Photoelectric conversion element, sensor, and electronic device

Abstract

To provide a photoelectric conversion element that can improve a charge extraction characteristic by reducing residual charges.SOLUTION: A photoelectric conversion element according to the present invention includes a first electrode, a second electrode, and a photoelectric conversion layer existing between the first electrode and the second electrode. The photoelectric conversion layer contains a first substance and a second substance that form pn junction, and a third substance that is different from the first substance and the second substance and includes an electron withdrawing group.SELECTED DRAWING: Figure 1A

Description

[Technical field]

[0001] The present invention relates to a photoelectric conversion element, a sensor, and an electronic device, and more particularly to a photoelectric conversion element, a sensor, and an electronic device that can reduce residual charge and improve charge extraction characteristics. [Background technology]

[0002] The photoelectric conversion element is an element that receives light and converts it into an electrical signal, and includes a photodiode and a phototransistor, and can be applied to a sensor or a photodetector. Sensors are required to have ever higher resolution, which has resulted in smaller pixel sizes. In the case of silicon photodiodes, which are currently the mainstream, the absorption area decreases as the pixel size becomes smaller, which can result in a decrease in sensitivity.

[0003] Therefore, research is being conducted into organic materials that can replace silicon. Organic materials have a large absorption coefficient and can selectively absorb light in a specific wavelength range depending on their molecular structure, so they can simultaneously replace photodiodes and color filters, which is advantageous for high integration.

[0004] However, organic materials can exhibit properties different from those of silicon due to their high binding energy and recombination behavior, making it difficult to accurately predict the properties of organic materials and to easily control the physical properties required for photoelectric conversion elements. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2014-17321 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in consideration of the above-mentioned problems in conventional photoelectric conversion elements, and an object of the present invention is to provide a photoelectric conversion element capable of reducing residual charges and improving charge extraction characteristics. Another object of the present invention is to provide a sensor including the photoelectric conversion element, and to provide an electronic device including the photoelectric conversion element or the sensor. [Means for solving the problem]

[0007] The photoelectric conversion element according to the present invention, which has been made to achieve the above-mentioned object, comprises a first electrode, a second electrode, and a photoelectric conversion layer disposed between the first electrode and the second electrode, wherein the photoelectric conversion layer comprises a first material and a second material forming a p-n junction, and a third material different from the first material and the second material and including an electron withdrawing group.

[0008] The third substance is an organic material including an electron donating moiety (EDM), an electron accepting moiety (EAM), and a π-conjugated linking moiety (LM) that connects the electron donating moiety and the electron accepting moiety, and it is preferable that at least one of the electron donating moiety, the electron accepting moiety, and the π-conjugated linking moiety includes the electron withdrawing group. The electron-withdrawing group preferably includes a halogen, a cyano group, a nitro group, an alkyl group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, an alkoxy group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, a cycloalkyl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, an aryl group having 6 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, or a heteroaryl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof.

[0009] The electron-withdrawing group preferably comprises fluorine, a cyano group, or a combination thereof. The electron donating moiety includes the electron withdrawing group, and the electron withdrawing group preferably includes a halogen, a cyano group, a nitro group, an alkyl group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, an alkoxy group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, a cycloalkyl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, an aryl group having 6 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, or a heteroaryl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof.

[0010] The third substance is preferably represented by the following chemical formula 1-1. [ka] (In the above chemical formula 1-1, X 1 are O, S, Se, Te, SO, and SO 2 , CO, CR'R'', NR''', SiR a R b , or GeR c R d EDM3 is the electron donating moiety, EAM3 is the electron accepting moiety, and R 1 , R 2, R', R'', R''', and R a ~R d are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; R 1 and R 2 , R' and R'', R a and R b , and R c and R d each independently exists or is joined to each other to form a ring; X 1 , EDM3, R 1 , R 2 and EAM3 are each independently present or adjacent two of them are bonded to form a ring, 1 , R 2 , R', R'', R''', and R a ~R d At least one of the groups contains an electron-withdrawing group.

[0011] The third substance is preferably represented by any one of the following chemical formulas 1-2 to 1-4. [ka] [ka] [ka] (In the above chemical formulas 1-2 to 1-4, X 1 are O, S, Se, Te, SO, and SO 2 , CO, CR'R'', NR''', SiR a R b , or GeR c R d EAM3 is the electron accepting moiety, and Ar 1 and Ar 2are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms; Ar 1 and Ar 2 at least one of the above is an alkyl group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an alkoxy group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a cycloalkyl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an aryl group having 6 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; or a heteroaryl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; 3 is a nitrogen-containing ring group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; G is a single bond, -O-, -S-, -Se-, -Te-, -N=, -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 and R 1 , R 2 , R', R'', R''', and R a ~R o are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; R 1 and R 2 , R' and R'', R a and R b , Rc 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 are present independently or are linked together to form a ring.

[0012] Ar of the above formula 1-2 or 1-3 1 and Ar 2at least one of the groups is a phenyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a naphthyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an anthracenyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a phenanthrenyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a pyridinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a pyridazinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a pyrimidinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a pyrazinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a quinolinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a halogen, a cyano group, a nitro group, or a combination thereof; a quinazolinyl group substituted with a halogen, a cyano group, a nitro group or a combination thereof; a naphthyridinyl group substituted with a halogen, a cyano group, a nitro group or a combination thereof; a cinnolinyl group substituted with a halogen, a cyano group, a nitro group or a combination thereof; a quinazolinyl group substituted with a halogen, a cyano group, a nitro group or a combination thereof; a phthalazinyl group substituted with a halogen, a cyano group, a nitro group or a combination thereof; a benzotriazinyl group substituted with a halogen, a cyano group, a nitro group or a combination thereof; a pyridopyrazinyl group substituted with a halogen, a cyano group, a nitro group or a combination thereof; a pyridopyrimidinyl group substituted with a halogen, a cyano group, a nitro group or a combination thereof; or a pyridopyridazinyl group substituted with a halogen, a cyano group, a nitro group or a combination thereof. Ar of the above formula 1-2 or 1-3 1 and Ar 2at least one of them is preferably 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 quinolinyl group, a fluorine-substituted isoquinolinyl 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.

[0013] The third substance is preferably represented by the following chemical formula 1-2a or 1-3a. [ka] [ka] (In the above chemical formula 1-2a or 1-3a, X 1 are O, S, Se, Te, SO, and SO 2 , CO, CR'R'', NR''', SiR a R b , or GeR c R d EAM3 is the electron accepting moiety, and G is a single bond, -O-, -S-, -Se-, -Te-, -N=, -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 and R 1 , R 2 , R', R'', R''', R a ~Ro , R 7f ~R 7j , and R 8f ~R 8g are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; R 7f ~R 7j each independently exists, or two adjacent ones are linked to each other to form a fused ring; R 8f ~R 8g each independently exists, or two adjacent ones are linked to each other to form a fused ring; R 7f ~R 7j and R 8f ~R 8g at least one of the groups is a halogen, a cyano group, a nitro group, an alkyl group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an alkoxy group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a cycloalkyl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an aryl group having 6 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; or a heteroaryl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof.

[0014] The EAM3 is preferably one of the groups listed in Group 1 below. [ka] (In Group 1 above, Y 1 ~Y 3 are each independently O, S, Se, Te, or C(R p )(CN)(where R p is hydrogen, a cyano group, or an alkyl group having 1 to 10 carbon atoms; 4is a substituted or unsubstituted aromatic ring having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaromatic ring having 3 to 30 carbon atoms, or two or more condensed rings selected from these, R 3 ~R 6 are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group, and * is a linking point.

[0015] At least one of the first material and the second material is preferably organic. The first substance is preferably an organic substance that does not contain an electron-withdrawing group. The first substance is preferably a fluorine-free organic substance. The HOMO energy level of the third material is preferably located between the HOMO energy level of the first material and the HOMO energy level of the second material. It is preferable that the HOMO energy level of the first substance is 5.0 eV to 5.8 eV, the HOMO energy level of the second substance is 6.2 eV to 7.2 eV, and the HOMO energy level of the third substance is 5.1 eV to 6.5 eV. The photoelectric conversion layer preferably contains a mixture of the first material, the second material, and the third material. The third substance is preferably contained in an amount of 50% by volume or less based on the total volume of the first substance and the third substance. It is preferable that the absorption spectrum of the photoelectric conversion layer has a maximum absorption wavelength in a first wavelength region, which is any one of the blue wavelength region, the green wavelength region, the red wavelength region, and the infrared wavelength region, and that the first substance and the third substance are each light-absorbing substances having a maximum absorption wavelength in the first wavelength region. The half width of the absorption spectrum of the photoelectric conversion layer is preferably narrower than the half width of the absorption spectrum of a thin film made of the first substance and the second substance. The photoelectric conversion layer is preferably a three-component system consisting of the first substance, the second substance, and the third substance.

[0016] The sensor according to the present invention, which has been made to achieve the above object, is characterized by including the photoelectric conversion element of the present invention.

[0017] It is preferable that the sensor is an image sensor, and the image sensor further includes a semiconductor substrate on which the photoelectric conversion element is stacked.

[0018] In order to achieve the above object, the present invention provides an electronic device including the sensor of the present invention.

[0019] Further, an electronic device according to the present invention, which has been made to achieve the above object, is characterized by including the photoelectric conversion element of the present invention. Effect of the Invention

[0020] According to the photoelectric conversion element, sensor, and electronic device of the present invention, it is possible to increase the wavelength selectivity of the photoelectric conversion element while simultaneously reducing residual charge and improving the charge extraction characteristics. [Brief description of the drawings]

[0021] [Figure 1A] 1 is a cross-sectional view showing an example of a schematic configuration of a photoelectric conversion element according to an embodiment of the present invention. [Figure 1B] FIG. 1B is an enlarged view of an example of region "A" of FIG. 1A. [Figure 1C] FIG. 1B is an enlarged view of another example of region "A" in FIG. 1A. [Diagram 2] FIG. 2 is a cross-sectional view showing another example of a schematic configuration of a photoelectric conversion element according to an embodiment of the present invention. [Diagram 3] 1 is a cross-sectional view showing an example of a schematic configuration of an image sensor according to an embodiment of the present invention. [Figure 4] FIG. 1 is a plan view illustrating an example of an image sensor according to an embodiment of the present invention. [Diagram 5]5 is a cross-sectional view showing an example of a schematic configuration of the image sensor shown in FIG. 4. [Figure 6] 5 is a cross-sectional view showing another example of the schematic configuration of the image sensor in FIG. [Figure 7] FIG. 11 is a plan view illustrating another example of an image sensor according to an embodiment of the present invention. [Figure 8] 8 is a cross-sectional view showing an example of a schematic configuration of the image sensor in FIG. 7. [Figure 9] FIG. 11 is a plan view illustrating another example of an image sensor according to an embodiment of the present invention. [Figure 10] 10 is a cross-sectional view showing an example of a schematic configuration of the image sensor in FIG. [Figure 11] FIG. 11 is a cross-sectional view showing another example of the schematic configuration of the image sensor according to the embodiment of the present invention. [Figure 12] FIG. 11 is a cross-sectional view showing yet another example of the schematic configuration of the image sensor according to the embodiment of the present invention. [Figure 13] 1 is a block diagram showing a schematic configuration of an electronic device according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Next, specific examples of embodiments for carrying out the semiconductor device according to the present invention will be described with reference to the drawings. However, actual applications may take many different forms and should not be construed as limited to the embodiments set forth herein.

[0023] In the drawings, the thicknesses of the various layers and regions are exaggerated for clarity. When a part such as a layer, film, region, or plate is said to be "on" another part, this includes not only the case where it is "directly on" the other part, but also the case where there is another part in between. Conversely, when one part is said to be "directly above" another, it means that there is no other part in between.

[0024] Unless otherwise defined below, "substituted" means that a hydrogen atom in a compound is replaced with a halogen atom, a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a 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 or a salt thereof, a silyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 6 to 8 carbon atoms, or a substituted or unsubstituted alkyl group having 6 to 8 carbon atoms. It means that the group is substituted with a substituent selected from an aryl group having from 7 to 30 carbon atoms, an arylalkyl group having from 7 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, a heteroalkyl group having from 1 to 20 carbon atoms, a heteroaryl group having from 3 to 20 carbon atoms, a heteroarylalkyl group having from 3 to 20 carbon atoms, a cycloalkyl group having from 3 to 30 carbon atoms, a cycloalkenyl group having from 3 to 15 carbon atoms, a cycloalkynyl group having from 6 to 15 carbon atoms, a heterocycloalkyl group having from 3 to 30 carbon atoms, and combinations thereof.

[0025] Unless otherwise defined below, "hetero" means containing 1 to 4 heteroatoms selected from N, O, S, Se, Te, Si, and P. Hereinafter, the term "combination" includes mixtures and laminated structures of two or more. Unless otherwise defined below, an energy level is the highest occupied molecular orbital (HOMO) energy level or the lowest unoccupied molecular orbital (LUMO) energy level. Unless otherwise defined below, work functions or energy levels are expressed as absolute values ​​from a vacuum level. In addition, a deep, high, or large work function or energy level means that the absolute value is large with the vacuum level being "0 eV", and a shallow, low, or small work function or energy level means that the absolute value is small with the vacuum level being "0 eV".

[0026] Hereinafter, a photoelectric conversion element according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1A is a cross-sectional view showing an example of a schematic configuration of a photoelectric conversion element according to an embodiment of the present invention, FIG. 1B is an enlarged view of an example of region "A" in FIG. 1A, and FIG. 1C is an enlarged view of another example of region "A" in FIG. 1A. Referring to FIG. 1A, a photoelectric conversion element 100 according to an embodiment of the present invention includes a first electrode 10, a second electrode 20, and a photoelectric conversion layer 30.

[0027] A substrate (not shown) is disposed on the first electrode 10 side and on the second electrode 20 side. The substrate can be, for example, an inorganic substrate such as a glass plate, a silicon wafer, or an organic substrate made of organic materials such as polycarbonate, polymethylmethacrylate, polyethyleneterephthalate, polyethylenenaphthalate, polyamide, polyethersulfone, or combinations thereof. The substrate may be omitted.

[0028] Either the first electrode 10 or the second electrode 20 is an anode, and the other is a cathode. For example, the first electrode 10 is an anode and the second electrode 20 is a cathode. For example, the first electrode 10 is a cathode and the second electrode 20 is an anode.

[0029] At least one of the first electrode 10 and the second electrode 20 is a transparent electrode. Here, the transparent electrode has a high transmittance of about 80% or more. The transparent electrode may include at least one of an oxide conductor, a carbon conductor, and a metal thin film, for example. The oxide conductor may be one or more selected from indium tin oxide (ITO), indium zinc oxide (IZO), zinc tin oxide (ZTO), aluminum tin oxide (AlTO), and aluminum zinc oxide (AZO). The carbon conductor may be one or more selected from graphene and carbon nanostructures. The metal thin film may be a very thin film including aluminum (Al), magnesium (Mg), silver (Ag), gold (Au), an alloy thereof, or a combination thereof.

[0030] Either the first electrode 10 or the second electrode 20 is a reflective electrode. The reflective electrode has, for example, a light transmittance of less than about 10% or a reflectance of about 5% or more. The reflective electrode may include a reflective conductor such as a metal, for example, aluminum (Al), silver (Ag), gold (Au), or alloys thereof. As an example, the first electrode 10 and the second electrode 20 are each a transparent electrode, and one of the first electrode 10 and the second electrode 20 is a light-receiving electrode located on the side that receives light. As an example, the first electrode 10 may be a transparent electrode, the second electrode 20 may be a reflective electrode, and the first electrode 10 may be a light-receiving electrode. As an example, 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.

[0031] The photoelectric conversion layer 30 is disposed between the first electrode 10 and the second electrode 20 . The photoelectric conversion layer 30 absorbs light in at least a portion of the wavelength range and converts it into an electrical signal, for example, converting some of the light in the blue wavelength range (hereinafter referred to as "blue light"), the light in the green wavelength range (hereinafter referred to as "green light"), the light in the red wavelength range (hereinafter referred to as "red light"), and the light in the infrared wavelength range (hereinafter referred to as "infrared light") into an electrical signal. As an example, the photoelectric conversion layer 30 selectively absorbs any one of blue light, green light, red light, and infrared light and converts it into an electrical signal.

[0032] Here, selective absorption of any one of blue light, green light, red light, and infrared light means that the absorption spectrum has a maximum absorption wavelength (λ max ) is present in any one of the wavelength regions of about 380 nm or more and less than 500 nm, about 500 nm to 600 nm, more than about 600 nm and less than 700 nm, and more than about 700 nm to 3,000 nm, and the absorption spectrum in that wavelength region is significantly higher than the absorption spectra in the other wavelength regions. Here, significantly higher means that, for example, about 70% to 100%, about 75% to 100%, about 80% to 100%, about 85% to 100%, about 90% to 100%, or about 95% to 100% of the total area of ​​the absorption spectrum belongs to that wavelength region.

[0033] Referring to FIG. 1B, the photoelectric conversion layer 30 includes a first material 30p and a second material 30n that form a pn junction (31). The first material 30p and the second material 30n absorb incident light to generate excitons, and then separate the generated excitons into holes and electrons. The first material 30p and the second material 30n are each a semiconductor, for example, the first material 30p is a p-type semiconductor and the second material 30n is an n-type semiconductor. As an example, the first material 30p and the second material 30n are each independently a light-absorbing material that absorbs light in a predetermined wavelength range, for example, at least one of the first material 30p and the second material 30n is an organic light-absorbing material. As an example, at least one of the first material 30p and the second material 30n is a wavelength-selective light-absorbing material that selectively absorbs light in a predetermined wavelength range, for example, at least one of the first material 30p and the second material 30n is a wavelength-selective organic light-absorbing material.

[0034] The absorption spectra of the first material 30p and the second material 30n may be the same as one another or may have maximum absorption wavelengths (λmax) in different wavelength regions. As an example, the absorption spectra of the first substance 30p and the second substance 30n each independently selectively absorb any one of blue light, green light, red light, and infrared light, and the maximum absorption wavelength (λmax) of the absorption spectrum of the first substance 30p or the second substance 30n may be present in any one of the wavelength regions of approximately 380 nm or more and less than 500 nm, approximately 500 nm to 600 nm, approximately more than 600 nm and less than 700 nm, and approximately more than 700 nm and less than 3,000 nm.

[0035] As an example, the first material 30p and / or the second material 30n are organic. As an example, the first substance 30p and / or the second substance 30n are low molecular weight compounds. As an example, the first material 30p and / or the second material 30n are vapor-depositable compounds. As an example, 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 (EAM).

[0036] The first substance 30p is represented by, for example, chemical formula A shown below, but is not limited thereto. (chemical A) EDM1-LM1-EAM1 ···Chemical formula A (In the above chemical formula A, EDM1 is an electron donating moiety, EAM1 is an electron accepting moiety, LM1 is a π-conjugated linking moiety that links the electron donating moiety and the electron accepting moiety.

[0037] As an example, the first substance 30p represented by chemical formula A is represented by chemical formula A-1 shown below, but is not limited thereto. [ka] (In the above chemical formula A-1, EDM1 is an electron donating moiety, EAM1 is an electron accepting moiety, X a are O, S, Se, Te, SO, and SO 2 , SiR a1 R b1 , or GeR c1 R d1 and R 1a , R 2a , and R a1 ~R d1 each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; R 1a and R 2a , R a1 and R b1 , and R c1 and R d1 may exist independently or may be linked together to form a ring.

[0038] As an example, the first substance 30p represented by chemical formula A-1 is represented by any one of chemical formulas A-2 to A-4 shown below, but is not limited thereto. [ka] [ka] [ka] (In the above chemical formulas A-2 to A-4, X a , R 1a , R 2a and EAM1 are as described above; Ar 1a and Ar 2a each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms; Ar 3a is a nitrogen-containing ring group, W is 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 R e1 ~R o1 each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; 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 o1may exist independently or may be linked together to form a ring.

[0039] As an example, Ar 1a and Ar 2a each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted naphthyridinyl group, naphthyridinyl groups, substituted or unsubstituted cinnolinyl groups, substituted or unsubstituted quinazolinyl groups, substituted or unsubstituted phthalazinyl groups, substituted or unsubstituted benzotriazinyl groups, substituted or unsubstituted pyridopyrazinyl groups, substituted or unsubstituted pyridopyrimidinyl groups, and substituted or unsubstituted pyridopyridazinyl groups.

[0040] As an example, the first substance 30p represented by chemical formula A-2 is represented, for example, by chemical formula A-2a shown below, and the first substance 30p represented by chemical formula A-3 is represented, for example, by chemical formula A-3a shown below, but is not limited to these. [ka] [ka] (In the above chemical formula A-2a or A-3a, EAM1,X a , R 1a , and R 2a is as described above, R 7a ~R 7e and R 8a ~R 8e each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; R 7a ~R 7e may exist independently, or two adjacent ones may be linked to each other to form a fused ring, R 8a ~R 8e may exist independently, or two adjacent ones may be linked to each other to form a condensed ring.

[0041] As an example, EAM1 can be, but is not limited to, one of the groups listed in Group A shown below. [ka] (Among Group A, Y 1a ~Y 3a are each independently O, S, Se, Te, or C(R p1 )(CN)(where R p1 is hydrogen, a cyano group, or an alkyl group having 1 to 10 carbon atoms; Ar 4a is a substituted or unsubstituted aromatic ring having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaromatic ring having 3 to 30 carbon atoms, or a combination of two or more fused rings selected from these, R 3a ~R 6a each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; * indicates a connection point.)

[0042] As an example, Y in group A 1a ~Y 3a Two of them are 0. As an example, Y in group A 1a and Y 2a are 0 respectively. As an example, Y in group A 1a and Y 2a are 0, and Y 3a is S. As an example, Y in group A 2a and Y 3a are 0 respectively. As an example, Ar 4a may be substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted thiophene, substituted or unsubstituted selenophene, substituted or unsubstituted tellurophene, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, or two or more fused rings selected from among these. As an example, R from Group A 3a can be hydrogen, deuterium, or a methyl group. As an example, the first material 30p may be free of electron-withdrawing groups such as halogens, cyano groups, and / or nitro groups, for example, the first material 30p may be free of fluorine.

[0043] By way of example, and without limitation, the first substance 30p can be one of the compounds listed in Group A1 below. [ka] TIFF0007630960000016.tif123144TIFF0007630960000017.tif250150TIFF0007630960000018.tif125152TIFF0007630960000019.tif245128TIFF0007630960000020.tif190129TIFF0007630960000021.tif163141TIFF0007630960000022.tif195142TIFF0007630960000023.tif132135(In group A1, R 1a , R 1b , R 11 , and R 12 each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; R 1a and R 1b are present independently or bonded to each other to form a ring.

[0044] The second material 30n can include, for example, organic, inorganic, and / or organic-inorganic, such as, but not limited to, a thiophene or thiophene derivative, a fullerene or a fullerene derivative. The photoelectric conversion layer 30 further includes a third material 30v in addition to the above-mentioned first material 30p and second material 30n. The third material 30v is a material different from the first material 30p and the second material 30n, and is a dopant capable of modifying the physical properties of the photoelectric conversion layer 30. The third material 30v may be an organic material, for example a low molecular weight compound, such as a vaporizable organic compound. As an example, the photoelectric conversion layer 30 may be a co-evaporated thin film of a first material 30p, a second material 30n, and a third material 30v.

[0045] The third material 30v may be, for example, a light-absorbing material that selectively absorbs any one of light in the blue wavelength region, the green wavelength region, the red wavelength region, and the infrared wavelength region. As an example, the absorption spectra of the first material 30p and the third material 30v may each have a maximum absorption wavelength (λmax) that commonly falls within one of the blue wavelength region, the green wavelength region, the red wavelength region, and the infrared wavelength region. As an example, the absorption spectra of first material 30p and third material 30v may each have a maximum absorption wavelength (λmax) in the blue wavelength region of approximately 380 nm or more and less than 500 nm. As an example, the absorption spectra of the first material 30p and the third material 30v may each have a maximum absorption wavelength (λmax) in the green wavelength region of approximately 500 nm to 600 nm. As an example, the absorption spectra of first material 30p and third material 30v may each have a maximum absorption wavelength (λmax) in the red wavelength region of approximately greater than 600 nm and less than or equal to 700 nm. As an example, the absorption spectra of first substance 30p and third substance 30v may each have a maximum absorption wavelength (λmax) in the infrared wavelength region of approximately more than 700 nm to 3,000 nm or less.

[0046] The third material 30v can be a small molecule compound that includes an electron withdrawing group, such as a halogen (F, Cl, Br and / or I), a cyano group and / or a nitro group. The third material 30v may be, for example, a low molecular weight compound that includes fluorine and / or a cyano group, for example, a low molecular weight compound that includes fluorine. Here, the electron-withdrawing group is a halogen, a cyano group, a nitro group, and / or a monovalent functional group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; For example, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 30 carbon atoms substituted with a halogen atom, a cyano group, a nitro group, or a combination thereof; an alkoxy group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a cycloalkyl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an aryl group having 6 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; Alternatively, it may include a heteroaryl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof.

[0047] As an example, the third material 30v may be a low molecular weight compound that includes fluorine, a monovalent functional group substituted with fluorine, a cyano group, a monovalent functional group substituted with a cyano group, or a combination thereof. As an example, the third material 30v is an organic material comprising an electron donating moiety, an electron accepting moiety, and a π-conjugated linking moiety connecting the electron donating moiety and the electron accepting moiety, and at least one of the electron donating moiety, the electron accepting moiety, and the π-conjugated linking moiety comprises an electron withdrawing group. For example, at least one of the electron donating moiety, the electron accepting moiety, and the π-conjugated linking moiety is a halogen, a cyano group, a nitro group, and / or a monovalent functional group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; For example, halogen, cyano group, nitro group, an alkyl group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an alkoxy group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a cycloalkyl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an aryl group having 6 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; Alternatively, it may include a heteroaryl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof.

[0048] As an example, at least one of the electron donating moiety, the electron accepting moiety, and the π-conjugated linking moiety can include fluorine, a monovalent functional group substituted with a fluorine, a cyano group, a monovalent functional group substituted with a cyano group, or a combination thereof. As an example, the electron donating moiety can include fluorine or a fluorine-substituted monovalent functional group. As an example, the electron accepting moiety can include fluorine or a fluorine-substituted monovalent functional group. As an example, a π-conjugated linking moiety can include fluorine or a fluorine-substituted monovalent functional group. As an example, the electron donating moieties, electron accepting moieties, and π-conjugated linking moieties can contain from 1 to 5 fluorines.

[0049] As an example, the monovalent functional group substituted with fluorine may include, but is not limited to, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkoxy group having 1 to 30 carbon atoms, a fluorine-substituted cycloalkyl group having 3 to 30 carbon atoms, a fluorine-substituted aryl group having 6 to 30 carbon atoms, and / or a fluorine-substituted heteroaryl group having 3 to 30 carbon atoms. As an example, the electron donating moiety can include a cyano group or a monovalent functional group substituted with a cyano group. As an example, the electron accepting moiety can include a cyano group or a monovalent functional group substituted with a cyano group. As an example, a π-conjugated linking moiety can include a cyano group or a monovalent functional group substituted with a cyano group. As an example, the electron donating moieties, the electron accepting moieties and the π-conjugated linking moieties can include 1 to 5 cyano groups. As an example, the monovalent functional group substituted with a cyano group may include a cyano-substituted alkyl group having 1 to 30 carbon atoms, a cyano-substituted alkoxy group having 1 to 30 carbon atoms, a cyano-substituted cycloalkyl group having 3 to 30 carbon atoms, a cyano-substituted aryl group having 6 to 30 carbon atoms, and / or a cyano-substituted heteroaryl group having 3 to 30 carbon atoms, but is not limited to these.

[0050] As an example, the third material 30v is represented by Chemical Formula 1 shown below. (chemical 1) EDM3-LM3-EAM3 ···Chemical formula 1 (In the above chemical formula A, EDM3 is an electron donating moiety, EAM3 is an electron accepting moiety, LM3 is a π-conjugated linking moiety that links an electron donating moiety and an electron accepting moiety; At least one of EDM3, EAM3, and LM3 contains an electron-withdrawing group.

[0051] As an example, the third material 30v represented by Chemical Formula 1 is represented by Chemical Formula 1-1 shown below, but is not limited thereto. [ka] (In the above chemical formula 1-1, X 1 are O, S, Se, Te, SO, and SO 2 , CO, CR'R'', NR''', SiR a R b , or GeR c R d and EDM3 is an electron donating moiety, EAM3 is an electron accepting moiety, R 1 , R 2 , R', R'', R''', and R a ~R d each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; R 1 and R 2 , R' and R'', R a and R b , and R c and Rd may each exist independently or may be linked together to form a ring; X 1 , EDM3, R 1 , R 2 and EAM3 may each be present independently, or adjacent two of them may be bonded to form a ring; EDM3, EAM3, R 1 , R 2 , R', R'', R''', and R a ~R d At least one of the groups contains an electron-withdrawing group.

[0052] As an example, EDM3 in Chemical Formula 1-1 includes an electron-withdrawing group, and for example, the third substance 30v represented by Chemical Formula 1-1 is represented by, for example, any one of Chemical Formulas 1-2 to 1-4 shown below. [ka] [ka] [ka] In the above chemical formulas 1-2 to 1-4, X 1 , R 1 , R 2 , and EAM3 are as described above, Ar 1 and Ar 2 each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms; Ar 1 and Ar 2 at least one of the above is an alkyl group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an alkoxy group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a cycloalkyl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an aryl group having 6 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; or a heteroaryl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; Ar 3 is a nitrogen-containing ring group substituted with halogen, cyano group, nitro group, or combinations thereof; G is a single bond, -O-, -S-, -Se-, -Te-, -N=, -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 and R e ~R o each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; 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 may exist independently or may be linked together to form a ring.

[0053] As an example, Ar 1 and Ar2 at least one of the groups is an aryl group having 6 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, or a heteroaryl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; For example, a phenyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a naphthyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an anthracenyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a phenanthrenyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a pyridinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a pyridazinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a pyrimidinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a pyrazinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a quinolinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an isoquinolinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a naphthyridinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a cinnolinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a quinazolinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a phthalazinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a benzotriazinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a pyridopyrazinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a pyridopyrimidinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof; or a pyridopyridazinyl group substituted with a halogen, a cyano group, a nitro group, or a combination thereof.

[0054] As an example, Ar 1 and Ar 2 At least one of the groups may be a fluorine-substituted aryl group having 6 to 30 carbon atoms or a fluorine-substituted heteroaryl group having 3 to 30 carbon atoms, and may be, for example, 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 quinolinyl group, a fluorine-substituted isoquinolinyl 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.

[0055] As an example, the third substance 30v represented by chemical formula 1-2 is represented, for example, by chemical formula 1-2a shown below, and the third substance 30v represented by chemical formula 1-3 is represented, for example, by chemical formula 1-3a shown below, but is not limited to these. [ka] [ka] (In the above chemical formula 1-2a or 1-3a, EAM3, X 1 , R 1 , R 2 , and G are as described above; R 7f ~R 7j and R 8f ~R 8geach independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; R 7f ~R 7j may exist independently, or two adjacent ones may be linked to each other to form a fused ring, R 8f ~R 8g may exist independently, or two adjacent ones may be linked to each other to form a fused ring, R 7f ~R 7j and R 8f ~R 8g at least one of the groups is an electron-withdrawing group; Here, the electron-withdrawing group is a halogen, a cyano group, a nitro group, an alkyl group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an alkoxy group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; a cycloalkyl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; an aryl group having 6 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof; Or, it may be a heteroaryl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof.)

[0056] As an example, R 7f ~R 7j Any one of may be an electron withdrawing group. As an example, R 8f ~R 8j Any one of may be an electron withdrawing group. As an example, R 7f ~R 7j Two of the groups may be electron-withdrawing groups. As an example, R 8f ~R 8j Two of the groups may be electron-withdrawing groups. As an example, R 7f ~R 7j Any one of the following and R 8f ~R 8j Any one of may be an electron withdrawing group. As an example, R 7f can be an electron withdrawing group. As an example, R 7g can be an electron withdrawing group. As an example, R 7h can be an electron withdrawing group. As an example, R 7i can be an electron withdrawing group. As an example, R 7j can be an electron withdrawing group. As an example, R 8f can be an electron withdrawing group. As an example, R 8g can be an electron withdrawing group. As an example, R 8h can be an electron withdrawing group. As an example, R 8i can be an electron withdrawing group. As an example, R 8j can be an electron withdrawing group.

[0057] As an example, R 7f ~R 7j Any one of may be fluorine or a fluorine-containing group. As an example, R 8f ~R 8j Any one of may be fluorine or a fluorine-containing group. As an example, R 7f ~R 7j Two of the groups may be fluorine or a fluorine-containing group. As an example, R 8f ~R 8j Two of the groups may be fluorine or a fluorine-containing group. As an example, R 7f ~R 7jAny one of the following and R 8f ~R 8j Any one of may be fluorine or a fluorine-containing group. As an example, R 7f can be fluorine or a fluorine-containing group. As an example, R 7g can be fluorine or a fluorine-containing group. As an example, R 7h can be fluorine or a fluorine-containing group. As an example, R 7i can be fluorine or a fluorine-containing group. As an example, R 7j can be fluorine or a fluorine-containing group. As an example, R 8f can be fluorine or a fluorine-containing group. As an example, R 8g can be fluorine or a fluorine-containing group. As an example, R 8h can be fluorine or a fluorine-containing group. As an example, R 8i can be fluorine or a fluorine-containing group. As an example, R 8j can be fluorine or a fluorine-containing group.

[0058] As an example, R 7f ~R 7j Any one of may be a cyano group or a cyano-containing group. As an example, R 8f ~R 8j Any one of may be a cyano group or a cyano-containing group. As an example, R 7f ~R 7j Two of the groups may be cyano or cyano-containing groups. As an example, R 8f ~R 8j Two of the groups may be cyano or cyano-containing groups. As an example, R 7f ~R 7j Any one of the following and R 8f ~R 8jAny one of may be a cyano group or a cyano-containing group. As an example, R 7f can be a cyano group or a cyano-containing group. As an example, R 7g can be a cyano group or a cyano-containing group. As an example, R 7h can be a cyano group or a cyano-containing group. As an example, R 7i can be a cyano group or a cyano-containing group. As an example, R 7j can be a cyano group or a cyano-containing group. As an example, R 8f can be a cyano group or a cyano-containing group. As an example, R 8g can be a cyano group or a cyano-containing group. As an example, R 8h can be a cyano group or a cyano-containing group. As an example, R 8i can be a cyano group or a cyano-containing group. As an example, R 8j can be a cyano group or a cyano-containing group.

[0059] By way of example, and not limitation, EAM3 can be one of the groups listed in Group 1 shown below. [ka] (Among Group 1 above, Y 1 ~Y 3 are each independently O, S, Se, Te, or C(R p )(CN)(where R p is hydrogen, a cyano group, or an alkyl group having 1 to 10 carbon atoms; Ar 4 represents a substituted or unsubstituted aromatic ring having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaromatic ring having 3 to 30 carbon atoms, or a combination of two or more fused rings selected from these, R 3 ~R6 each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; * indicates a connection point.)

[0060] As an example, Y in group 1 1 ~Y 3 Two of them are 0. As an example, Y in group 1 1 and Y 2 are 0 respectively. As an example, Y in group 1 1 and Y 2 are 0, and Y 3 is S. As an example, Y in group 1 2 and Y 3 are 0 respectively. As an example, Ar in group 1 4 may be substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted thiophene, substituted or unsubstituted selenophene, substituted or unsubstituted tellurophene, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, or two or more fused rings selected from among these. As an example, R in group 1 3 can be hydrogen, deuterium, or a methyl group. By way of example, and without limitation, third material 30v can be one of the compounds listed in Group A2 below. [ka] TIFF0007630960000032.tif166150TIFF0007630960000033.tif175146TIFF0007630960000034.tif116146TIFF0007630960000035.tif11414 5TIFF0007630960000036.tif115146TIFF0007630960000037.tif73145TIFF0007630960000038.tif173144TIFF0007630960000039.tif177146

[0061] 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 other physical properties required for the photoelectric conversion layer 30, for example, it may be included in an amount equal to or less than that of the first material 30p or the second material 30n. For example, the third material 30v can be contained in an amount of about 50 volume % or less relative to the total volume of the first material 30p and the third material 30v, and within the above ranges, can be contained in an amount of about 1 to 50 volume %, about 1 to 40 volume %, about 1 to 30 volume %, about 1 to 25 volume %, about 1 to 20 volume %, about 1 to 15 volume %, about 1 to 10 volume %, about 3 to 50 volume %, about 3 to 40 volume %, about 3 to 30 volume %, about 3 to 25 volume %, about 3 to 20 volume %, about 3 to 15 volume %, or about 3 to 10 volume %.

[0062] The third material 30v is mixed with the first material 30p and the second material 30n, and is arranged to contact the first material 30p and / or the second material 30n on an atomic scale to form a pn junction, and can change the morphology or molecular conformation of the first material 30p and / or the second material 30n. As a result, the diversity of morphology and molecular form of the photoelectric conversion layer 30 including the first material 30p, the second material 30n, and the third material 30v is different from the diversity of morphology and molecular form of a thin film consisting of the first material 30p and the second material 30n, and therefore the physical properties of the photoelectric conversion layer 30 including the first material 30p, the second material 30n, and the third material 30v are different from the physical properties of a thin film consisting of the first material 30p and the second material 30n. For example, the photoelectric conversion layer 30 including the first material 30p, the second material 30n, and the third material 30v has improved electrical properties, optical properties, and heat resistance properties compared to a thin film consisting of the first material 30p and the second material 30n.

[0063] For example, according to a quantum calculation based on morphology, the third material 30v including the above-mentioned electron-withdrawing group changes the distribution of energy levels of the first material 30p and / or the second material 30n. For example, the third material 30v including the electron-withdrawing group described above modifies the distribution of the HOMO energy levels or the distribution of the LUMO energy levels of the first material 30p or the second material 30n. As a result, 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 (without the third material 30v) is different from the HOMO energy level distribution or the LUMO energy level distribution of a thin film consisting of the first material 30p and the second material 30n. In this manner, by including the third material 30v, the photoelectric conversion layer 30 can be adjusted so that the first material 30p or the second material 30n has a HOMO energy level distribution or a LUMO energy level distribution in a desired region, or can be adjusted so that it does not have a HOMO energy level distribution or a LUMO energy level distribution in an undesired region.

[0064] As an example, if the first material 30p is a p-type material and the second material 30n is an n-type material, the third material 30v is a p-type material that modifies the distribution of the HOMO energy levels of the first material 30p. For example, the distribution of the HOMO energy levels of the first material 30p modified by the third material 30v shifts toward a deeper HOMO energy level compared to the distribution of the original HOMO energy levels of the first material 30p. This shift in the distribution of HOMO energy levels of the p-type semiconductor may be used to expand a desired region in the distribution of HOMO energy levels or to reduce or eliminate an undesired region in the distribution of HOMO energy levels. For example, it is possible to reduce or eliminate the shallow HOMO energy level region in which there are relatively many trap sites for charges (e.g., holes) within the distribution of HOMO energy levels of a p-type material, for example, by reducing or eliminating the HOMO energy level region shallower than about 5.2 eV within the distribution of HOMO energy levels of a p-type semiconductor.

[0065] As an example, the distribution of the HOMO energy levels of the first material 30p modified by the third material 30v is shifted toward a deeper HOMO energy level. For example, the HOMO energy level of the first material 30p modified by the third material 30v is deeper than the original HOMO energy level of the first material 30p by about 0.0001 eV to 1.2 eV. In this case, the HOMO energy level of the third material 30v may be deeper than the inherent HOMO energy level of the first material 30p. For example, the inherent HOMO energy level of the first material 30p is about 5.0 eV to 5.8 eV, and the HOMO energy level of the third material 30v is about 5.1 eV to 6.5 eV.

[0066] For example, 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, for example, the HOMO energy level of the third material 30v may be located between the HOMO energy level of the first material 30p and the HOMO energy level of the second material 30n. For example, the difference between the HOMO energy level of the third material 30v and the HOMO energy level of the second material 30n can be less than the difference between the HOMO energy level of the first material 30p and the HOMO energy level of the second material 30n. Within the above range, the inherent HOMO energy level of the first material 30p is, for example, about 5.0 eV to 5.8 eV, the HOMO energy level of the second material 30n is, for example, about 6.2 eV to 7.2 eV, and the HOMO energy level of the third material 30v is, for example, about 5.1 eV to 6.5 eV.

[0067] As a result, the HOMO energy level of the photoelectric conversion layer 30 including the first material 30p, the second material 30n, and the third material 30v may be deeper than the HOMO energy level of a thin film made of the first material 30p and the second material 30n (without the third material 30v). For example, the HOMO energy level of the photoelectric conversion layer 30 may be deeper by about 0.001 eV or more than the HOMO energy level of a thin film made of the first material 30p and the second material 30n (without the third material 30v), for example, by about 0.001 eV to 1.2 eV. In this way, by adjusting the distribution of energy levels of the first material 30p or the second material 30n to reduce or eliminate an energy level region (e.g., a shallow HOMO energy level region) in which there are relatively many charge trap regions in the photoelectric conversion layer 30, it is possible to reduce or prevent remaining charges that remain in the trap regions among the charges that move from the photoelectric conversion layer 30 to the first electrode 10 and / or the second electrode 20. As a result, image retention due to residual charges accumulated in the photoelectric conversion layer 30 can be reduced or prevented, and the electrical performance of the photoelectric conversion element 100 can be improved.

[0068] As an example, the third material 30v can change the absorption spectrum of the photoelectric conversion layer 30. For example, 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 made of the first material 30p and the second material 30n (without the third material 30v); for example, the full width at half maximum (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 full width at half maximum (FWHM) of the absorption spectrum of a thin film made of the first material 30p and the second material 30n (without the third material 30v). Here, the half-width is the wavelength width at half the peak absorption point (maximum absorption wavelength), and a small half-width means that light in a narrow wavelength range is absorbed and wavelength selectivity is high. For example, the half-width 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 about 2 nm to 30 nm narrower than the half-width of the absorption spectrum of a thin film consisting of the first material 30p and the second material 30n (without the third material 30v), and may be about 3 nm to 30 nm, about 5 nm to 30 nm, about 5 nm to 25 nm, or about 5 nm to 20 nm narrower within the above range.

[0069] As an example, the third material 30v can change the heat resistance property of the photoelectric conversion layer 30. For example, the heat resistance of the photoelectric conversion layer 30 including the first material 30p, the second material 30n, and the third material 30v is improved compared to the heat resistance of a thin film including the first material 30p and the second material 30n (without the third material 30v), and for example, the photoelectric conversion layer 30 including the first material 30p, the second material 30n, and the third material 30v can substantially maintain optical and electrical properties even at high temperature subsequent processes of about 180° C., about 190° C., or about 200° C. The photoelectric conversion layer 30 may be an intrinsic layer in which the above-mentioned first material 30p, the second material 30n, and the third material 30v are mixed in the form of a bulk heterojunction.

[0070] The first substance 30p and the second substance 30n can be mixed in a volume ratio of about 1:9 to 9:1, and can be mixed in a volume ratio within the above range, for example, about 2:8 to 8:2, and can be mixed in a volume ratio within the above range, for example, about 3:7 to 7:3, for example, about 4:6 to 6:4, or about 5:5. As an example, the photoelectric conversion layer 30 may be a ternary system including the first material 30p, the second material 30n, and the third material 30v described above. As another example, referring to FIG. 1C, the photovoltaic layer 30 may include at least two layers (32-1, 32-2) including different combinations of the first material 30p, the second material 30n, and the third material 30v described above. Any one of the at least two layers (32-1, 32-2) may contain two materials selected from the first material 30p, the second material 30n, and the third material 30v, and may not contain any one of the first material 30p, the second material 30n, and the third material 30v, and the other of the at least two layers (32-1, 32-2) may contain two materials selected from the first material 30p, the second material 30n, and the third material 30v, but may contain any one of the first material 30p, the second material 30n, and the third material 30v that is not included in the aforementioned layers. For example, the first layer (32-1) may include a first material 30p and a third material 30v, and the second layer (32-2) may include a second material 30n and a third material 30v. For example, the first layer (32-1) and the second layer (32-2) may be in contact with each other. The first material 30p, the second material 30n, and the third material 30v have been described above in detail.

[0071] The photoelectric conversion element 100 may further include an anti-reflection layer (not shown) disposed on one surface of the first electrode 10 or the second electrode 20. The anti-reflection layer is disposed on the light incident side to reduce the reflectance of the incident light, thereby further improving the light absorption. For example, when light is incident on the first electrode 10 side, the anti-reflection layer is disposed on one side of the first electrode 10, and when light is incident on the second electrode 20 side, the anti-reflection layer is disposed on one side of the second electrode 20. The anti-reflective layer may include, for example, a material having a refractive index of about 1.6 to 2.5, and may include, for example, at least one of a metal oxide, a metal sulfide, and an organic material having a refractive index in the above range. The antireflective layer can include, but is not limited to, metal oxides such as aluminum-containing oxides, molybdenum-containing oxides, tungsten-containing oxides, vanadium-containing oxides, rhenium-containing oxides, niobium-containing oxides, tantalum-containing oxides, titanium-containing oxides, nickel-containing oxides, copper-containing oxides, cobalt-containing oxides, manganese-containing oxides, chromium-containing oxides, tellurium-containing oxides, or combinations thereof; metal sulfides such as zinc sulfide; or organics such as amine derivatives.

[0072] When light is incident on the photoelectric conversion element 100 from the first electrode 10 or second electrode 20 side and the photoelectric conversion layer 30 absorbs the light in a predetermined wavelength region, excitons are generated inside the photoelectric conversion element 100. The excitons separate into holes and electrons in the photoelectric conversion layer 30, and the separated holes move to one of the anodes, the first electrode 10 and the second electrode 20, and the separated electrons move to the other of the first electrode 10 and the second electrode 20, causing a current to flow.

[0073] FIG. 2 is a cross-sectional view showing another example of the schematic configuration of a photoelectric conversion element according to an embodiment of the present invention. 2, the photoelectric conversion element 100 according to this embodiment includes a first electrode 10, a second electrode 20, and a photoelectric conversion layer 30, similar to the above-described embodiments. However, unlike the above-described embodiments, the photoelectric conversion element 100 according to this embodiment further includes auxiliary layers (40, 50) between the first electrode 10 and the photoelectric conversion layer 30 and between the second electrode 20 and the photoelectric conversion layer 30.

[0074] The auxiliary layers (40, 50) can be, but are not limited to, a hole injecting layer (HIL) that facilitates hole injection, a hole transporting layer (HTL) that facilitates hole transport, an electron blocking layer (EBL) that blocks electron transport, an electron injecting layer (EIL) that facilitates electron injection, an electron transporting layer (ETL) that facilitates electron transport, and / or a hole blocking layer (HBL) that blocks hole transport.

[0075] The auxiliary layers (40, 50) can each independently comprise organic, inorganic and / or organic-inorganic. As an example, either one of the sublayers (40, 50) can include an inorganic sublayer. The inorganic sublayer may include, for example, a lanthanum group element, calcium (Ca), potassium (K), aluminum (Al), or an alloy thereof. The lanthanide group elements can include, for example, ytterbium (Yb). The inorganic helplayer can have a thickness of, for example, about 5 nm or less. As an example, either one of the sublayers (40, 50) may include an organic sublayer.

[0076] The organic auxiliary layer may include, for example, a compound represented by Formula 2A or 2B shown below, but is not limited thereto. [ka] [ka] (In the above chemical formula 2A or 2B, M 1 and M 2 are each independently O, S, Se, Te, or CR q R r , SiRs R t , or NR u and Ar 1c , Ar 2c , Ar 3c , and Ar 4c each independently represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, G 2 and G 3 are each independently a single bond, -(CR v R w ) n3 -, -O-, -S-, -Se-, -Te, -N=, -NR x - or -SiR y R z - (wherein n3 is 1 or 2); R 30 ~R 37 and R q ~R z are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, halogen, a cyano group, or a nitro group.

[0077] As an example, the organic auxiliary layer may be a compound represented by the following formula 2A-1 or 2B-1, but is not limited thereto. [ka] [ka] (In the above chemical formula 2A-1 or 2B-1, M 1 , M 2 , G 2 , G 3 , R 30 ~R 37 is as described above, R 38 ~R 45are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group.

[0078] As an example, the organic auxiliary layer can be a compound represented by the following formula 2A-1a or 2B-1a, but is not limited thereto. [ka] [ka]

[0079] As an example, one of the sublayers (40, 50) is an inorganic sublayer and the other of the sublayers (40, 50) is an organic sublayer. As an example, one of the auxiliary layers (40, 50) may be omitted.

[0080] The above-described photoelectric conversion element 100 can be applied to, for example, a sensor, and the sensor is, for example, an image sensor. An image sensor using the above-mentioned photoelectric conversion element 100 has improved optical and electrical characteristics as described above, and can be used as an image sensor suitable for high-speed photography by reducing image retention caused by residual charges. An example of an image sensor to which the above-described element is applied will be described below with reference to the drawings. Here, an organic CMOS image sensor will be described as an example of the image sensor.

[0081] FIG. 3 is a cross-sectional view showing an example of a schematic configuration of an image sensor according to an embodiment of the present invention. Referring to FIG. 3, an image sensor 300 according to an embodiment of the present invention includes a semiconductor substrate 110, an insulating layer 80, a photoelectric conversion element 100, and a color filter layer .

[0082] The semiconductor substrate 110 is a silicon substrate on which a transfer transistor (not shown) and a charge reservoir 155 are integrated. A transfer transistor and / or charge reservoir 155 is integrated for each pixel. The charge reservoir 155 is electrically connected to the photoelectric conversion element 100 . Furthermore, metal wiring (not shown) and pads (not shown) are formed on the semiconductor substrate 110 . The metal lines and pads are made of metals having low resistivity to reduce signal delay, such as, but not limited to, aluminum (Al), copper (Cu), silver (Ag), and alloys thereof.

[0083] An insulating layer 80 is formed over the metal lines and pads. The insulating layer 80 is made of inorganic insulating materials such as silicon oxide and / or silicon nitride or low dielectric constant (low K) materials such as SiC, SiCOH, SiCO, and SiOF. The insulating layer 80 has a trench 85 exposing the charge reservoir 155 . The trench 85 is filled with a filling material.

[0084] The photoelectric conversion element 100 is formed on the insulating layer 80 . Photoelectric conversion element 100 has the structure shown in FIG. 1A or FIG. 2, and the specific description is as described above. One of the first electrode 10 and the second electrode 20 of the photoelectric conversion element 100 is a light receiving electrode, and the other of the first electrode 10 and the second electrode 20 of the photoelectric conversion element 100 is connected to a charge reservoir 155 . A color filter layer 70 is formed on the photoelectric conversion element 100 . The color filter layer 70 includes blue filters 70a formed in blue pixels, red filters 70b formed in red pixels, and green filters 70c formed in green pixels. However, without being limited thereto, a cyan filter, a magenta filter, and / or a yellow filter may alternatively or additionally be included.

[0085] An insulating film 180 is formed between the photoelectric conversion element 100 and the color filter layer 70 . The insulating film 180 may be omitted. A condenser lens (not shown) is further formed on the color filter layer 70 . A focusing lens controls the direction of incoming light to focus it at a single point. The focusing lens may be, for example, cylindrical or hemispherical, but is not limited thereto.

[0086] FIG. 4 is a plan view showing an example of an image sensor according to an embodiment of the present invention, and FIG. 5 is a cross-sectional view showing an example of a schematic configuration of the image sensor of FIG. 4 and 5, an image sensor 400 according to an embodiment of the present invention includes a semiconductor substrate 110 in which photo-sensing elements (150a, 150b), transfer transistors (not shown), and charge storages 155 are integrated, a lower insulating layer 60, a color filter layer 70, an upper insulating layer 80, and a photoelectric conversion element 100.

[0087] The semiconductor substrate 110 is a silicon substrate on which the light sensing elements (150a, 150b), a transfer transistor (not shown) and a charge reservoir 155 are integrated. The light sensing elements (150a, 150b) are photodiodes. A light sensing element (150a, 150b), a transfer transistor and / or a charge reservoir 155 are integrated for each pixel, and as an example, as can be seen from the drawing, a light sensing element (150a, 150b) is included in the blue pixel and the red pixel respectively, and a charge reservoir 155 is included in the green pixel.

[0088] The light sensing elements (150a, 150b) sense light, and the sensed information is transmitted by a transmission transistor. The charge storage 155 is electrically connected to the photoelectric conversion element 100, and the information of the charge storage 155 is transmitted by the transmission transistor. Furthermore, metal wiring (not shown) and pads (not shown) are formed on the semiconductor substrate 110 . The metal lines and pads are made of metals having low resistivity to reduce signal delay, such as, but not limited to, aluminum (Al), copper (Cu), silver (Ag), and alloys thereof. However, the present invention is not limited to the above structure, and the metal wiring and pads may be disposed under the photo-sensing elements 150a and 150b.

[0089] A lower insulating layer 60 is formed over the metal lines and pads. The lower insulating layer 60 is made of inorganic insulating materials such as silicon oxide and / or silicon nitride, or low dielectric constant (low K) materials such as SiC, SiCOH, SiCO, and SiOF. The lower insulating layer 60 has a trench 85 exposing the charge reservoir 155 . The trench 85 is filled with a filling material.

[0090] A color filter layer 70 is formed on the lower insulating film 60 . The color filter layer 70 includes blue filters 70a formed in blue pixels and red filters 70b formed in red pixels. However, without being limited thereto, a cyan filter, a magenta filter and / or a yellow filter may alternatively or additionally be included. In this embodiment, an example in which a green filter is not provided will be described, but in some cases a green filter may be provided. An upper insulating layer 80 is formed over the color filter layer 70 . The upper insulating layer 80 removes the steps caused by the color filter layer 70 and flattens the surface. The upper insulating layer 80 and the lower insulating layer 60 have contact holes (not shown) exposing the pads and trenches 85 exposing the charge reservoirs 155 of the green pixels.

[0091] The photoelectric conversion element 100 is formed on the upper insulating layer 80 . The photoelectric conversion element 100 has the structure shown in FIG. 1 or FIG. 2, and the specific description is as described above. One of the first electrode 10 and the second electrode 20 of the photoelectric conversion element 100 is a light receiving electrode, and the other of the first electrode 10 and the second electrode 20 of the photoelectric conversion element 100 is connected to a charge reservoir 155 . A condenser lens (not shown) is further formed on the photoelectric conversion element 100 . A focusing lens controls the direction of incoming light to focus it at a single point. The focusing lens may be, for example, cylindrical or hemispherical, but is not limited thereto.

[0092] FIG. 6 is a cross-sectional view showing another example of the schematic configuration of the image sensor of FIG. Referring to FIG. 6, the image sensor 500 according to this embodiment includes a semiconductor substrate 110 in which photo-sensing elements (150a, 150b), transfer transistors (not shown) and charge storages 155 are integrated, a lower insulating layer 60, a color filter layer 70, an upper insulating layer 80 and a photoelectric conversion element 100, similar to the above-described embodiments.

[0093] However, in the image sensor 500 according to the present embodiment, the photo-sensing elements 150a and 150b are stacked vertically, and the color filter layer 70 is omitted, unlike the above-described embodiments. The light-sensing elements (150a, 150b) are electrically connected to a charge reservoir (not shown) and are conveyed by a transfer transistor. The light sensing elements (150a, 150b) selectively absorb light in each wavelength region depending on the layer depth. The photoelectric conversion element 100 has the structure shown in FIG. 1 or FIG. 2, and the specific description is as described above. One of the first electrode 10 and the second electrode 20 of the photoelectric conversion element 100 is a light receiving electrode, and the other of the first electrode 10 and the second electrode 20 of the photoelectric conversion element 100 is connected to a charge reservoir 155 .

[0094] FIG. 7 is a plan view showing another example of an image sensor according to an embodiment of the present invention, and FIG. 8 is a cross-sectional view showing an example of a schematic configuration of the image sensor of FIG. The image sensor 600 according to this embodiment has a structure in which green elements that selectively absorb light in the green wavelength region, blue elements that selectively absorb light in the blue wavelength region, and red elements that selectively absorb light in the red wavelength region are stacked. The image sensor 600 according to this embodiment includes a semiconductor substrate 110, a lower insulating layer 60, an intermediate insulating layer 65, an upper insulating layer 80, a first photoelectric conversion element 100a, a second photoelectric conversion element 100b, and a third photoelectric conversion element 100c.

[0095] The semiconductor substrate 110 is a silicon substrate on which transfer transistors (not shown) and charge reservoirs (155a, 155b, 155c) are integrated. Metal wiring (not shown) and pads (not shown) are formed on the semiconductor substrate 110, and a lower insulating layer 60 is formed on the metal wiring and pads. On the lower insulating layer 60, a first photoelectric conversion element 100a, a second photoelectric conversion element 100b, and a third photoelectric conversion element 100c are formed in sequence. The first, second, and third photoelectric conversion elements (100a, 100b, 100c) each independently have the structure shown in FIG. 1 or FIG. 2, and the specific description is as described above. One of the first electrode 10 and the second electrode 20 of the first, second, and third photoelectric conversion elements (100a, 100b, 100c) is 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 elements (100a, 100b, 100c) is connected to a charge storage (155a, 155b, 155c).

[0096] The first photoelectric conversion element 100a selectively absorbs light in any one of the wavelength regions of red, blue, and green and performs photoelectric conversion. For example, the first photoelectric conversion element 100a is a red photoelectric conversion element. An intermediate insulating layer 65 is formed on the first photoelectric conversion element 100a. On the intermediate insulating layer 65, the second photoelectric conversion element 100b is formed. The second photoelectric conversion element 100b selectively absorbs light in any one of the wavelength regions of red, blue, and green and performs photoelectric conversion. For example, the second photoelectric conversion element 100b is a blue photoelectric conversion element.

[0097] An upper insulating layer 80 is formed on the second photoelectric conversion element 100b. The lower insulating layer 60, the middle insulating layer 65, and the upper insulating layer 80 have a plurality of trenches (85a, 85b, 85c) exposing the charge reservoirs (155a, 155b, 155c). On the upper insulating layer 80, the third photoelectric conversion element 100c is formed. The third photoelectric conversion element 100c selectively absorbs light in any one of the wavelength regions of red, blue, and green and performs photoelectric conversion. For example, the third photoelectric conversion element 100c is a green photoelectric conversion element.

[0098] A condenser lens (not shown) is further formed on the third photoelectric conversion element 100c. A focusing lens controls the direction of incoming light to focus it at a single point. The focusing lens may be, for example, cylindrical or hemispherical, but is not limited thereto. Although the drawings show a structure in which the first photoelectric conversion element 100a, the second photoelectric conversion element 100b, and the third photoelectric conversion element 100c are stacked in order, the stacking order is not limited thereto and may be changed in various ways. As described above, by having a stacked structure of the first photoelectric conversion element 100a, the second photoelectric conversion element 100b, and the third photoelectric conversion element 100c, which absorb light in different wavelength ranges, the size of the image sensor can be further reduced, thereby achieving a miniaturized image sensor.

[0099] FIG. 9 is a plan view showing another example of an image sensor according to an embodiment of the present invention, and FIG. 10 is a cross-sectional view showing an example of a schematic configuration of the image sensor of FIG. 9 and 10, an image sensor 1100 includes a photoelectric conversion element 90 disposed on a semiconductor substrate 110, and the photoelectric conversion element 90 includes a plurality of photoelectric conversion elements (90-1, 90-2, 90-3). The multiple photoelectric conversion elements (90-1, 90-2, 90-3) convert light in different wavelength regions (for example, blue light, green light, or red light) into electrical signals.

[0100] 10, a plurality of photoelectric conversion elements (90-1, 90-2, 90-3) are arranged side by side in the horizontal direction on a semiconductor substrate 110, and overlap each other partially or entirely in a direction extending parallel to a surface 110a of the semiconductor substrate 110. Each photoelectric conversion element (90-1, 90-2, 90-3) is connected to a charge reservoir 155 integrated in the semiconductor substrate 110 through a trench 85. Each of the photoelectric conversion elements (90-1, 90-2, 90-3) is one of the photoelectric conversion elements (100, 200) described above.

[0101] As an example, the two or more photoelectric conversion elements (90-1, 90-2, 90-3) may include different portions of a common continuous layer that extends continuously between the photoelectric conversion elements (90-1, 90-2, 90-3). As an example, the multiple photoelectric conversion elements (90-1, 90-2, 90-3) share a common first electrode 10 and / or a common second electrode 20. As an example, the two or more photoelectric conversion elements (90-1, 90-2, 90-3) have different photoelectric conversion layers 30 capable of absorbing light in different wavelength regions of the incident light. The rest of the structure of image sensor 1100 is similar to one or more of the image sensors described with reference to FIGS.

[0102] FIG. 11 is a cross-sectional view showing another example of the schematic configuration of the image sensor according to the embodiment of the present invention. Referring to FIG. 11, an image sensor 1200 includes a semiconductor substrate 110 and photoelectric conversion elements (90-1, 91) stacked on the semiconductor substrate 110. The photoelectric conversion element 91 includes a plurality of photoelectric conversion elements (90-2, 90-3), which are arranged so as to overlap each other in a direction extending parallel to the surface 110a of the semiconductor substrate 110. The multiple photoelectric conversion elements (90-1, 90-2, 90-3) photoelectrically convert light in different wavelength regions (for example, blue light, green light, or red light) into electrical signals.

[0103] As an example, the photoelectric conversion element 91 (90-2, 90-3) includes a plurality of photoelectric conversion elements arranged in the horizontal direction, each of which can absorb light in a different wavelength range. As an example, the photoelectric conversion element (90-1) performs photoelectric conversion on light in one wavelength region selected from blue light, green light, and red light. As an example, the photoelectric conversion element 91 entirely or partially overlaps with the photoelectric conversion element (90-1). The rest of the structure of the organic CMOS image sensor 1200 is similar to one or more of the image sensors described in FIGS.

[0104] FIG. 12 is a cross-sectional view showing still another example of the schematic configuration of the image sensor according to the embodiment of the present invention. Referring to FIG. 12, the image sensor 1300 includes a semiconductor substrate 110 in which photo-sensing elements (150a, 150b), transfer transistors (not shown) and charge storage elements 155 are integrated, an upper insulating layer 80 located on the upper part of the semiconductor substrate 110, a color filter layer 70, a lower insulating layer 60 located on the lower part of the semiconductor substrate 110, and a photoelectric conversion element 90.

[0105] The photoelectric conversion element 90 corresponds to the photoelectric conversion element 100 in FIGS. In FIG. 12, the photoelectric conversion element 90 is disposed under the semiconductor substrate 110, so that the photoelectric conversion element 90 and the color filter layer 70 are disposed separately from the light sensing elements (150a, 150b). The rest of the structure of image sensor 1300 is similar to one or more of the image sensors described in FIGS. The above-mentioned photoelectric conversion elements and sensors can be applied to various electronic devices, such as, but not limited to, mobile phones, cameras, biometric recognition devices, and / or automotive electrical components.

[0106] FIG. 13 is a block diagram showing a schematic configuration of an electronic device according to an embodiment of the present invention. Referring to FIG. 13, an electronic device 1700 includes a processor 1720, a memory 1730, and an image sensor 1740 that are electrically connected to each other via a bus 1710. The image sensor 1740 may be any one of the embodiments described above. The non-transitory computer readable medium memory 1730 stores a program of instructions. The processor 1720 executes stored programs of instructions to perform one or more functions. As an example, the processor 1720 processes the electrical signals generated by the image sensor 1740 . The processor 1720 may generate an output (eg, an image to be displayed on a display interface) based on such processing.

[0107] The above-described embodiment will now be described in more detail with reference to examples. However, the following examples are merely illustrative and are not intended to limit the scope of the present invention.

[0108] <<Synthesis Example>> <Synthesis Example 1> [ka] [ka]

[0109] (i) Synthesis of Compound I-1 2-iodotellurophene (compound I-1) was synthesized with reference to the method described 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".

[0110] (ii) Synthesis of Compound I-2 2-Iodotellurophene (compound I-1) (15.0 g (49.1 mmol)) and 10,10-dimethyl-5,10-dihydrodibenzo[b,e][1,4]azasiline (10.0 g (44.6 mmol)) were dissolved in 200 mL of anhydrous toluene and dissolved in 5 mol% bis(dibenzylideneacetone)palladium(0) (Pd(dba)). 2 ), 5 mol% tri-t-butylphosphine (tri-t-butylphosphine, P(tBu) 3 The mixture was heated to reflux for 2 hours in the presence of 12.9 g (133.9 mmol) of sodium t-butoxide (NaOtBu). The resulting product was separated and purified by silica gel column chromatography (toluene:hexane = 1:4 volume ratio) to obtain 6.8 g (yield 37.8%) of 10,10-dimethyl-5-(tellurophen-2-yl)-5,10-dihydrodibenzo[b,e][1,4]azasiline (compound I-2).

[0111] (iii) Synthesis of Compound I-3 6.2 ml of phosphoryl chloride was added dropwise to 30.0 ml of N,N-dimethylformamide at −15° C., and the mixture was stirred at room temperature (24° C.) for 2 hours. The mixture was slowly added dropwise to a mixture of 300 ml of dichloromethane and 6.8 g of compound I-2 at -15°C, and then stirred at room temperature for 30 minutes and concentrated under reduced pressure. 300 ml of water was added thereto, and aqueous sodium hydroxide solution was added thereto until the pH value reached 14, followed by stirring at room temperature (24° C.) for 2 hours. The organic layer extracted with dichloromethane was washed with aqueous sodium chloride solution, and then dried with anhydrous magnesium sulfate. The resulting product was purified by silica gel column chromatography (hexane:ethyl acetate = 4:1 volume ratio) to obtain 2.82g (yield 38.8%) of 5-(10,10-dimethyldibenzo[b,e][1,4]azasilin-5(10H)-yl)tellurophene-2-carbaldehyde (compound I-3).

[0112] (iv) Synthesis of Compound 1 The obtained compound I-3 (2.82 g (6.54 mmol)) was suspended in ethanol, and 1.35 g (7.85 mmol) of 1,3-dimethyl-2-thiobarbituric acid was added thereto and reacted at 50° C. for 2 hours to obtain compound 1 (2.98 g) (yield 77.8%). The resulting compound was purified by sublimation to a purity of 99.9%. 1 H-NMR (500MHz, Methylene Chloride-d 2):δ8.46(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)

[0113] <Synthesis Example 2> [ka] [ka]

[0114] (i) Synthesis of Compound I-4 2-iodosellenophene (compound I-4) was synthesized with reference to the method described 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".

[0115] (ii) Synthesis of Compound I-5 2-Iodoselenophene (compound I-4) (10.0 g (38.9 mmol)) and 3-fluoro-9,9-dimethyl-9,10-dihydroacridine (8.04 g (35.4 mmol)) were dissolved in 200 mL of anhydrous toluene and diluted with 5 mol% Pd(dba) 2 , 5mol% P(tBu) 3 and 10.2 g (106.2 mmol) of NaOtBu, and the mixture was heated to reflux for 2 hours. 3-fluoro-9,9-dimethyl-9,10-dihydroacridine was synthesized with reference 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 obtained product was separated and purified by silica gel column chromatography (toluene:hexane=1:4 volume ratio) to obtain 6.8 g (yield 53.9%) of 2-fluoro-9,9-dimethyl-10-(selenophen-2-yl)-9,10-dihydroacridine (compound I-5).

[0116] (iii) Synthesis of Compound I-6 5.2 ml of phosphoryl chloride was added dropwise to 10.0 ml of N,N-dimethylformamide at −15° C., and the mixture was stirred at room temperature (24° C.) for 2 hours. The mixture was slowly added dropwise to a mixture of 150 ml of dichloromethane and 5.0 g of compound I-5 at −15° C., and then stirred at room temperature for 30 minutes and concentrated under reduced pressure. 300 ml of water was added thereto, and aqueous sodium hydroxide solution was added thereto until the pH value reached 14, followed by stirring at room temperature (24° C.) for 2 hours. The organic layer extracted with dichloromethane was washed with aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate. The obtained product was separated and purified by silica gel column chromatography (hexane:ethyl acetate = 4:1 volume ratio) to obtain 2.24 g (yield 39.9%) of 5-(2-fluoro-9,9-dimethylacridin-10(9H)-yl)selenophene-2-carbaldehyde (compound I-6).

[0117] (iv) Synthesis of Compound 2 The obtained compound I-6 (1.30 g (3.37 mmol)) was suspended in ethanol, and 0.64 g (3.71 mmol) of 1,3-dimethyl-2-thiobarbituric acid was added thereto and reacted at 50° C. for 2 hours to obtain compound 2 (1.52 g) (yield 83.8%). The resulting compound was purified by sublimation to a purity of 99.9%. 1 H-NMR (500MHz, Methylene Chloride-d 2 ):δ8.52(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)

[0118] <Synthesis Example 3> [ka] [ka]

[0119] (i) Synthesis of Compound I-7 2-iodotellurophene (compound I-7) was synthesized by referring to the method described 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".

[0120] (ii) Synthesis of Compound I-8 2-Iodotellurophene (compound I-7) (10.0 g (38.9 mmol)) and 3-fluoro-10,10-dimethyl-5,10-dihydrodibenzo[b,e][1,4]azasiline (8.62 g (35.38 mmol)) were dissolved in 200 mL of anhydrous toluene and diluted with 5 mol% Pd(dba) 2 , 5mol% P(tBu) 3 and 10.2 g (106.2 mmol) of NaOtBu, and the mixture was heated to reflux for 2 hours. 3-fluoro-10,10-dimethyl-5,10-dihydrodibenzo[b,e][1,4]azasiline was synthesized with reference to the method described in "Y. Kitamoto, T. Namikawa, T. Suzuki, Y. Miyata, H. Kita, T. Sato, S. Oi. Tetrahedron Letters, 2016, 57, 4914-4917". The obtained product was separated and purified by silica gel column chromatography (toluene:hexane = 1:4 volume ratio) to obtain 6.5 g (yield 49.5%) of 3-fluoro-10,10-dimethyl-5-(tellurophen-2-yl)-5,10-dihydrodibenzo[b,e][1,4]azasiline (compound I-8).

[0121] (iii) Synthesis of Compound I-9 4.9 ml of phosphoryl chloride was added dropwise to 8.4 ml of N,N-dimethylformamide at −15° C., and the mixture was stirred at room temperature (24° C.) for 2 hours. The mixture was slowly added dropwise to a mixture of 160 ml of dichloromethane and 5.0 g of compound I-8 at −15° C., and then stirred at room temperature for 30 minutes and concentrated under reduced pressure. 300 ml of water was added thereto, and aqueous sodium hydroxide solution was added thereto until the pH value reached 14, followed by stirring at room temperature (24° C.) for 2 hours. The organic layer extracted with dichloromethane was washed with aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate. The resulting product was separated and purified by silica gel column chromatography (hexane:ethyl acetate = 4:1 volume ratio) to obtain 2.30 g (yield 42.8%) of 5-(3-fluoro-10,10-dimethyldibenzo[b,e][1,4]azasilin-5(10H)-yl)tellurophene-2-carbaldehyde (compound I-9). 1 H-NMR (500MHz, Methylene Chloride-d 2 ):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)

[0122] (iv) Synthesis of Compound 3 The obtained compound I-9 (1.2 g (2.28 mmol)) was suspended in ethanol, and 1,3-dimethyl-2-thiobarbituric acid (0.33 g (2.51 mmol)) was added thereto and reacted at 50° C. for 2 hours to obtain compound 3 (0.92 g) (yield 72.8%). The resulting compound was purified by sublimation to a purity of 99.9%.

[0123] <Synthesis Example 4> [ka] [ka]

[0124] (i) Synthesis of Compound I-10 2-iodoselenophene (compound I-10) was synthesized by referring to the method described 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".

[0125] (ii) Synthesis of Compound I-11 2-Iodoselenophene (compound I-10) (10.0 g (38.9 mmol)) and 3-fluoro-9,9-dimethyl-9,10-dihydroacridine (8.04 g (35.4 mmol)) were dissolved in 200 ml of anhydrous toluene and diluted with 5 mol% Pd(dba) 2 , 5mol% P(tBu) 3 and 10.2 g (106.2 mmol) of NaOtBu, and the mixture was heated to reflux for 2 hours. 3-fluoro-9,9-dimethyl-9,10-dihydroacridine was synthesized with reference 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 obtained product was separated and purified by silica gel column chromatography (toluene:hexane=1:4 volume ratio) to obtain 6.8 g (yield 53.9%) of 2-fluoro-9,9-dimethyl-10-(selenophen-2-yl)-9,10-dihydroacridine (compound I-11).

[0126] (iii) Synthesis of Compound I-12 5.2 ml of phosphoryl chloride was added dropwise to 10.0 ml of N,N-dimethylformamide at −15° C., and the mixture was stirred at room temperature (24° C.) for 2 hours. The mixture was slowly added dropwise to a mixture of 150 ml of dichloromethane and 5.0 g of compound I-11 at −15° C., and then stirred at room temperature for 30 minutes and concentrated under reduced pressure. 300 ml of water was added thereto, and aqueous sodium hydroxide solution was added thereto until the pH value reached 14, followed by stirring at room temperature (24° C.) for 2 hours. The organic layer extracted with dichloromethane was washed with aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate. The obtained product was separated and purified by silica gel column chromatography (hexane:ethyl acetate = 4:1 volume ratio) to obtain 2.24 g (yield 39.9%) of 5-(2-fluoro-9,9-dimethylacridin-10(9H)-yl)selenophene-2-carbaldehyde (compound I-12).

[0127] (iv) Synthesis of Compound 4 The obtained compound I-12 (0.94 g (2.44 mmol)) was suspended in ethanol, and 1,3-indandione (0.37 g (2.56 mmol)) was added thereto, and the mixture was reacted at 50° C. for 2 hours to obtain compound 4 (1.02 g) (yield 81.6%). The resulting compound was purified by sublimation to a purity of 99.9%. 1 H-NMR (500MHz, Methylene Chloride-d 2 ):δ8.48(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)

[0128] <<Evaluation I>> The energy levels of the compounds obtained in the synthesis examples were evaluated. The energy levels were evaluated by simulation using Gaussian software (Gaussian.Inc). [Table 1]

[0129] <<Fabrication of photoelectric conversion elements>> <Example 1> ITO was deposited on a glass substrate by sputtering to form an anode with a thickness of 150 nm. Next, a compound represented by the following formula 2B-1aa was deposited on the anode to form an electron blocking layer having a thickness of 5 nm. Next, Compound 1 (first substance) (λ max:545nm), fullerene (C 60 ) (second substance) and Compound 2 (third substance) (λ max : 530 nm) was co-evaporated to form a photoelectric conversion layer with a thickness of 95 nm. At this time, the first and second substances were co-deposited at a volume ratio (bulk ratio) of 1:1, and the third substance was co-deposited at 3 volume % with respect to the total volume of the first and third substances. Next, Yb was thermally evaporated onto the photoelectric conversion layer to form an electron auxiliary layer having a thickness of 1.5 nm. Next, ITO was sputtered onto the electron assist layer to form a 7 nm thick cathode. Next, aluminum oxide (Al 2 O 3 ) was evaporated to form an antireflection layer having a thickness of 50 nm, and the resultant was sealed with a glass plate to produce a photoelectric conversion element. [ka]

[0130] <Example 2> A photoelectric conversion element was manufactured in the same manner as in Example 1, except that the third material was co-deposited to be 5 volume % of the total volume of the first material and the third material to form a photoelectric conversion layer having a thickness of 105 nm. <Example 3> A photoelectric conversion element was manufactured in the same manner as in Example 1, except that the third material was co-deposited to be 10 volume % relative to the total volume of the first material and the third material to form a photoelectric conversion layer having a thickness of 94 nm. <Example 4> A photoelectric conversion element was manufactured in the same manner as in Example 1, except that the third material was co-deposited to account for 33 volume % of the total volume of the first material and the third material to form a photoelectric conversion layer having a thickness of 99 nm. <Example 5> A photoelectric conversion element was manufactured in the same manner as in Example 1, except that the third material was co-deposited to form a photoelectric conversion layer having a thickness of 88 nm, at 50 volume % of the total volume of the first material and the third material.

[0131] <Comparative Example 1> A photoelectric conversion element was manufactured in the same manner as in Example 1, except that the third material was not used and the first material and the second material were co-deposited to form a photoelectric conversion layer having a thickness of 102 nm. <Comparative Example 2> A photoelectric conversion element was manufactured in the same manner as in Example 1, except that the photoelectric conversion layer was formed by co-evaporating the second and third materials without including the first material.

[0132] <<Evaluation II>> The light absorption characteristics of the photoelectric conversion elements according to the example and the comparative example were evaluated. The light absorption characteristics were evaluated in the ultraviolet-visible light (UV-Vis) region using a Cary 5000UV spectroscopy (Varian). The results are shown in Table 2. [Table 2] Referring to Table 2, it was confirmed that the photoelectric conversion element according to the embodiment had improved wavelength selectivity without a change in maximum absorption wavelength compared to the photoelectric conversion element according to the comparative example.

[0133] <<Evaluation III>> The electrical characteristics of the photoelectric conversion elements according to the example and the comparative example were evaluated. The photoelectric conversion efficiency is max ) and was evaluated using the "Incident Photon to Current Efficiency (IPCE)" method in the wavelength range of 400 nm to 720 nm. The results are shown in Table 3. [Table 3] Referring to Table 3, it was confirmed that the photoelectric conversion devices according to the examples exhibited equivalent or improved external quantum efficiency compared to the photoelectric conversion devices according to the comparative examples.

[0134] <<Evaluation IV>> The remaining charges characteristics of the photoelectric conversion elements according to the example and the comparative example were evaluated. Residual charge characteristics refer to the amount of charge that remains after photoelectric conversion in one frame without being used for signal processing and that is read in the next frame from the previous frame. The elements according to the embodiment and comparative example were irradiated with light in the green wavelength range in which photoelectric conversion can occur for a certain period of time, and then the light was turned off. After that, the amount of charge was measured using a Keithley 2400 device for 10 -6 The evaluation was based on the amount of current measured in seconds. The amount of residual electrons is h+ / s / μm at 5,000 lux. 2 Evaluated in units. The results are shown in Table 4. [Table 4] Referring to Table 4, it can be seen that the photoelectric conversion element according to the embodiment has improved residual charge characteristics compared to the photoelectric conversion element according to the comparative example.

[0135] <<Evaluation V>> The heat resistance characteristics of the photoelectric conversion elements according to the example and the comparative example were evaluated. The heat resistance characteristics were evaluated by heat treating the photoelectric conversion elements according to the examples and comparative examples at 180° C. for 3 hours, 190° C. for 1 hour, and 200° C. for 1 hour, and then checking the changes in the external quantum efficiency and residual charge. The results are shown in Tables 5 and 6. [Table 5] [Table 6] Referring to Tables 5 and 6, it was confirmed that the photoelectric conversion element according to the embodiment has high heat resistance, and even after heat treatment at a high temperature of about 200 degrees, the thin film is not damaged and the electrical characteristics do not change significantly, and the residual charge characteristics are actually improved.

[0136] The present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the technical scope of the present invention. [Explanation of symbols]

[0137] 10 1st electrode 20 2nd electrode 30 Photoelectric conversion layer 40, 50 auxiliary layer 60 Lower insulating layer 65 Intermediate insulation layer 70 color filter layers 70a, 70b, 70c (blue, red, green) filters 80 (Top) Insulation layer 85, 85a, 85b, 85c trenches 90, 90-1, 90-2, 90-3, 91, 100 Photoelectric conversion element 100a, 100b, 100c (first to third) photoelectric conversion elements 110 Semiconductor substrate 150a, 150b, 150c Light sensing element 155 Charge reservoir 180 Insulating Film 300, 400, 500, 600, 1100, 1200, 1300 Image Sensor 1700 Electronic equipment 1710 Bus 1720 Processor 1730 Memory 1740 Image Sensor

Claims

1. A first electrode; A second electrode; a photoelectric conversion layer disposed between the first electrode and the second electrode; The photoelectric conversion layer includes a first material and a second material forming a pn junction, The third material is different from the first material and the second material and includes an electron withdrawing group; The first substance is represented by the following chemical formula A-3: the third material is an organic material including an electron donating moiety (EDM), an electron accepting moiety (EAM), and a π-conjugated linking moiety (LM) connecting the electron donating moiety and the electron accepting moiety; at least one of the electron donating moiety, the electron accepting moiety, and the π-conjugated linking moiety comprises the electron withdrawing group; The third material is represented by the following chemical formula 1-3a: In the formula 1-3a, EAM3 is the electron accepting moiety and is a group of Group 1 shown below: The photoelectric conversion element, wherein the electron-withdrawing group contains fluorine, a cyano group, or a combination thereof. 【Chemical A-3】 (In the above chemical formula A-3, EAM1 is an electron accepting moiety; X a is S, Se, or Te; R 1a and R 2a are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen atom, a cyano group, or a nitro group; Ar 1a and Ar 2a are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms; W is -SiR h1 R i1 -, R h1 and R i1 each independently represent an unsubstituted alkyl group having 1 carbon atom. 【Chemistry 1-3a】 (In the above chemical formula 1-3a, X 1 is S, Se, or Te; EAM3 is the electron accepting moiety; G is -(CR f R g ) n2 - (n2 is 1); R f and R g each independently represent an unsubstituted alkyl group having 1 carbon atom; R 1 , R 2 , R 7f to R 7g , and R 8f to R 8g are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a halogen, a cyano group, or a nitro group; At least one of R 7f to R 7g and R 8f to R 8g is a halogen, a cyano group, a nitro group, an alkyl group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, an alkoxy group having 1 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, a cycloalkyl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, an aryl group having 6 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof, or a heteroaryl group having 3 to 30 carbon atoms substituted with a halogen, a cyano group, a nitro group, or a combination thereof. 【group1】 (Among group 1 above, Y 1 and Y 2 are each independently O; Y 3 is S; R 3 is hydrogen, R 4 and R 5 are each independently an unsubstituted alkyl group having 1 carbon atom, * indicates a connection point.)

2. 2. The photoelectric conversion element according to claim 1, wherein at least one of the first substance and the second substance is an organic substance.

3. 2. The photoelectric conversion element according to claim 1, wherein the first substance is an organic substance that does not contain an electron-withdrawing group.

4. 2. The photoelectric conversion element according to claim 1, wherein the first substance is an organic substance that does not contain fluorine.

5. 2. The photoelectric conversion element according to claim 1, wherein the HOMO energy level of the third material is located between the HOMO energy level of the first material and the HOMO energy level of the second material.

6. 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; 6. The photoelectric conversion element according to claim 5, wherein the HOMO energy level of the third substance is 5.1 eV to 6.5 eV.

7. The photoelectric conversion element according to claim 1 , wherein the photoelectric conversion layer includes a mixture of the first material, the second material, and the third material.

8. The photoelectric conversion layer includes a first layer including the first material and the third material; 2. The photoelectric conversion element according to claim 1, further comprising: a second layer containing the second material and the third material.

9. 2 . The photoelectric conversion element according to claim 1 , wherein the third material is contained in an amount of 50% by volume or less with respect to a total volume of the first material and the third material.

10. The light absorption spectrum of the photoelectric conversion layer has a maximum absorption wavelength in a first wavelength region that is any one of a blue wavelength region, a green wavelength region, a red wavelength region, and an infrared wavelength region; 2 . The photoelectric conversion element according to claim 1 , wherein the first substance and the third substance are light-absorbing substances each having a maximum absorption wavelength in the first wavelength region.

11. 2. The photoelectric conversion element according to claim 1, wherein the half width of the absorption spectrum of the photoelectric conversion layer is narrower than the half width of the absorption spectrum of a thin film made of the first substance and the second substance.

12. 2. The photoelectric conversion element according to claim 1, wherein the photoelectric conversion layer is a three-component system including the first substance, the second substance, and the third substance.

13. A sensor comprising: The sensor comprises the photoelectric conversion element according to claim 1 .

14. the sensor is an image sensor, The sensor of claim 13 , wherein the image sensor further comprises a semiconductor substrate on which the photoelectric conversion element is stacked.

15. 1. An electronic device comprising: The electronic device comprises a sensor according to claim 13.

16. An electronic device comprising the photoelectric conversion element according to claim 1 .

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