof; a pyrimidinyl group substituted by halogen, cyano, nitro, or a combination thereof; a pyrazinyl group substituted by halogen, cyano, nitro, or a combination thereof substituted with halogen, cyano, nitro, or a combination thereof; quinolinylene substituted with halogen, cyano, nitro, or a combination thereof; isoquinolinylene substituted with halogen, cyano, nitro, or a combination thereof; naphthyridinylene substituted with halogen, cyano, nitro, or a combination thereof; cinnolinylene substituted with halogen, cyano, nitro, or a combination thereof; quinazolinylene substituted with halogen, cyano, nitro, or a combination thereof; phthalazinylene substituted with halogen, cyano, nitro, or a combination thereof; benzotriazinylene substituted with halogen, cyano, nitro, or a combination thereof; pyridopyrazinylene substituted with halogen, cyano, nitro, or a combination thereof; pyridopyrimidinylene substituted with halogen, cyano, nitro, or a combination thereof; or pyridopyridazinylene substituted with halogen, cyano, nitro, or a combination thereof.

[0234] In some example embodiments, Ar in Formulas 1-3 1 or Ar 2 At least one of the groups may be a fluorine-substituted C6-C30 arylene group or a fluorine-substituted C3-C30 heteroarylene group, such as a fluorine-substituted phenylene group, a fluorine-substituted naphthylene group, a fluorine-substituted anthrylene group, a fluorine-substituted phenanthrenyl group, a fluorine-substituted pyridylene group, a fluorine-substituted pyridazinylene group, a fluorine-substituted pyrimidinylene group, a fluorine-substituted pyrazinylene group, a fluorine-substituted quinolylene group, a fluorine-substituted isoquinolylene group, a fluorine-substituted naphthyridylene group, a fluorine-substituted cinnolinylene group, a fluorine-substituted quinazolinylene group, a fluorine-substituted phthalazinylene group, a fluorine-substituted benzotriazinylene group, a fluorine-substituted pyridopyrazinylene group, a fluorine-substituted pyridopyrimidinylene group, or a fluorine-substituted pyridopyridazinylene group.

[0235] In some example embodiments, the third material 30v represented by Chemical Formula 1-2 may be represented by Chemical Formula 1-2a, for example, and the third material 30v represented by Chemical Formula 1-3 may be represented by Chemical Formula 1-3a, for example, so that the third material 30v may be represented by Chemical Formula 1-2a or Chemical Formula 1-3a, but example embodiments are not limited thereto.

[0236]

[0237]

[0238] In Chemical Formula 1-2a or 1-3a,

[0239] EAM3, X 1 、R 1 、R 2 , and G are the same as described above,

[0240] R 7f 、R 7g 、R 7h 、R 7i 、R 7j 、R 8f 、R 8g 、R 8h 、R 8i , and R 8j may independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro,

[0241] R 7f -R 7j may exist independently or two adjacent thereof may be connected to each other to form a fused ring,

[0242] R 8f -R 8j may exist independently or two adjacent thereof may be linked to each other to form a fused ring, and

[0243] R 7f 、R 7g 、R 7h 、R 7i 、R 7j 、R 8f 、R 8g 、R 8h 、R 8i , or R 8j At least one of the may be an electron-withdrawing group, wherein the electron-withdrawing group may include halogen; cyano; nitro; C1-C30 alkyl substituted by halogen, cyano, nitro, or a combination thereof; C1-C30 alkoxy substituted by halogen, cyano, nitro, or a combination thereof; C3-C30 cycloalkyl substituted by halogen, cyano, nitro, or a combination thereof; C6-C30 aryl substituted by halogen, cyano, nitro, or a combination thereof; or C3-C30 heteroaryl substituted by halogen, cyano, nitro, or a combination thereof.

[0244] In some example embodiments, R 7f -R 7j One of the groups may be an electron withdrawing group.

[0245] In some example embodiments, R8f -R 8j One of the groups may be an electron withdrawing group.

[0246] In some example embodiments, R 7f -R 7j Two of them may be electron withdrawing groups.

[0247] In some example embodiments, R 8f -R 8j Two of them may be electron withdrawing groups.

[0248] In some example embodiments, R 7f -R 7j One and R 8f -R 8j One of the groups may be an electron withdrawing group.

[0249] In some example embodiments, R 7f It may be an electron-withdrawing group.

[0250] In some example embodiments, R 7g It may be an electron-withdrawing group.

[0251] In some example embodiments, R 7h It may be an electron-withdrawing group.

[0252] In some example embodiments, R 7i It may be an electron-withdrawing group.

[0253] In some example embodiments, R 7j It may be an electron-withdrawing group.

[0254] In some example embodiments, R 8f It may be an electron-withdrawing group.

[0255] In some example embodiments, R 8g It may be an electron-withdrawing group.

[0256] In some example embodiments, R 8h It may be an electron-withdrawing group.

[0257] In some example embodiments, R 8i It may be an electron-withdrawing group.

[0258] In some example embodiments, R 8j It may be an electron-withdrawing group.

[0259] In some example embodiments, R 7f -R 7j One of them may be fluorine or a fluorine-containing group.

[0260] In some example embodiments, R 8f -R 8j One of them may be fluorine or a fluorine-containing group.

[0261] In some example embodiments, R 7f -R 7j Two of them may be fluorine or fluorine-containing groups.

[0262] In some example embodiments, R 8f -R 8j Two of them may be fluorine or fluorine-containing groups.

[0263] In some example embodiments, R 7f -R 7j One and R 8f -R 8j One of them may be fluorine or a fluorine-containing group.

[0264] In some example embodiments, R 7f It may be fluorine or a fluorine-containing group.

[0265] In some example embodiments, R 7g It may be fluorine or a fluorine-containing group.

[0266] In some example embodiments, R 7h It may be fluorine or a fluorine-containing group.

[0267] In some example embodiments, R 7i It may be fluorine or a fluorine-containing group.

[0268] In some example embodiments, R 7j It may be fluorine or a fluorine-containing group.

[0269] In some example embodiments, R 8f It may be fluorine or a fluorine-containing group.

[0270] In some example embodiments, R 8g It may be fluorine or a fluorine-containing group.

[0271] In some example embodiments, R 8h It may be fluorine or a fluorine-containing group.

[0272] In some example embodiments, R 8i It may be fluorine or a fluorine-containing group.

[0273] In some example embodiments, R 8j It may be fluorine or a fluorine-containing group.

[0274] In some example embodiments, R 7f -R 7j One of them may be a cyano group or a group containing a cyano group.

[0275] In some example embodiments, R 8f -R 8j One of them may be a cyano group or a group containing a cyano group.

[0276] In some example embodiments, R 7f -R 7j Both of the groups may be cyano groups or groups containing cyano groups.

[0277] In some example embodiments, R 8f -R 8j Both of the groups may be cyano groups or groups containing cyano groups.

[0278] In some example embodiments, R 7f -R 7j One and R 8f -R 8j One of them may be a cyano group or a group containing a cyano group.

[0279] In some example embodiments, R 7f It may be a cyano group or a group containing a cyano group.

[0280] In some example embodiments, R 7g It may be a cyano group or a group containing a cyano group.

[0281] In some example embodiments, R 7h It may be a cyano group or a group containing a cyano group.

[0282] In some example embodiments, R 7i It may be a cyano group or a group containing a cyano group.

[0283] In some example embodiments, R 7j It may be a cyano group or a group containing a cyano group.

[0284] In some example embodiments, R 8f It may be a cyano group or a group containing a cyano group.

[0285] In some example embodiments, R 8g It may be a cyano group or a group containing a cyano group.

[0286] In some example embodiments, R 8h It may be a cyano group or a group containing a cyano group.

[0287] In some example embodiments, R 8i It may be a cyano group or a group containing a cyano group.

[0288] In some example embodiments, R 8j It may be a cyano group or a group containing a cyano group.

[0289] In some example embodiments, EAM3 may be one of the group listed in Group 1, but is not limited thereto.

[0290] [Group 1]

[0291]

[0292] In Group 1,

[0293] Y 1 、Y 2 , and Y 3 can be independently O, S, Se, Te, or C(R p )(CN), where R p is hydrogen, cyano, or C1-C10 alkyl,

[0294] Ar 4 It may be a substituted or unsubstituted C6-C30 aromatic ring, a substituted or unsubstituted C3-C30 heteroaromatic ring, or a condensed ring of two or more thereof (e.g., two or more of a substituted or unsubstituted C6-C30 aromatic ring and a substituted or unsubstituted C3-C30 heteroaromatic ring),

[0295] R 3 、R 4 、R 5 , and R 6 may independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and

[0296] *Can be a connection point.

[0297] In some example embodiments, Y of Group 1 1 -Y 3 Both of can be O.

[0298] In some example embodiments, Y of Group 1 1 and Y 2 Each can be O.

[0299] In some example embodiments, Y of Group 1 1 and Y 2 Each can be O and Y 3 Can be S.

[0300] In some example embodiments, Y of Group 1 2 and Y 3 Each can be O.

[0301] In some example embodiments, Ar of Group 1 4 It may be a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted thiophene ring, a substituted or unsubstituted selenophene ring, a substituted or unsubstituted tellurophene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrimidine ring, or a fused ring of two or more of the foregoing.

[0302] In some example embodiments, R of Group 1 3 It can be hydrogen, deuterium, or methyl.

[0303] In some example embodiments, the third material 30v may be one selected from Group A2:

[0304] [Group A2]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312] The third material 30v may be included in an amount that does not affect the molecular stability of the first material 30p and the second material 30n and desired characteristics in the photoelectric conversion layer 30, and in some example embodiments, may be included in an amount equal to or less than the first material 30p or the second material 30n. In some example embodiments, the third material 30v may be included in an amount that is less than or equal to about 50 volume percent (based on the total volume of the first material 30p and the third material 30v), within the range of about 1 volume percent to about 50 volume percent, about 1 volume percent to about 40 volume percent, about 1 volume percent to about 30 volume percent, about 1 volume percent to about 25 volume percent, about 1 volume percent to about 20 volume percent, about 1 volume percent to about 15 volume percent, about 1 volume percent to about 10 volume percent, about 3 volume percent to about 50 volume percent, about 3 volume percent to about 40 volume percent, about 3 volume percent to about 30 volume percent, about 3 volume percent to about 25 volume percent, about 3 volume percent to about 20 volume percent, about 3 volume percent to about 15 volume percent, or about 3 volume percent to about 10 volume percent, based on the total amount of the first material 30p and the third material 30v.

[0313] The third material 30v may be mixed with the first material 30p and the second material 30n. Thus, the photoelectric conversion layer 30 may include a mixture of the first material 30p, the second material 30n, and the third material 30v. The third material 30v may contact the first material 30p and / or the second material 30n at the atomic scale to alter the morphology or molecular conformation of the first material 30p and / or the second material 30n that form the pn junction. Therefore, the diversity of the morphology and molecular conformation of the photoelectric conversion layer 30 including the first material 30p, the second material 30n, and the third material 30v may differ from the morphology and molecular conformation of a thin film composed of the first material 30p and the second material 30n. Therefore, the properties of the photoelectric conversion layer 30 including the first material 30p, the second material 30n, and the third material 30v may differ from the properties of a thin film formed from the first material 30p and the second material 30n without the third material 30v. In some example embodiments, the photoelectric conversion layer 30 including the first material 30 p , the second material 30 n , and the third material 30 v may have improved electrical, optical, and heat resistance properties compared to a thin film formed of the first material 30 p and the second material 30 n .

[0314] In some example embodiments, according to quantum computing based on such a morphology, the aforementioned third material 30v having the electron-withdrawing group may change the energy level distribution of the first material 30p and / or the second material 30n. In some example embodiments, the aforementioned third material 30v having the electron-withdrawing group may change the HOMO energy level distribution or the LUMO energy level distribution of the first material 30p or the second material 30n. Therefore, the HOMO energy level distribution or the LUMO energy level distribution of the photoelectric conversion layer 30 including the first material 30p, the second material 30n, and the third material 30v may be different from the HOMO energy level distribution or the LUMO energy level distribution of a thin film composed of the first material 30p and the second material 30n (without the third material 30v).

[0315] As such, the photoelectric conversion layer 30 includes the third material 30v as a dopant and can thus be adjusted so that the first material 30p or the second material 30n may have a distribution of HOMO or LUMO energy levels in a desired region or may not have a distribution of HOMO or LUMO energy levels in an undesirable region.

[0316] In some example embodiments, when the first material 30 p is a p-type material and the second material 30 n is an n-type material, the third material 30 v may be a p-type material that changes the distribution of the HOMO level of the first material 30 p. In some example embodiments, the distribution of the HOMO level of the first material 30 p changed by the third material 30 v may shift toward a deeper HOMO level compared to the original distribution of the HOMO level of the first material 30 p.

[0317] In this manner, as the HOMO energy level distribution of the first material 30p of the p-type semiconductor shifts, desirable regions of the HOMO energy level distribution can be increased, or undesirable regions of the HOMO energy level distribution can be reduced or eliminated. In some example embodiments, regions of the p-type material having a shallow HOMO energy level where a relatively large number of charge carrier (e.g., hole) trap sites exist within the HOMO energy level distribution region can be reduced or eliminated. In some example embodiments, regions of the p-type semiconductor having a HOMO energy level shallower than approximately 5.2 eV can be reduced or eliminated.

[0318] In some example embodiments, the distribution of the HOMO energy level of the first material 30p modified by the third material 30v may be shifted toward a deeper HOMO energy level. In some example embodiments, the HOMO energy level of the first material 30p modified by the third material 30v may be deeper than the original HOMO energy level of the first material 30p within a range of approximately 0.0001 eV to approximately 1.2 eV. The HOMO energy level of the third material 30v may be deeper than the original HOMO energy level of the first material 30p. In some example embodiments, the original HOMO energy level of the first material 30p may be approximately 5.0 eV to approximately 5.8 eV, and the HOMO energy level of the third material 30v may be approximately 5.1 eV to approximately 6.5 eV.

[0319] In some example embodiments, the HOMO energy level of the second material 30n, which is an n-type material, may be deeper than the HOMO energy levels of the first material 30p and the third material 30v. Furthermore, in some example embodiments, the HOMO energy level of the third material 30v may be between the HOMO energy levels of the first material 30p and the second material 30n. In some example embodiments, the difference between the HOMO energy levels of the third material 30v and the second material 30n may be smaller than the difference between the HOMO energy levels of the first material 30p and the second material 30n. Within this range, the HOMO energy level of the first material 30p may be, for example, approximately 5.0 eV to approximately 5.8 eV, the HOMO energy level of the second material 30n may be, for example, approximately 6.2 eV to approximately 7.2 eV, and the HOMO energy level of the third material 30v may be, for example, approximately 5.1 eV to approximately 6.5 eV.

[0320] Therefore, the HOMO energy level of the photoelectric conversion layer 30 including the first, second and third materials 30p, 30n and 30v can be deeper than the HOMO energy level of the thin film formed by the first and second materials 30p and 30n (without the third material 30v), and in some example embodiments, it is deeper than the HOMO energy level of the thin film formed by the first and second materials 30p and 30n (without the third material 30v) by greater than or equal to about 0.001eV, and in some example embodiments, it is deeper by about 0.001eV to about 1.2eV.

[0321] In this way, the energy level distribution of the first material 30p or the second material 30n can be adjusted so that the energy level region (e.g., a region with a shallow HOMO energy level) in which there are relatively many trapping sites for charge carriers in the photoelectric conversion layer 30 can be reduced or eliminated, and thus, among the charge carriers moving from the photoelectric conversion layer 30 to the first electrode 10 and / or the second electrode 20, the remaining charge carriers can be reduced or prevented from remaining in the trapping sites. Therefore, afterimages (image sticking) caused by the remaining charge carriers accumulated in the photoelectric conversion layer 30 can be reduced or prevented, resulting in improved electrical performance of the photoelectric conversion device 100.

[0322] In some example embodiments, the third material 30v may change the absorption spectrum of the photoelectric conversion layer 30. In some example embodiments, the wavelength selectivity of the photoelectric conversion layer 30 including the first material 30p, the second material 30n, and the third material 30v may be higher than the wavelength selectivity of a thin film of the first material 30p and the second material 30n (without the third material 30v). In some example embodiments, the half-width (FWHM) of the absorption spectrum of the photoelectric conversion layer 30 including the first material 30p, the second material 30n, and the third material 30v may be narrower than the half-width (e.g., FWHM) of the absorption spectrum of a thin film composed of (e.g., formed from) the first material 30p and the second material 30n (without the third material 30v). In this document, the half-width (FWHM) is the width of the wavelength range corresponding to half the peak absorption point (maximum absorption wavelength). A small FWHM means high wavelength selectivity by absorbing light within a narrow wavelength spectrum. In some example embodiments, the FWHM of the absorption spectrum of the photoelectric conversion layer 30 including the first material 30p, the second material 30n, and the third material 30v may be narrower by about 2 nm to about 30 nm, within the range of about 3 nm to about 30 nm, about 5 nm to about 30 nm, about 5 nm to about 25 nm, or about 5 nm to about 20 nm, than the FWHM of the absorption spectrum of the thin film of the first material 30p and the second material 30n (without the third material 30v).

[0323] In some example embodiments, third material 30v may change the heat resistance characteristics of photoelectric conversion layer 30. In some example embodiments, the heat resistance of photoelectric conversion layer 30 including first material 30p, second material 30n, and third material 30v may be improved relative to the heat resistance of a thin film composed of first material 30p and second material 30n (without third material 30v). In some example embodiments, photoelectric conversion layer 30 including first material 30p, second material 30n, and third material 30v may substantially maintain optical and electrical properties even in a subsequent high-temperature process of approximately 180°C, approximately 190°C, or approximately 200°C.

[0324] like Figure 1B As shown in , the photoelectric conversion layer 30 may be an intrinsic layer 30I in which the aforementioned first material 30p, second material 30n, and third material 30v are blended in the form of a bulk heterojunction.

[0325] The first material 30p and the second material 30n may be blended in a volume ratio of about 1:9 to about 9:1, for example, 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.

[0326] In some example embodiments, the photoelectric conversion layer 30 may be a ternary system of a first material 30 p , a second material 30 n , and a third material 30 v .

[0327] like Figure 1C As shown in , the photoelectric conversion layer 30 may include at least two separate thin film layers (e.g., thin film layers) 32-1 and 32-2, which contain different combinations of the first to third materials 30p, 30n, and 30v. For example, in some example embodiments, the first thin film layer 32-1 includes at least one of the aforementioned first material 30p, second material 30n, and third material 30v and does not include at least one other (other) material of the aforementioned first material 30p, second material 30n, and third material 30v, and the separate second thin film layer 32-2 on the thin film layer 32-1 includes the at least one other material of the aforementioned first material 30p, second material 30n, and third material 30v and does not include the at least one material of the aforementioned first material 30p, second material 30n, and third material 30v. Figure 1C In the embodiment, the one material is the first material 30 p and the other material is the second material 30 n , and both the first and second thin film layers 32 - 1 and 32 - 2 include the third material 30 v , but example embodiments are not limited thereto.

[0328] In some example embodiments, the first thin film layer 32-1 may include both the first and second materials 30p and 30n (where either the first or second material 30p or 30n is the one material) and does not include the third material 30v, while the second thin film layer 32-2 may include the third material 30v and does not include both the first and second materials 30p and 30n.

[0329] In some example embodiments, the first film layer 32-1 may include the aforementioned first material 30p and the third material 30v (e.g., a mixture thereof), either the first or third material 30p or 30v being the aforementioned one material, and the other material in the second film layer 32-2 may include the aforementioned second material 30n. In some example embodiments, the first film layer 32-1 may include the aforementioned second material 30n and the third material 30v (e.g., a mixture thereof), either the second or third material 30n or 30v being the aforementioned one material, and the other material in the second film layer 32-2 may include the aforementioned first material 30p.

[0330] In some example embodiments, the photoelectric conversion layer 30 may include an additional third thin film layer (not shown). Figure 1C ), and the first, second, and third thin film layers of the photoelectric conversion layer may include separate different materials of a first material 30p, a second material 30n, or a third material 30v.

[0331] like Figure 1C As shown in FIG, the second thin film layer 32-2 is in direct contact with the first thin film layer 32-1, but example embodiments are not limited thereto, and the first and second thin film layers 32-1 and 32-2 may be isolated from direct contact with each other by one or more intervening layers (e.g., auxiliary layers according to any example embodiment as described herein).

[0332] like Figure 1C As shown in , the first thin film layer 32-1 may be between the second thin film layer 32-2 and the first electrode 10 (e.g., in contact with the first electrode 10), and the second thin film layer 32-2 may be between the first thin film layer 32-1 and the second electrode 20 (e.g., in contact with the second electrode 20), but example embodiments are not limited thereto, and in some example embodiments, the respective positions of the first and second thin film layers 32-1 and 32-2 may be interchanged, so that the second thin film layer 32-2 may be between the first thin film layer 32-1 and the first electrode 10 (e.g., in contact with the first electrode 10), and the first thin film layer 32-1 may be between the second thin film layer 32-2 and the second electrode 20 (e.g., in contact with the second electrode 20).

[0333] In some example embodiments, the photoelectric conversion layer 30 may be provided (disposed) independently of other elements of the photoelectric conversion device 100 .

[0334] The photoelectric conversion device 100 may further include an anti-reflection layer (not shown) on one surface of the first electrode 10 or the second electrode 20. The anti-reflection layer may be provided on the light incident side and reduce the light reflectivity of the incident light, thereby further improving the absorbance. In some example embodiments, when light is incident on the first electrode 10, the anti-reflection layer may be provided on the first electrode 10, and when light is incident on the second electrode 20, the anti-reflection layer may be provided below the second electrode 20.

[0335] The anti-reflection layer may include, for example, a material having a refractive index of about 1.6 to about 2.5, and may include, for example, at least one of an organic material, an oxide, or a sulfide having a refractive index within the range. The anti-reflection layer may include, for example, an oxide such as an aluminum-containing oxide, a molybdenum-containing oxide, a tungsten-containing oxide, a vanadium-containing oxide, a rhenium-containing oxide, a niobium-containing oxide, a tantalum-containing oxide, a titanium-containing oxide, a nickel-containing oxide, a copper-containing oxide, a cobalt-containing oxide, a manganese-containing oxide, a chromium-containing oxide, a tellurium-containing oxide, or a combination thereof; a sulfide such as zinc sulfide; or an organic material such as an amine derivative, but is not limited thereto.

[0336] In the photoelectric conversion device 100, when light enters from the first electrode 10 or the second electrode 20, and the photoelectric conversion layer 30 may be configured to absorb light within a specific (or alternatively, predetermined) wavelength spectrum, excitons may be generated therein. The excitons are separated into holes and electrons in the photoelectric conversion layer 30, and the separated holes are transferred to the anode, which is one of the first electrode 10 or the second electrode 20, and the separated electrons are transferred to the cathode, which is the other of the first electrode 10 and the second electrode 20, to allow current to flow.

[0337] Figure 2 is a cross-sectional view showing an example of a photoelectric conversion device according to some example embodiments.

[0338] Reference Figure 2 As in the aforementioned example embodiments, the photoelectric conversion device 100 according to some example embodiments includes a first electrode 10, a second electrode 20, and a photoelectric conversion layer 30. However, unlike the aforementioned example embodiments, the photoelectric conversion device 100 according to some example embodiments may further include auxiliary layers 40 and 50 formed between the first electrode 10 and the photoelectric conversion layer 30 and between the second electrode 20 and the photoelectric conversion layer 30.

[0339] The auxiliary layers 40 and 50 may include a hole injection layer (HIL) for facilitating injection of holes, a hole transport layer (HTL) for facilitating transport of holes, an electron blocking layer (EBL) for blocking movement of electrons, an electron injection layer (EIL) for facilitating electron injection, an electron transport layer (ETL) for facilitating electron transport, and / or a hole blocking layer (HBL) for blocking movement of holes, but are not limited thereto.

[0340] The auxiliary layers 40 and 50 may independently include an organic material, an inorganic material, and / or an organic / inorganic material.

[0341] In some example embodiments, one of the auxiliary layers 40 and 50 may include an inorganic auxiliary layer. In some example embodiments, the inorganic auxiliary layer may include a lanthanide element, calcium (Ca), potassium (K), aluminum (Al), or an alloy thereof. In some example embodiments, the lanthanide element may include ytterbium (Yb). The inorganic auxiliary layer may have a thickness of less than or equal to about 5 nm.

[0342] In some example embodiments, one of the auxiliary layers 40 and 50 may include an organic auxiliary layer. In some example embodiments, the organic auxiliary layer may include a compound represented by Chemical Formula 2A or 2B, but is not limited thereto.

[0343] [Chemical Formula 2A]

[0344]

[0345] [Chemical Formula 2B]

[0346]

[0347] In Chemical Formula 2A or 2B,

[0348] M 1 and M 2 Can be independently O, S, Se, Te, CR q R r 、SiR s R t , or NR u ,

[0349] Ar 1c 、Ar 2c 、Ar 3c , and Ar 4c may independently be a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C3-C30 heteroaryl group,

[0350] G 2 and G 3 Can be independently a single bond, -(CR v Rw ) n3 -, -O-, -S-, -Se-, -N=, -NR x -, or -SiR y R z -, where n3 is 1 or 2, and

[0351] R 30 -R 37 and R q -R z They may independently be hydrogen, deuterium, 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 halogen, a cyano group, or a nitro group.

[0352] In some example embodiments, the organic auxiliary layer may include a compound represented by Chemical Formula 2A-1 or 2B-1, but is not limited thereto.

[0353] [Chemical Formula 2A-1]

[0354]

[0355] [Chemical Formula 2B-1]

[0356]

[0357] In Chemical Formula 2A-1 or 2B-1,

[0358] M 1 、M 2 , G 2 , G 3 , and R 30 -R 37 Same as described above,

[0359] R 38 -R 45 and may independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro.

[0360] In some example embodiments, the organic auxiliary layer may include a compound represented by Chemical Formula 2A-1a or 2B-1a, but is not limited thereto.

[0361] [Chemical Formula 2A-1a]

[0362]

[0363] [Chemical Formula 2B-1a]

[0364]

[0365] In some example embodiments, one of the auxiliary layers 40 and 50 may be an inorganic auxiliary layer, and the other of the auxiliary layers 40 and 50 may be an organic auxiliary layer.

[0366] In some example embodiments, one of the auxiliary layers 40 and 50 may be omitted.

[0367] In some example embodiments, the aforementioned photoelectric conversion device 100 may be applied to a sensor (e.g., included in a sensor), and in some example embodiments, the sensor may be an image sensor. The image sensor to which the aforementioned photoelectric conversion device 100 is applied may have improved optical and electrical characteristics as described above, and may be suitable for high-speed shooting (photography) by reducing afterimages due to residual charge carriers.

[0368] Hereinafter, examples of image sensors to which the aforementioned device is applied are described with reference to the accompanying drawings. An organic CMOS image sensor is described as an example of the image sensor.

[0369] Figure 3 is a cross-sectional view showing an example of an image sensor according to some example embodiments.

[0370] Reference Figure 3 The image sensor 300 according to some example embodiments includes a semiconductor substrate 110, an upper insulating layer 80, a photoelectric conversion device 100, and a color filter layer 70. The photoelectric conversion device 100 shown in any of the drawings may be any of the example embodiments of the photoelectric conversion device, including Figure 1A and / or Figure 2 The photoelectric conversion device 100 shown in FIG.

[0371] The semiconductor substrate 110 may be a silicon substrate and may be integrated with a transfer transistor (not shown) and a charge storage 155. The transfer transistor and / or the charge storage 155 may be integrated in each pixel. The charge storage 155 is electrically connected to the photoelectric conversion device 100.

[0372] Metal lines (not shown) and pads (not shown) are formed on the semiconductor substrate 110. To reduce signal delay, the metal lines and pads may be made of a metal having low resistivity, such as aluminum (Al), copper (Cu), silver (Ag), and alloys thereof in some example embodiments, but not limited thereto.

[0373] An upper insulating layer 80 is formed on the metal lines and pads. Upper insulating layer 80 may be made of an inorganic insulating material such as silicon oxide and / or silicon nitride, or a low-dielectric constant (low-K) material such as SiC, SiCOH, SiCO, and SiOF. Upper insulating layer 80 has a trench 85 that exposes charge storage 155. Trench 85 may be filled with a filler.

[0374] The color filter layer 70 is formed on the photoelectric conversion device 100 .

[0375] A color filter layer 70 is formed on the photoelectric conversion device 100. The color filter layer 70 includes a blue filter 70a formed in a blue pixel, a red filter 70b formed in a red pixel, and a green filter 70c formed in a green pixel. However, it may include a cyan filter, a magenta filter, and / or a yellow filter instead of the above filters, or may further include them in addition to the above filters.

[0376] The insulating layer 180 is formed between the photoelectric conversion device 100 and the color filter layer 70. The insulating layer 180 may be omitted.

[0377] A focusing lens (not shown) may be further formed on the color filter layer 70. The focusing lens may control the direction of incident light and focus the light in one area. In some example embodiments, the focusing lens may have a cylindrical or hemispherical shape, but is not limited thereto.

[0378] Figure 4 is a plan view showing an example of an image sensor according to some example embodiments, and Figure 5 To display Figure 4 A cross-sectional view of an example of an image sensor.

[0379] Reference Figure 4 and 5 According to some example embodiments, the image sensor 400 includes: a semiconductor substrate 110 integrated with light sensing devices 150a and 150b, a transfer transistor (not shown) and a charge storage 155, a lower insulating layer 60, a color filter layer 70, an upper insulating layer 80, and the aforementioned photoelectric conversion device 100.

[0380] The semiconductor substrate 110 may be a silicon substrate, and is integrated with light sensing devices 150a and 150b, a transfer transistor (not shown), and a charge storage 155. The light sensing devices 150a and 150b may be photodiodes.

[0381] The light sensing devices 150a and 150b, the transfer transistors, and / or the charge storage 155 may be integrated in each pixel, and as shown in the figure, the light sensing devices 150a and 150b may be included in the blue pixel and the red pixel, respectively, and the charge storage 155 may be included in the green pixel.

[0382] The light sensing devices 150a and 150b sense light, and information sensed by the light sensing devices can be transferred by the transfer transistors. The charge storage 155 is electrically connected to the aforementioned photoelectric conversion device 100, and information of the charge storage 155 can be transferred by the transfer transistors.

[0383] Metal lines (not shown) and pads (not shown) are formed on the semiconductor substrate 110. To reduce signal delay, the metal lines and pads may be made of a metal with low resistivity, such as aluminum (Al), copper (Cu), silver (Ag), and alloys thereof in some example embodiments, but not limited thereto. However, it is not limited to this structure, and the metal lines and pads may be disposed below the light sensing devices 150a and 150b.

[0384] A lower insulating layer 60 is formed on the metal lines and pads. Lower insulating layer 60 may be made of an inorganic insulating material such as silicon oxide and / or silicon nitride, or a low-dielectric constant (low-K) material such as SiC, SiCOH, SiCO, and SiOF. Lower insulating layer 60 has a trench 85 that exposes charge storage 155. Trench 85 may be filled with a filler.

[0385] A color filter layer 70 is formed on the lower insulating layer 60. The color filter layer 70 includes a blue filter 70a formed in a blue pixel and a red filter 70b formed in a red pixel. However, the present disclosure is not limited thereto and may alternatively or additionally include a cyan filter, a magenta filter, and / or a yellow filter. In some example embodiments, a green filter is not included, but a green filter may be further included.

[0386] An upper insulating layer 80 is formed on the color filter layer 70. The upper insulating layer 80 eliminates steps (stairs) caused by the color filter layer 70 and smoothes the surface. The upper insulating layer 80 and the lower insulating layer 60 may include a contact hole (not shown) exposing the pad and a trench 85 exposing the charge storage 155 of the green pixel.

[0387] The aforementioned photoelectric conversion device 100 is formed on the upper insulating layer 80. The photoelectric conversion device 100 may have Figure 1A2, and its detailed description is the same as that described above. One of the first electrode 10 or the second electrode 20 of the photoelectric conversion device 100 may be a light receiving electrode, and the other of the first electrode 10 and the second electrode 20 of the photoelectric conversion device 100 may be connected to the charge storage 155.

[0388] A focusing lens (not shown) may be further formed on the photoelectric conversion device 100. The focusing lens may control the direction of incident light and focus the light in one area. In some example embodiments, the focusing lens may have a cylindrical or hemispherical shape, but is not limited thereto.

[0389] Figure 6 To display Figure 4 A cross-sectional view of another example of an image sensor.

[0390] Reference Figure 6 The image sensor 500 according to some example embodiments includes a semiconductor substrate 110 integrated with light sensing devices 150 a and 150 b , a transfer transistor (not shown), and a charge storage 155 , an upper insulating layer 80 , and a photoelectric conversion device 100 .

[0391] However, in the image sensor 500 according to some example embodiments, unlike the aforementioned example embodiments, the light sensing devices 150a and 150b are stacked in a vertical direction and the color filter layer 70 is omitted. The light sensing devices 150a and 150b are electrically connected to a charge storage (not shown), and information sensed by the light sensing devices 150a and 150b can be transmitted through a transfer transistor. The light sensing devices 150a and 150b can be selectively configured to absorb light within various wavelength spectrums depending on the stacking depth.

[0392] The photoelectric conversion device 100 may have Figure 1A 2, and its detailed description is the same as that described above. One of the first electrode 10 or the second electrode 20 of the photoelectric conversion device 100 may be a light receiving electrode, and the other of the first electrode 10 or the second electrode 20 of the photoelectric conversion device 100 may be connected to the charge storage 155.

[0393] Figure 7 is a plan view showing another example of an image sensor according to some example embodiments, and Figure 8 To display Figure 7 A cross-sectional view of an example of an image sensor.

[0394] The image sensor 600 according to some example embodiments has a structure in which a green device configured to selectively absorb light in a green wavelength spectrum, a blue device configured to selectively absorb light in a blue wavelength spectrum, and a red device configured to selectively absorb light in a red wavelength spectrum are stacked.

[0395] An image sensor 600 according to some example embodiments includes a semiconductor substrate 110 , a lower insulating layer 60 , an intermediate insulating layer 65 , an upper insulating layer 80 , a first photoelectric conversion device 100 a , a second photoelectric conversion device 100 b , and a third photoelectric conversion device 100 c .

[0396] The semiconductor substrate 110 may be a silicon substrate and integrated with a transfer transistor (not shown) and charge storages 155 a , 155 b , and 155 c .

[0397] Metal lines (not shown) and pads (not shown) are formed on the semiconductor substrate 110 , and a lower insulating layer 60 is formed on the metal lines and pads.

[0398] A first photoelectric conversion device 100 a , a second photoelectric conversion device 100 b , and a third photoelectric conversion device 100 c are sequentially formed on the lower insulating layer 60 .

[0399] The first, second, and third photoelectric conversion devices 100a, 100b, and 100c may each independently have Figure 1A 2, and its detailed description is the same as that described above. One of the first electrode 10 or the second electrode 20 of the first, second, and third photoelectric conversion devices 100a, 100b, and 100c may be a light receiving electrode, and the other of the first electrode 10 and the second electrode 20 of the first, second, and third photoelectric conversion devices 100a, 100b, and 100c may be connected to the charge storage 155a, 155b, and 155c.

[0400] The first photoelectric conversion device 100a can be selectively configured to absorb light within one of the red, blue, or green wavelength spectrums and photoelectrically convert it. In some example embodiments, the first photoelectric conversion device 100a can be a red photoelectric conversion device. An intermediate insulating layer 65 is formed on the first photoelectric conversion device 100a.

[0401] The second photoelectric conversion device 100 b is formed on the intermediate insulating layer 65 .

[0402] The second photoelectric conversion device 100b may be selectively configured to absorb light within one of the red, blue, or green wavelength spectrums and may photoelectrically convert it. In some example embodiments, the second photoelectric conversion device 100b may be a blue photoelectric conversion device.

[0403] The upper insulating layer 80 is formed on the second photoelectric conversion device 100b. The lower insulating layer 60, the intermediate insulating layer 65, and the upper insulating layer 80 have a plurality of trenches 85a, 85b, and 85c exposing the charge storages 155a, 155b, and 155c.

[0404] The third photoelectric conversion device 100c is formed on the upper insulating layer 80. The third photoelectric conversion device 100c can be selectively configured to absorb and photoelectrically convert light within one of the red, blue, or green wavelength spectrums. In some example embodiments, the third photoelectric conversion device 100c can be a green photoelectric conversion device.

[0405] A focusing lens (not shown) may be further formed on the third photoelectric conversion device 100c. The focusing lens may control the direction of incident light and focus the light in one area. In some example embodiments, the focusing lens may have a cylindrical or hemispherical shape, but is not limited thereto.

[0406] In the drawing, the first photoelectric conversion device 100 a , the second photoelectric conversion device 100 b , and the third photoelectric conversion device 100 c are sequentially stacked, but the present disclosure is not limited thereto, and they may be stacked in various orders (different orders).

[0407] As described above, the first photoelectric conversion device 100 a , the second photoelectric conversion device 100 b , and the third photoelectric conversion device 100 c are stacked, and thus the size of the image sensor may be reduced to realize a miniaturized image sensor.

[0408] Figure 9 is a plan view showing another example of an image sensor according to some example embodiments, and Figure 10 To display Figure 9 A cross-sectional view of an example of an image sensor.

[0409] Reference Figure 9 and 10 The image sensor 1100 includes a photoelectric conversion device 90 disposed on a semiconductor substrate 110, and the photoelectric conversion device 90 includes a plurality of photoelectric conversion devices 90-1, 90-2, and 90-3. The plurality of photoelectric conversion devices 90-1, 90-2, and 90-3 can convert light within different wavelength spectra (for example, blue light, green light, or red light) into electrical signals. Figure 10, a plurality of photoelectric conversion devices 90-1, 90-2, and 90-3 may be arranged in a horizontal direction on the semiconductor substrate 110 such that the photoelectric conversion devices 90-1, 90-2, and 90-3 may partially or completely overlap with each other in a direction extending parallel to the surface 110a of the semiconductor substrate 110. Each of the photoelectric conversion devices 90-1, 90-2, and 90-3 is connected to a charge storage device 155 integrated into the semiconductor substrate 110 through a trench 85.

[0410] Each photoelectric conversion device 90-1, 90-2, and 90-3 may be one of the aforementioned photoelectric conversion devices 100. In some example embodiments, two or more photoelectric conversion devices 90-1, 90-2, and 90-3 may include different portions of a common continuous layer that extends continuously between the photoelectric conversion devices 90-1, 90-2, and 90-3. In some example embodiments, the plurality of photoelectric conversion devices 90-1, 90-2, and 90-3 may share a common first electrode 10 and / or a common second electrode 20. In some example embodiments, two or more of the photoelectric conversion devices 90-1, 90-2, and 90-3 may have different photoelectric conversion layers 30 that are configured to absorb different wavelength spectra of incident light. Other configurations of the image sensor 1100 may be similar to those described with reference to FIG. Figure 3-8 One or more of the described image sensors are the same.

[0411] Figure 11 is a cross-sectional view showing an example of an image sensor according to some example embodiments.

[0412] Reference Figure 11 The organic CMOS image sensor 1200 includes a semiconductor substrate 110 and photoelectric conversion devices 90-1 and 91 stacked on the semiconductor substrate 110. The photoelectric conversion device 91 includes a plurality of photoelectric conversion devices 90-2 and 90-3, and the plurality of photoelectric conversion devices 90-2 and 90-3 may be arranged to overlap with each other in a direction extending parallel to a surface 110a of the semiconductor substrate 110. The plurality of photoelectric conversion devices 90-1, 90-2, and 90-3 may convert light within different wavelength spectrums (e.g., blue light, green light, or red light) into electrical signals.

[0413] As an example, the photoelectric conversion device 90-1 may include a plurality of photoelectric conversion devices arranged horizontally and configured to absorb light in different wavelength spectrums. As an example, the photoelectric conversion device 91 may photoelectrically convert light of a wavelength spectrum selected from blue light, green light, and red light. As an example, the photoelectric conversion device 91 may partially or completely overlap with the photoelectric conversion device 90-1. Other configurations of the organic CMOS image sensor 1200 may be similar to those described in reference to FIG. Figure 3-8 One or more of the described image sensors are the same.

[0414] Figure 12 is a cross-sectional view showing another example of an image sensor according to some example embodiments.

[0415] Reference Figure 12 The image sensor 1300 includes: a semiconductor substrate 110 integrated with light sensing devices 150a and 150b, a transfer transistor (not shown), and a charge storage 155; an upper insulating layer 80 and a color filter layer 70 disposed on the semiconductor substrate 110; a lower insulating layer 60 and a photoelectric conversion device 90 disposed below the semiconductor substrate 110. The photoelectric conversion device 90 may be the aforementioned photoelectric conversion device 100. Figure 12 As shown in FIG, the photoelectric conversion device 90 is provided below the semiconductor substrate 110, and thus the photoelectric conversion device 90 and the color filter layer 70 are separated relative to the light sensing devices 150a and 150b. Other configurations of the image sensor 1300 may be the same as those of the reference image sensor 1300. Figure 3-8 One or more of the described image sensors are the same.

[0416] The aforementioned photoelectric conversion device and sensor may be applied to various electronic devices such as mobile phones, cameras, biometric devices, and / or automotive electronic components, but is not limited thereto.

[0417] Figure 13 is a schematic diagram showing an electronic device according to some example embodiments.

[0418] Reference Figure 13 , the electronic device 1700 may include a processor 1720, a memory 1730, and a sensor 1740 electrically coupled (connected) together via a bus 1710. The sensor 1740 may be a sensor according to any of the example embodiments (e.g., an image sensor). The memory 1730 may be a non-transitory computer-readable medium that may store an instruction program. The processor 1720 may execute the stored instruction program to implement one or more functions. In some example embodiments, the processor 1720 may be configured to process the electrical signals generated by the sensor 1740. The processor 1720 may be configured to generate an output (e.g., an image to be displayed on a display interface) based on, for example, the processing.

[0419] Hereinafter, some example embodiments are described in more detail with reference to Examples, but the present scope is not limited to these Examples.

[0420] Synthesis Example

[0421] Synthesis Example 1

[0422] [Compound 1]

[0423]

[0424] [Reaction Scheme 1]

[0425]

[0426] (i) Synthesis of Compound I-1

[0427] 2-Iodotellurophene (Compound I-1) was synthesized according to the method disclosed in Efficient Synthesis of 2-Iodo and 2-Dicyanomethyl Derivatives of Thiophene, Selenophene, Tellurophene and Thieno[3,2-b]thiophene, K. Takahashi, S. Tarutani, Heterocycles 1996, 43, 1927-1935.

[0428] (ii) Synthesis of Compound I-2

[0429] 15.0 g (49.1 mmol) of 2-iodotellurophene (Compound I-1) and 10.0 g (44.6 mmol) of 10,10-dimethyl-5,10-dihydrodibenzo[b,e][1,4]azasilane were heated and refluxed in 200 ml of anhydrous toluene in the presence of 5 mol% of bis(dibenzylideneacetone)palladium(0) (Pd(dba)2), 5 mol% of tri-tert-butylphosphine (P(tBu)3) (based on 10,10-dimethyl-5,10-dihydrodibenzo[b,e][1,4]azasilane), and 12.9 g (133.9 mmol) of sodium tert-butoxide (NaOtBu) for 2 hours. The product obtained therefrom was separated and purified by silica gel column chromatography (toluene:hexane=1:4 volume ratio) to obtain 6.8 g (37.8% yield) of 10,10-dimethyl-5-(tellurophen-2-yl)-5,10-dihydrodibenzo[b,e][1,4]azasilacyclohexane (Compound I-2).

[0430] (iii) Synthesis of Compound I-3

[0431] 6.2ml of phosphorus oxychloride was added dropwise to 30.0ml of N, N-dimethylformamide at -15°C, and then stirred at room temperature of 24°C for 2 hours. The resulting mixture was slowly added dropwise to a mixture of 300ml of dichloromethane and 6.8g of compound I-2 at -15°C, then stirred at room temperature for 30 minutes and concentrated under reduced pressure. 300ml of water was added thereto, and a sodium hydroxide aqueous solution was added thereto until the pH became 14, and then stirred at room temperature (24°C) for 2 hours. The organic layer extracted with dichloromethane was washed with a sodium chloride aqueous solution and then dried over anhydrous magnesium sulfate. The product obtained therefrom was separated and purified by silica gel column chromatography (hexane:ethyl acetate = 4:1 volume ratio) to obtain 2.82 g (38.8% yield) of 5-(10,10-dimethyldibenzo[b,e][1,4]azasilan-5(10H)-yl)tellurphene-2-carbaldehyde (Compound I-3).

[0432] (iv) Synthesis of Compound 1

[0433] 2.82 g (6.54 mmol) of compound I-3 was suspended in ethanol, and 1.35 g (7.85 mmol) of 1,3-dimethyl-2-thiobarbituric acid was added thereto, and then reacted therewith at 50° C. for 2 hours to obtain 2.98 g (77.8% yield) of compound 1 (5-((5-(10,10-dimethyldibenzo[b,e][1,4]azasilan-5(10H)-yl)tellurphen-2-yl)methylene)-1,3-dimethyl-2-thiodihydropyrimidine-4,6(1H,5H)-dione). The obtained compound was sublimed and purified to a purity of 99.9%.

[0434] 1 H-NMR (500 MHz, dichloromethane-d2): δ 8.46 (s, 1H), 8.26 (d, 1H), 7.80 (d, 2H), 7.71 (d, 2H), 7.54 (t, 2H), 7.42 (t, 2H), 6.93 (d, 1H), 3.68 (d, 6H), 0.45 (s, 6H).

[0435] Synthesis Example 2

[0436] [Compound 2]

[0437]

[0438] [Reaction Scheme 2]

[0439]

[0440] (i) Synthesis of Compound I-4

[0441] 2-Iodoselenophene (Compound I-4) was synthesized by referring to the method disclosed in Efficient Synthesis of 2-Iodo and 2-Dicyanomethyl Derivatives of Thiophene, Selenophene, Tellurophene and Thieno[3,2-b]thiophene, K. Takahashi, S. Tarutani, Heterocycles 1996, 43, 1927-1935.

[0442] (ii) Synthesis of Compound I-5

[0443] 10.0 g (38.9 mmol) of 2-iodoselenophene (Compound I-4) and 8.04 g (35.4 mmol) of 3-fluoro-9,9-dimethyl-9,10-dihydroacridine were heated and refluxed in 200 ml of anhydrous toluene in the presence of 5 mol% Pd(dba)2, 5 mol% P(tBu)3, and 10.2 g (106.2 mmol) of NaOtBu for 2 hours. 3-Fluoro-9,9-dimethyl-9,10-dihydroacridine was synthesized according to the method described in Preparation and Some Reactions of Phenoxazine and Phenoselenazine, Paulette Muller, N.P. Buu-Hol, and R. RIPS, J. Org. Chem., 1959, 24, 37-39. The product obtained therefrom was separated and purified by silica gel column chromatography (toluene:hexane=1:4 volume ratio) to obtain 6.8 g (53.9% yield) of 2-fluoro-9,9-dimethyl-10-(selenophene-2-yl)-9,10-dihydroacridine (Compound I-5).

[0444] (iii) Synthesis of Compound I-6

[0445] 5.2 ml of phosphorus oxychloride was added dropwise to 10.0 ml of N, N-dimethylformamide at -15 ° C, and then stirred at room temperature (24 ° C) for 2 hours. The resulting mixture was slowly added dropwise to a mixture of 150 ml of dichloromethane and 5.0 g of compound I-5 at -15 ° C, then stirred at room temperature for 30 minutes and concentrated under reduced pressure. Subsequently, 300 ml of water was added thereto, and then, a sodium hydroxide aqueous solution was added thereto until the pH became 14, and then stirred at room temperature (24 ° C) for 2 hours. The organic layer extracted with dichloromethane was washed with a sodium chloride aqueous solution and then dried over anhydrous magnesium sulfate. The product obtained therefrom was separated and purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1 volume ratio) to obtain 2.24 g (39.9% yield) of 5- (2-fluoro-9,9-dimethylacridine-10 (9H) -yl) selenophene-2-carboxaldehyde (compound I-6).

[0446] (iv) Synthesis of Compound 2

[0447] 1.30 g (3.37 mmol) of compound I-6 was suspended in ethanol, and 0.64 g (3.71 mmol) of 1,3-dimethyl-2-thiobarbituric acid was added thereto, and then reacted therewith at 50° C. for 2 hours to obtain 1.12 g (83.8% yield) of compound 2 (5-((5-(3-fluoro-9,9-dimethylacridin-10(9H)-yl)selenophene-2-yl)methylene)-1,3-dimethyl-2-thiodihydropyrimidine-4,6(1H,5H)-dione). The obtained compound was sublimed and purified to a purity of 99.9%.

[0448] 1 H-NMR (500 MHz, dichloromethane-d2): δ 8.52 (s, 1H), 7.99 (d, 1H), 7.84 (d, 1H), 7.55 (m, 3H), 7.47 (t, 1H), 7.45 (t, 1H), 7.14 (d, 1H), 7.11 (t, 1H), 5.65 (d, 6H), 1.55 (s, 6H).

[0449] Synthesis Example 3

[0450] [Compound 3]

[0451]

[0452] [Reaction Scheme 3]

[0453]

[0454] (i) Synthesis of Compound I-7

[0455] 2-Iodotellurophene (Compound I-7) was synthesized by referring to the method disclosed in Efficient Synthesis of 2-Iodo and 2-Dicyanomethyl Derivatives of Thiophene, Selenophene, Tellurophene and Thieno[3,2-b]thiophene, Takahashi, K.; Tarutani, S. Heterocycles 1996, 43, 1927-1935.

[0456] (ii) Synthesis of Compound I-8

[0457] 10.0 g (38.9 mmol) of 2-iodotellurophene (Compound I-7) and 8.62 g (35.38 mmol) of 3-fluoro-10,10-dimethyl-5,10-dihydrodibenzo[b,e][1,4]azasilane were heated and refluxed in 200 ml of anhydrous toluene in the presence of 5 mol% Pd(dba)2, 5 mol% P(tBu)3, and 10.2 g (106.2 mmol) of NaOtBu for 2 hours. 3-Fluoro-10,10-dimethyl-5,10-dihydrodibenzo[b,e][1,4]azasilane was synthesized with reference to the method disclosed in Y. Kitamoto, T. Namikawa, T. Suzuki, Y. Miyata, H. Kita, T. Sato, S. Oi. Tetrahedron Letters, 2016, 57, 4914-4917. The product obtained therefrom was separated and purified by silica gel column chromatography (toluene: hexane = 1:4 volume ratio) to obtain 6.5 g (49.5% yield) of 3-fluoro-10,10-dimethyl-5-(tellurophen-2-yl)-5,10-dihydrodibenzo[b,e][1,4]azasilane (Compound I-8).

[0458] (iii) Synthesis of Compound I-9

[0459] 4.9ml of phosphorus oxychloride was added dropwise to 8.4ml of N, N-dimethylformamide at -15°C, and then stirred for 2 hours at room temperature (24°C). The resulting mixture was slowly added dropwise to a mixture of 160ml of dichloromethane and 5.0g of compound I-8 at -15°C, then stirred at room temperature for 30 minutes and concentrated under reduced pressure. Subsequently, 300ml of water was added thereto, and a sodium hydroxide aqueous solution was added thereto until the pH became 14, and then stirred for 2 hours at room temperature (24°C). The organic layer extracted with dichloromethane was washed with a sodium chloride aqueous solution and then dried over anhydrous magnesium sulfate. The product obtained therefrom was separated and purified by silica gel column chromatography (hexane:ethyl acetate = 4:1 volume ratio) to obtain 2.30 g (42.8% yield) of 5-(3-fluoro-10,10-dimethyldibenzo[b,e][1,4]azasilanol-5(10H)-yl)tellurphene-2-carbaldehyde (Compound I-9).

[0460] (iv) Synthesis of Compound 3

[0461] 1.2 g (2.28 mmol) of compound I-9 was suspended in ethanol, and 0.33 g (2.51 mmol) of 1,3-dimethyl-2-thiobarbituric acid was added thereto and reacted therewith at 50° C. for 2 hours to obtain 0.92 g (72.8% yield) of compound 3 (5-((5-(3-fluoro-10,10-dimethyldibenzo[b,e][1,4]azasilan-5(10H)-yl)tellurphen-2-yl)methylene)-1,3-dimethyl-2-thiodihydropyrimidine-4,6(1H,5H)-dione). The obtained compound was sublimed and purified to a purity of 99.9%.

[0462] 1 H-NMR (500 MHz, dichloromethane-d2): δ8.46 (s, 1H), 8.26 (d, 1H), 7.78 (d, 2H), 7.70 (d, 2H), 7.56 (t, 1H), 7.42 (t, 2H), 6.93 (d, 1H), 3.68 (d, 6H), 0.45 (s, 6H).

[0463] Synthesis Example 4

[0464] [Compound 4]

[0465]

[0466] [Reaction Scheme 4]

[0467]

[0468] (i) Synthesis of Compound I-10

[0469] 2-Iodoselenophene (Compound I-10) was synthesized by referring to the method disclosed in Efficient Synthesis of 2-Iodo and 2-Dicyanomethyl Derivatives of Thiophene, Selenophene, Tellurophene and Thieno[3,2-b]thiophene, K. Takahashi, S. Tarutani, Heterocycles 1996, 43, 1927-1935.

[0470] (ii) Synthesis of Compound I-11

[0471] 10.0 g (38.9 mmol) of 2-iodoselenophene (Compound I-10) and 8.04 g (35.4 mmol) of 3-fluoro-9,9-dimethyl-9,10-dihydroacridine were heated and refluxed in 200 ml of anhydrous toluene in the presence of 5 mol% Pd(dba)2, 5 mol% P(t-Bu)3, and 10.2 g (106.2 mmol) of NaOtBu for 2 hours. 3-Fluoro-9,9-dimethyl-9,10-dihydroacridine was synthesized according to the method described in Preparation and Some Reactions of Phenoxazine and Phenoselenazine, Paulette Muller, N.P. Buu-Hol, and R. RIPS, J. Org. Chem., 1959, 24, 37-39. The product obtained therefrom was separated and purified by silica gel column chromatography (toluene:hexane=1:4 volume ratio) to obtain 6.8 g (53.9% yield) of 2-fluoro-9,9-dimethyl-10-(selenophene-2-yl)-9,10-dihydroacridine (Compound I-11).

[0472] (iii) Synthesis of Compound I-12

[0473] 5.2ml of phosphorus oxychloride was added dropwise to 10.0ml of N, N-dimethylformamide at -15°C, and then stirred for 2 hours at room temperature (24°C). The resulting mixture was slowly added dropwise to a mixture of 150ml of dichloromethane and 5.0g of compound I-11 at -15°C, then stirred at room temperature for 30 minutes and concentrated under reduced pressure. Subsequently, 300ml of water was added thereto, and then, a sodium hydroxide aqueous solution was added thereto until the pH became 14, and then stirred for 2 hours at room temperature (24°C). The organic layer extracted with dichloromethane was washed with a sodium chloride aqueous solution and then dried over anhydrous magnesium sulfate. The product obtained therefrom was separated and purified by silica gel column chromatography (hexane:ethyl acetate = 4:1 volume ratio) to obtain 2.24 g (39.9% yield) of 5-(2-fluoro-9,9-dimethylacridin-10(9H)-yl)selenophene-2-carbaldehyde (Compound I-12).

[0474] (iv) Synthesis of Compound 4

[0475] 0.94 g (2.44 mmol) of compound I-12 was suspended in ethanol, and 0.37 g (2.56 mmol) of 1,3-dihydroindanedione was added thereto, followed by reaction at 50° C. for 2 hours to obtain 1.02 g (81.6% yield) of compound 4 (2-((5-(3-fluoro-9,9-dimethylacridin-10(9H)-yl)selenophene-2-yl)methylene)-1H-indene-1,3(2H)-dione). The obtained compound was sublimed and purified to a purity of 99.9%.

[0476] 1 H-NMR (500 MHz, dichloromethane-d2): δ 8.48 (s, 1H), 7.74 (t, 4H), 7.42-7.34 (m, 4H), 7.24-7.19 (m, 4H), 6.82 (d, 1H), 0.48 (s, 6H).

[0477] Evaluation I

[0478] The energy levels of the compounds of Synthesis Examples were evaluated.

[0479] The energy levels were evaluated by simulation using Gaussian software (Gaussian, Inc.).

[0480] Table 1

[0481]

[0482] Manufacturing of photoelectric conversion devices

[0483] Example 1

[0484] An anode with a thickness of 150 nm was formed by sputtering ITO on a glass substrate. Subsequently, the compound represented by Chemical Formula 2B-1aa was deposited on the anode to form an electron blocking layer with a thickness of 5 nm. On this electron blocking layer, Compound 1 (first material 30p) obtained in Synthesis Example 1 (λ 最大 :545nm)、fullerene (C 60 , second material 30n) and compound 2 obtained in Synthesis Example 2 (third material 30v) (λ 最大 :530nm) co-deposited to form a 95nm thick photoelectric conversion layer. Here, the first material 30p and the second material 30n are co-deposited with a volume ratio (thickness ratio) of 1:1, and the third material 30v is co-deposited in an amount of 3 volume %, based on the total volume of the first material 30p and the third material 30v. Then, on the photoelectric conversion layer, Yb is thermally deposited to form a 1.5nm thick electronic auxiliary layer. Then, on the electronic auxiliary layer, ITO is sputtered to form a 7nm thick cathode. Subsequently, on the cathode, aluminum oxide (Al2O3) is deposited to form a 50nm thick anti-reflection layer, which is then sealed with a glass plate and thus a photoelectric conversion device is manufactured.

[0485] [Chemical Formula 2B-1aa]

[0486]

[0487] Example 2

[0488] A photoelectric conversion device was manufactured according to the same method as in Example 1, except that a 105 nm thick photoelectric conversion layer was formed by co-depositing 5 volume % of the third material 30v based on the total volume of the first material 30p and the third material 30v.

[0489] Example 3

[0490] A photoelectric conversion device was manufactured according to the same method as in Example 1, except that a 94 nm thick photoelectric conversion layer was formed by co-depositing 10 volume % of the third material 30v based on the total volume of the first material 30p and the third material 30v.

[0491] Example 4

[0492] A photoelectric conversion device was manufactured according to the same method as in Example 1, except that a 99 nm thick photoelectric conversion layer was formed by co-depositing 33 volume % of the third material 30v based on the total volume of the first material 30p and the third material 30v.

[0493] Example 5

[0494] A photoelectric conversion device was manufactured according to the same method as in Example 1, except that an 88 nm thick photoelectric conversion layer was formed by co-depositing 50 volume % of the third material 30v based on the total volume of the first material 30p and the third material 30v.

[0495] Comparative Example 1

[0496] A photoelectric conversion device was manufactured according to the same method as in Example 1, except that a 102 nm thick photoelectric conversion layer was formed by co-depositing the first material 30 p and the third material 30 v without the third material 30 v .

[0497] Comparative Example 2

[0498] A photoelectric conversion device was manufactured according to the same method as in Example 1, except that a 102 nm thick photoelectric conversion layer was formed by co-depositing the second material 30 n and the third material 30 v without the first material 30 p .

[0499] Evaluation II

[0500] The light absorption characteristics of the photoelectric conversion devices according to Examples and Comparative Examples were evaluated.

[0501] Light absorption properties were evaluated in ultraviolet-visible (UV-Vis) spectroscopy by using a Cary 5000 UV spectrometer (Varian Medical Systems Inc.).

[0502] The results are shown in Table 2.

[0503] Table 2

[0504] <![CDATA[λ 最大 (nm)]]> FWHM(nm) Example 3 540 97.4 Example 4 540 101 Comparative Example 1 540 106 Comparative Example 2 530 106

[0505] Referring to Table 2, the photoelectric conversion device according to the embodiment exhibited improved wavelength selectivity without a change in the maximum absorption wavelength, compared with the photoelectric conversion device of the comparative example.

[0506] Evaluation III

[0507] The electrical characteristics of the photoelectric conversion devices according to Examples and Comparative Examples were evaluated.

[0508] The incident photon-current efficiency (IPCE) method can be used to determine the peak absorption wavelength (λ 最大 ) was used to evaluate the photoelectric conversion efficiency.

[0509] The results are shown in Table 3.

[0510] Table 3

[0511] <![CDATA[EQE(λ 最大 ,%)]]> Example 1 70 Example 2 71 Example 3 69 Example 4 68 Comparative Example 1 69 Comparative Example 2 52

[0512] Referring to Table 3, the photoelectric conversion device of the embodiment exhibited equal or improved external quantum efficiency compared to the photoelectric conversion device of the comparative example.

[0513] Evaluation IV

[0514] The residual charge carrier characteristics of the photoelectric conversion devices according to the examples and comparative examples were evaluated.

[0515] The residual charge carrier characteristic represents the amount of charge that is photoelectrically converted in one frame but not used and remains in the next frame, and was evaluated by irradiating photoelectrically convertible light of a green wavelength spectrum to the devices of the examples and comparative examples and turning off the light, and then obtaining a 10 -6 The amount of current measured in seconds. The amount of residual electrons is measured in h+ / s / μm 2 Units are rated at 5000 lux.

[0516] The results are shown in Table 4.

[0517] Table 4

[0518]

[0519] Referring to Table 4, the photoelectric conversion device according to the embodiment exhibited improved residual charge characteristics compared to the photoelectric conversion device according to the comparative example.

[0520] Rating V

[0521] The photoelectric conversion devices according to Examples and Comparative Examples were evaluated for heat resistance properties.

[0522] Heat resistance properties were evaluated by examining changes in each of external quantum efficiency and residual charge after annealing the photoelectric conversion devices according to Examples and Comparative Examples at 180° C. for 3 hours, 190° C. for 1 hour, and 200° C. for 1 hour.

[0523] The results are shown in Tables 5 and 6.

[0524] Table 5

[0525]

[0526] *Unmeasurable: Due to damage to the film, electrical properties are not measurable

[0527] Table 6

[0528]

[0529] *Unmeasurable: Due to damage to the film, electrical properties are not measurable

[0530] Referring to Tables 5 and 6, the photoelectric conversion devices according to the embodiments exhibited high heat resistance and thus considerably improved residual charge characteristics as well as no large change in electrical characteristics without damage to the thin films after annealing them at a high temperature of about 200°C.

[0531] While the present disclosure has been described with respect to what are presently considered to be practical example embodiments, it is to be understood that the inventive concepts are not limited to the disclosed embodiments, but are intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. Photoelectric conversion devices, including: a first electrode and a second electrode; as well as a photoelectric conversion layer between the first electrode and the second electrode, The photoelectric conversion layer comprises: a first material and a second material, the first material and the second material being configured to collectively define a pn junction, and a third material different from the first material and the second material, the third material including an electron-withdrawing group, The third material is an organic material including an electron-donating portion, an electron-accepting portion, and a π-conjugated connecting portion, wherein the π-conjugated connecting portion connects the electron-donating portion and the electron-accepting portion, and The electron donating moiety includes the electron withdrawing group.

2. The photoelectric conversion device according to claim 1 , wherein the electron-withdrawing group comprises a halogen; a cyano group; a nitro group; a C1-C30 alkyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a C1-C30 alkoxy group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a C3-C30 cycloalkyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a C6-C30 aryl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; or a C3-C30 heteroaryl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof. The photoelectric conversion device according to claim 1 , wherein the electron-withdrawing group comprises a fluorine group, a cyano group, or a combination thereof.

4. The photoelectric conversion device according to claim 1, wherein the third material is represented by Chemical Formula 1-1: [Chemical Formula 1-1] in, In Chemical Formula 1-1, X 1 For O, S, Se, Te, SO, SO2, CO, CR'R", NR'", SiR a R b , or GeR c R d , EDM3 is the electron-donating part, EAM3 is the electron-accepting part, R 1 、R 2 , R', R", R'", and R a 、R b 、R c , and R d are independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and R 1 and R 2 , R' and R", R a and R b , and R c and R d exist independently or are connected to each other to form a ring, X 1 、EDM3、R 1 、R 2 , and EAM3 exist independently or two adjacent thereof are connected to each other to form a ring, and EDM3, EAM3, R 1 、R 2 , R', R", R'", R a 、R b 、R c , or R d At least one of the molecules comprises an electron-withdrawing group.

5. The photoelectric conversion device according to claim 4, wherein the third material is represented by one of Chemical Formulas 1-2 to 1-4: in, In Chemical Formulas 1-2 to 1-4, X 1 For O, S, Se, Te, SO, SO2, CO, CR'R", NR'", SiR a R b , or GeR c R d , EAM3 is the electron-accepting part, Ar in Chemical Formula 1-2 1 and Ar 2 are independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl, Ar in Chemical Formula 1-2 1 or Ar 2 At least one of the groups is a C1-C30 alkyl group substituted by halogen, cyano, nitro, or a combination thereof; a C1-C30 alkoxy group substituted by halogen, cyano, nitro, or a combination thereof; a C3-C30 cycloalkyl group substituted by halogen, cyano, nitro, or a combination thereof; a C6-C30 aryl group substituted by halogen, cyano, nitro, or a combination thereof; or a C3-C30 heteroaryl group substituted by halogen, cyano, nitro, or a combination thereof, Ar in chemical formulas 1-3 1 and Ar 2 are independently substituted or unsubstituted C1-C30 alkylene, substituted or unsubstituted C3-C30 cycloalkylene, substituted or unsubstituted C6-C30 arylene, or substituted or unsubstituted C3-C30 heteroarylene, Ar in chemical formulas 1-3 1 or Ar 2 At least one of the groups is a C1-C30 alkylene group substituted by halogen, cyano, nitro, or a combination thereof; a C3-C30 cycloalkylene group substituted by halogen, cyano, nitro, or a combination thereof; a C6-C30 arylene group substituted by halogen, cyano, nitro, or a combination thereof; or a C3-C30 heteroarylene group substituted by halogen, cyano, nitro, or a combination thereof, Ar 3 is a nitrogen-containing cyclic group substituted by halogen, cyano, nitro, or a combination thereof, G is a single bond, -O-, -S-, -Se-, -Te-, -N=, or -NR e -, where n2 is 1 or 2 -(CR f R g ) n2 -、-SiR h R i -、-GeR j R k -、-(C(R l )=C(R m ))-, or SnR n R o ,as well as R 1 、R 2 , R', R", R'", R a 、R b 、R c 、R c 、R d 、R e 、R f 、R g 、R h 、R i 、R j 、R k 、R l 、R m 、R n , and R o are independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and R 1 and R 2 , R' and R", R a and R b 、R c and R d 、R f and R g 、R h and R i 、R j and R k 、R l and R m , and R n and R o They may exist independently or be linked to each other to form a ring.

6. The photoelectric conversion device according to claim 5, wherein Ar 1 or Ar 2 At least one of the phenyl groups is substituted by halogen, cyano, nitro, or a combination thereof; naphthyl is substituted by halogen, cyano, nitro, or a combination thereof; anthracenyl is substituted by halogen, cyano, nitro, or a combination thereof; phenanthrenyl is substituted by halogen, cyano, nitro, or a combination thereof; pyridinyl is substituted by halogen, cyano, nitro, or a combination thereof; pyridazinyl is substituted by halogen, cyano, nitro, or a combination thereof; pyrimidinyl is substituted by halogen, cyano, nitro, or a combination thereof; pyrazinyl is substituted by halogen, cyano, nitro, or a combination thereof; quinolyl is substituted by halogen, cyano, nitro, or a combination thereof; isoquinolinyl substituted with halogen, cyano, nitro, or a combination thereof; naphthyridinyl substituted with halogen, cyano, nitro, or a combination thereof; cinnolinyl substituted with halogen, cyano, nitro, or a combination thereof; quinazolinyl substituted with halogen, cyano, nitro, or a combination thereof; phthalazinyl substituted with halogen, cyano, nitro, or a combination thereof; benzotriazinyl substituted with halogen, cyano, nitro, or a combination thereof; pyridopyrazinyl substituted with halogen, cyano, nitro, or a combination thereof; pyridopyrimidinyl substituted with halogen, cyano, nitro, or a combination thereof; or pyridopyridazinyl substituted with halogen, cyano, nitro, or a combination thereof, and Ar in chemical formula 1-3 1 or Ar 2 At least one of them is a phenylene substituted by halogen, cyano, nitro, or a combination thereof; a naphthylene substituted by halogen, cyano, nitro, or a combination thereof; an anthrylene substituted by halogen, cyano, nitro, or a combination thereof; a phenanthrenyl substituted by halogen, cyano, nitro, or a combination thereof; a pyridinyl substituted by halogen, cyano, nitro, or a combination thereof; a pyridazinyl substituted by halogen, cyano, nitro, or a combination thereof; a pyrimidinyl substituted by halogen, cyano, nitro, or a combination thereof; a pyrazinyl substituted by halogen, cyano, nitro, or a combination thereof; a quinolyl substituted by halogen, cyano, nitro, or a combination thereof; , nitro, or a combination thereof; isoquinolinylene substituted by halogen, cyano, nitro, or a combination thereof; naphthyridinylene substituted by halogen, cyano, nitro, or a combination thereof; cinnolinylene substituted by halogen, cyano, nitro, or a combination thereof; quinazolinylene substituted by halogen, cyano, nitro, or a combination thereof; phthalazinylene substituted by halogen, cyano, nitro, or a combination thereof; benzotriazinylene substituted by halogen, cyano, nitro, or a combination thereof; pyridopyrazinylene substituted by halogen, cyano, nitro, or a combination thereof; pyridopyrimidinylene substituted by halogen, cyano, nitro, or a combination thereof; or pyridopyridazinylene substituted by halogen, cyano, nitro, or a combination thereof.

7. The photoelectric conversion device according to claim 5, wherein Ar 1 or Ar 2 at least one of which is fluorine-substituted phenyl, fluorine-substituted naphthyl, fluorine-substituted anthracenyl, fluorine-substituted phenanthrenyl, fluorine-substituted pyridinyl, fluorine-substituted pyridazinyl, fluorine-substituted pyrimidinyl, fluorine-substituted pyrazinyl, fluorine-substituted quinolyl, fluorine-substituted isoquinolyl, fluorine-substituted naphthyridinyl, fluorine-substituted cinnolinyl, fluorine-substituted quinazolinyl, fluorine-substituted phthalazinyl, fluorine-substituted benzotriazinyl, fluorine-substituted pyridopyrazinyl, fluorine-substituted pyridopyrimidinyl, or fluorine-substituted pyridopyridazinyl, and Ar in chemical formula 1-3 1 or Ar 2 At least one of the fluorine-substituted phenylene, fluorine-substituted naphthylene, fluorine-substituted anthrylene, fluorine-substituted phenanthrenylene, fluorine-substituted pyridinylene, fluorine-substituted pyridazinylene, fluorine-substituted pyrimidinylene, fluorine-substituted pyrazinylene, fluorine-substituted quinolylene, fluorine-substituted isoquinolylene, fluorine-substituted naphthyridinylene, fluorine-substituted cinnolinylene, fluorine-substituted quinazolinylene, fluorine-substituted phthalazinylene, fluorine-substituted benzotriazinylene, fluorine-substituted pyridopyrazinylene, fluorine-substituted pyridopyrimidinylene, or fluorine-substituted pyridopyridazinylene.

8. The photoelectric conversion device according to claim 5, wherein the third material is represented by Chemical Formula 1-2a or 1-3a: in, In Chemical Formula 1-2a or 1-3a, X 1 For O, S, Se, Te, SO, SO2, CO, CR'R", NR'", SiR a R b , or GeR c R d , EAM3 is the electron-accepting part, G is a single bond, -O-, -S-, -Se-, -Te-, -N=, or -NR e -, where n2 is 1 or 2 -(CR f R g ) n2 -、-SiR h R i -、-GeR j R k -、-(C(R l )=C(R m ))-, or SnR n R o , R 1 、R 2 , R', R", R'", R a 、R b 、R c 、R c 、R d 、R e 、R f 、R g 、R h 、R i 、R j 、R k 、R l 、R m 、R n 、R o 、R 7f 、R 7g 、R 7h 、R 7i 、R 7j 、R 8f 、R 8g 、R 8h 、R 8i , or R 8j are independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, R 7f 、R 7g 、R 7h 、R 7i , and R 7j exist independently or two adjacent thereof are connected to each other to form a fused ring, R 8f 、R 8g 、R 8h 、R 8i , and R 8j exist independently or two adjacent thereof are connected to each other to form a fused ring, and R 7f 、R 7g 、R 7h 、R 7i 、R 7j 、R 8f 、R 8g 、R 8h 、R 8i , or R 8j At least one of is an electron-withdrawing group, and the electron-withdrawing group includes halogen; cyano group; Nitro; C1-C30 alkyl substituted by halogen, cyano, nitro, or a combination thereof; C1-C30 alkoxy substituted by halogen, cyano, nitro, or a combination thereof; C3-C30 cycloalkyl substituted by halogen, cyano, nitro, or a combination thereof; C6-C30 aryl substituted by halogen, cyano, nitro, or a combination thereof; or C3-C30 heteroaryl substituted by halogen, cyano, nitro, or a combination thereof.

9. The photoelectric conversion device of claim 5, wherein EAM3 is one of the groups listed in Group 1: [Group 1] in, In Group 1, Y 1 、Y 2 , and Y 3 are independently O, S, Se, Te, or C(R p )(CN), where R p is hydrogen, cyano, or C1-C10 alkyl, Ar 4 is a substituted or unsubstituted C6-C30 aromatic ring, a substituted or unsubstituted C3-C30 heteroaromatic ring, or a condensed ring of two or more substituted or unsubstituted C6-C30 aromatic rings and substituted or unsubstituted C3-C30 heteroaromatic rings, R 3 、R 4 、R 5 , and R 6 are independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, cyano, or nitro, and * indicates the connection point. 10 . The photoelectric conversion device according to claim 1 , wherein at least one of the first material or the second material is an organic material. 11 . The photoelectric conversion device according to claim 1 , wherein the first material is an organic material that does not include any electron-withdrawing group. 12 . The photoelectric conversion device according to claim 1 , wherein the first material is an organic material that does not include any fluorine. 13 . The photoelectric conversion device according to claim 1 , wherein a highest occupied molecular orbital (HOMO) energy level of the third material is between the HOMO energy level of the first material and the HOMO energy level of the second material.

14. The photoelectric conversion device according to claim 13, wherein The HOMO energy level of the first material is 5.0 eV to 5.8 eV, The HOMO energy level of the second material is 6.2 eV to 7.2 eV, and The HOMO energy level of the third material is 5.1 eV to 6.5 eV. 15 . The photoelectric conversion device according to claim 1 , wherein the photoelectric conversion layer comprises a mixture of the first material, the second material, and the third material.

16. The photoelectric conversion device according to claim 1, wherein the photoelectric conversion layer comprises: a first film layer, the first film layer comprising the first material and the third material; and A second film layer includes the second material and the third material. 17 . The photoelectric conversion device according to claim 1 , wherein the third material is included in an amount less than or equal to 50 volume % based on the total volume of the first material and the third material.

18. The photoelectric conversion device according to claim 1, wherein an absorption spectrum of the photoelectric conversion layer has a maximum absorption wavelength within a first wavelength spectrum that is one of a blue wavelength spectrum, a green wavelength spectrum, a red wavelength spectrum, or an infrared wavelength spectrum, and The first material and the third material are each a light-absorbing material having a maximum absorption wavelength within the first wavelength spectrum. 19 . The photoelectric conversion device according to claim 18 , wherein a full width at half maximum (FWHM) of an absorption spectrum of the photoelectric conversion layer is smaller than the FWHM of an absorption spectrum of a thin film formed of the first material and the second material. 20 . The photoelectric conversion device according to claim 1 , wherein the photoelectric conversion layer is a ternary system of the first material, the second material, and the third material.

21. The photoelectric conversion device according to claim 1, wherein the photoelectric conversion layer comprises: a first film layer including one of the first material, the second material, or the third material and excluding the other of the first material, the second material, or the third material, and A second film layer on the first film layer, the second film layer including the other of the first material, the second material, or the third material and excluding the one of the first material, the second material, or the third material.

22. The photoelectric conversion device according to claim 21, wherein The one material is the first material, and The other material is the second material.

23. The photoelectric conversion device according to claim 21, wherein the first film layer includes both the first material and the second material and does not include the third material, and The second thin film layer includes the third material and excludes the first material and the second material.

24. The photoelectric conversion device according to claim 22, wherein Both the first film layer and the second film layer include the third material.

25. The photoelectric conversion device according to claim 21, wherein The second film layer is in direct contact with the first film layer.

26. A sensor comprising the photoelectric conversion device according to any one of claims 1 to 25.

27. The sensor of claim 26, wherein The sensor is an image sensor, and The image sensor further includes a semiconductor substrate stacked on the photoelectric conversion device.

28. An electronic device comprising the sensor according to claim 26 or 27 or the photoelectric conversion device according to any one of claims 1 to 25.

Images