Optoelectronic conversion device and sensor and electronic device

Abstract

Optoelectronic conversion devices, and sensors and electronic devices including the optoelectronic conversion devices are disclosed. The optoelectronic conversion device can include a first electrode and a second electrode and an optoelectronic conversion layer between the first electrode and the second electrode. The optoelectronic conversion layer includes a first material and a second material forming a pn junction, and a third material different from the first material and the second material. The third material is configured to adjust an energy level distribution of the first material or the second material.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2019-0140289, filed on November 5, 2019, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Disclosed photoelectric conversion devices, sensors, and electronic devices. Background Technology

[0004] Photoelectric conversion devices utilize the photoelectric effect to convert light into electrical signals. These devices include photodiodes and phototransistors, and can be applied to sensors or photodetectors.

[0005] Sensors increasingly demand higher resolution, leading to smaller pixel sizes. With currently used silicon photodiodes, sensitivity can decrease as the absorption area shrinks with pixel size. Therefore, organic materials that can replace silicon have been investigated.

[0006] The organic material can have a high extinction coefficient and be configured to selectively absorb light in a specific wavelength region depending on its molecular structure, and thus can simultaneously replace photodiodes and color filters, resulting in improved sensitivity and contribution to high integration.

[0007] However, due to their high binding energy and recombination behavior, organic materials can exhibit properties different from silicon, and it is difficult to accurately predict the properties of organic materials, which makes it difficult to easily control the properties required for photoelectric conversion devices. Summary of the Invention

[0008] Example implementations provide photoelectric conversion devices that can reduce residual charge carriers and improve charge carrier extraction characteristics.

[0009] Example implementations provide a sensor including the aforementioned photoelectric conversion device.

[0010] Example implementations provide electronic devices that include the photoelectric conversion device or the sensor.

[0011] According to an example embodiment, a photoelectric conversion device includes a first electrode and a second electrode, and a photoelectric conversion layer between the first electrode and the second electrode. The photoelectric conversion layer includes a first material, a second material, and a third material. The first material and the second material form a pn junction. The third material is different from the first material and the second material, and the third material is configured to adjust (change, modify) the energy level distribution of the first material or the second material.

[0012] In some embodiments, the dipole moment of the third material may be greater than or equal to about 5.5 Debyes.

[0013] In some embodiments, the third material may be configured to adjust the HOMO level distribution of the first material, and the HOMO level of the third material may be deeper or shallower than the HOMO level of the first material by a value in the range of less than or equal to about 0.3 eV.

[0014] In some embodiments, the HOMO level of the third material may be about 4.7 eV to about 6.2 eV, and the HOMO level of the first material may be about 5.0 eV to about 5.8 eV.

[0015] In some embodiments, the HOMO level of the third material may be about 5.1 eV to about 6.0 eV, and the HOMO level of the first material may be about 5.0 eV to about 5.8 eV.

[0016] In some embodiments, the third material provides an adjusted HOMO level of the first material, and the adjusted HOMO level of the first material may be deeper than the HOMO level of the first material.

[0017] In some embodiments, the adjusted HOMO level of the first material may be between the HOMO level of the first material and the HOMO level of the second material.

[0018] In some embodiments, the absorption spectrum of the photoelectric conversion layer may have a maximum absorption wavelength in a first wavelength region. The first wavelength region may be one of a blue wavelength region, a green wavelength region, a red wavelength region, and an infrared wavelength region. The first material and the third material may each be a light-absorbing material having a maximum absorption wavelength in the first wavelength region.

[0019] In some embodiments, the photoelectric conversion layer may include a mixture of the first material, the second material, and the third material.

[0020] In some implementations, the third material may be included in an amount less than or equal to about 30% of the total volume of the first material and the third material.

[0021] In some embodiments, the HOMO energy level distribution of the photoelectric conversion layer may differ from the HOMO energy level distribution of the thin film formed from the first material and the second material.

[0022] In some embodiments, the HOMO level of the photoelectric conversion layer may be deeper than the HOMO level of the thin film formed from the first material and the second material.

[0023] In some embodiments, the HOMO level of the photoelectric conversion layer may be about 0.001 eV to about 1.2 eV deeper than the HOMO level of the thin film formed from the first material and the second material.

[0024] In some embodiments, the third material may be an organic material.

[0025] In some embodiments, at least one of the first material and the second material may be an organic material.

[0026] In some embodiments, the first material may be represented by the chemical formula A-1.

[0027] [Chemical Formula A-1]

[0028]

[0029] In chemical formula A-1,

[0030] X 1 It can be O, S, Se, Te, SO, SO2, SiR a R b , or GeR c R d ,

[0031] Ar 1 It may be a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heterocyclic group, or a fused ring including combinations thereof.

[0032] Ar 1a and Ar 2a It can be independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl.

[0033] Ar 1a and Ar 2a They can exist independently or connect with each other to form fused rings, and

[0034] R 1 -R 3 and R a -R dIt can be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano.

[0035] In some embodiments, the second material may include inorganic materials, thiophene or thiophene derivatives, fullerene or fullerene derivatives, or combinations thereof.

[0036] In some embodiments, the third material may be represented by chemical formula 1-1.

[0037] [Chemical Formula 1-1]

[0038]

[0039] In chemical formula 1-1,

[0040] X 2 It can be O, S, Se, Te, SO, SO2, SiR a R b , or GeR c R d ,

[0041] Ar 2 It may be a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heterocyclic group, or a fused ring including combinations thereof.

[0042] Ar 1b and Ar 2b It can be independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl.

[0043] Ar 1b and Ar 2b They can exist independently or connect with each other to form fused rings, and

[0044] R 4 -R 6 and R a -R d It can be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano.

[0045] According to an exemplary embodiment, a photoelectric conversion device includes a first electrode and a second electrode, and a photoelectric conversion layer between the first electrode and the second electrode. The photoelectric conversion layer includes a mixture of a first material, a second material, and a third material. The first material, the second material, and the third material are different from each other. The first material and the third material are light-absorbing materials having a maximum absorption wavelength in a first wavelength region. The first wavelength region is one of a blue wavelength region, a green wavelength region, a red wavelength region, and an infrared wavelength region. The dipole moment of the third material is greater than or equal to about 5.5 Debyes. Based on the total volume of the first material and the third material, the third material is included in an amount less than or equal to about 30% by volume.

[0046] In some embodiments, the first material and the third material may be p-type materials, and the second material may be an n-type material.

[0047] In some embodiments, the HOMO level of the third material may be deeper than the HOMO level of the first material, or the HOMO level of the third material may be shallower than the HOMO level of the first material by a value in the range of less than or equal to about 0.3 eV.

[0048] In some embodiments, the HOMO level of the third material may be about 4.7 eV to about 6.2 eV, and the HOMO level of the first material may be about 5.0 eV to about 5.8 eV.

[0049] In some embodiments, the HOMO level of the third material may be about 5.1 eV to about 6.0 eV, and the HOMO level of the first material may be about 5.0 eV to about 5.8 eV.

[0050] In some embodiments, the third material may be included in an amount of about 1% to about 10% of the total volume of the first material and the third material.

[0051] In some embodiments, the photoelectric conversion layer may be a ternary system composed of the first material, the second material, and the third material.

[0052] In some embodiments, the second material may include inorganic materials, thiophene or thiophene derivatives, fullerenes or fullerene derivatives, or combinations thereof. The first material may be represented by the chemical formula A-1.

[0053] [Chemical Formula A-1]

[0054]

[0055] In chemical formula A-1,

[0056] X 1 It can be O, S, Se, Te, SO, SO2, SiR a R b , or GeR c R d ,

[0057] Ar 1 It may be a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heterocyclic group, or a fused ring including combinations thereof.

[0058] Ar 1a and Ar 2a It can be independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl.

[0059] Ar 1a and Ar 2a They can exist independently or connect with each other to form fused rings, and

[0060] R 1 -R 3 and R a -R d It can be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano.

[0061] In some embodiments, the third material may be represented by chemical formula 1-1.

[0062] [Chemical Formula 1-1]

[0063]

[0064] In chemical formula 1-1,

[0065] X 2 It can be O, S, Se, Te, SO, SO2, SiR a R b , or GeR c R d ,

[0066] Ar 2 It may be a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heterocyclic group, or a fused ring including combinations thereof.

[0067] Ar 1b and Ar2b It can be independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl.

[0068] Ar 1b and Ar 2b They can exist independently or connect with each other to form fused rings, and

[0069] R 4 -R 6 and R a -R d It can be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano.

[0070] According to an example implementation, a sensor including any of the above-described photoelectric conversion devices is provided.

[0071] According to an example implementation, an electronic device including any of the above-described photoelectric conversion devices or sensors is provided.

[0072] In an exemplary embodiment of the inventive concept, residual charge carriers can be reduced and charge carrier extraction characteristics can be improved. Attached Figure Description

[0073] Figure 1 To show a cross-sectional view of an example of a photoelectric conversion device according to an exemplary embodiment,

[0074] Figure 2 To show a cross-sectional view of another example of the photoelectric conversion device according to the exemplary embodiment,

[0075] Figure 3 To show a cross-sectional view of an example image sensor according to an exemplary implementation,

[0076] Figure 4 To show a top view of an example of an image sensor according to an exemplary implementation,

[0077] Figure 5 To display Figure 4 A cross-sectional view of an example of an image sensor.

[0078] Figure 6 To display Figure 4 A cross-sectional view of another example of an image sensor.

[0079] Figure 7To show a top view of another example of an image sensor according to an exemplary implementation,

[0080] Figure 8 To display Figure 7 A cross-sectional view of an example of an image sensor.

[0081] Figure 9 To show a top view of another example of an image sensor according to an exemplary implementation,

[0082] Figure 10 To display Figure 9 A cross-sectional view of an example of an image sensor.

[0083] Figure 11 To show a cross-sectional view of an example image sensor according to an exemplary implementation,

[0084] Figure 12 To show a cross-sectional view of another example of an image sensor according to an exemplary implementation,

[0085] Figure 13 To illustrate a schematic diagram of an electronic device according to an example embodiment,

[0086] Figure 14 A graph showing the changes in the HOMO energy level distribution of the first material.

[0087] Figure 15 and 16 A graph showing the variation of residual charge carriers depending on the HOMO energy level distribution of the first material; and

[0088] Figure 17 A block diagram of a digital camera including an image sensor according to an embodiment. Detailed Implementation

[0089] Example implementations will be described in detail below, and they can be readily performed by those skilled in the art. However, this disclosure may be embodied in many different forms and should not be construed as limited to the exemplary implementations set forth herein.

[0090] In the accompanying drawings, the thickness of layers, films, panels, regions, etc., is magnified for clarity.

[0091] It will be understood that when an element, such as a layer, film, region, or substrate, is referred to as being "on" another element, it may be directly on said other element or there may be intermediate elements present. Conversely, when an element is referred to as being "directly on" another element, there are no intermediate elements present.

[0092] In the following text, as used herein, unless otherwise defined, “substituted” means that the hydrogen atom of a compound or group is replaced by a substituent selected from the following: halogen atom, hydroxyl, alkoxy, nitro, cyano, amino, azide, amido, hydrazine, hydrazone, carbonyl, carbamoyl, thiol group, ester group, carboxyl group or a salt thereof, sulfonic acid group or a salt thereof, phosphate group or a salt thereof, silyl, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C30 aryl, C7-C30 aralkyl, C1-C30 alkoxy, C1-C20 heteroalkyl, C3-C20 heteroaryl, C3-C20 heteroaryl, C3-C30 cycloalkyl, C3-C15 cycloalkenyl, C6-C15 cycloalkynyl, C3-C30 heterocycloalkyl, and combinations thereof.

[0093] As used herein, unless otherwise specifically defined, “hybrid” refers to a mixture of 1 to 4 heteroatoms selected from N, O, S, Se, Te, Si, and P.

[0094] In the following text, "combination" refers to a mixture or stacked structure of two or more.

[0095] As used herein, unless otherwise specifically defined, energy levels refer to the highest occupied molecular orbital (HOMO) energy level and the lowest unoccupied molecular orbital (LUMO) energy level. As used herein, "HOMO energy level of the first material" and "original HOMO energy level of the first material" are used interchangeably, both referring to the HOMO energy level of the first material before it has been modified by the third material.

[0096] In the following text, the work function or energy level is expressed as an absolute value relative to the vacuum energy level. Furthermore, when the work function or energy level is referred to as deep, high, or large, it may have a large absolute value based on the vacuum energy level "0 eV", while when the work function or energy level is referred to as shallow, low, or small, it may have a small absolute value based on the vacuum energy level "0 eV".

[0097] In the following text, unless otherwise specifically defined, the work function and energy level can be values ​​calculated using the B3LYP / def2-SVP basis set via Turboomole.

[0098] When the terms “about” or “substantially” are used in this specification to refer to numerical values, it is intended that the relevant numerical value includes manufacturing or operational tolerances (e.g., ±10%) around the stated numerical value. Similarly, when the terms “generally (usually)” and “substantially” are used to refer to geometry, it is intended that the geometry is not required to be precise, but rather that the range of the shape is within the scope of this disclosure. Furthermore, regardless of whether a numerical value or shape is modified by “about” or “substantially”, it will be understood that these values ​​and shapes should be interpreted as including manufacturing or operational tolerances (e.g., ±10%) around the stated numerical value or shape.

[0099] Hereinafter, the photoelectric conversion device according to the embodiments is described with reference to the accompanying drawings.

[0100] Figure 1 A cross-sectional view showing an example of a photoelectric conversion device according to an exemplary embodiment.

[0101] Reference Figure 1 According to an example embodiment, the photoelectric conversion device 100 includes a first electrode 10, a second electrode 20, and a photoelectric conversion layer 30.

[0102] A substrate (not shown) may be disposed on the side of the first electrode 10 or the second electrode 20. The substrate may be made, for example, of inorganic materials such as glass, silicon wafers, or organic materials such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyethersulfone, or combinations thereof.

[0103] The substrate can be omitted.

[0104] One of the first electrode 10 and the second electrode 20 is an anode and the other is a cathode. For example, the first electrode 10 may be an anode and the second electrode 20 may be a cathode.

[0105] At least one of the first electrode 10 and the second electrode 20 may be a transparent electrode. Here, the transparent electrode may have a high light transmittance of greater than or equal to about 80%. The transparent electrode may include at least one of, for example, an oxide conductor, a carbon conductor, and a metal thin film. The oxide conductor may include at least one of, for example, 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 include at least one of graphene and carbon nanostructures; and the metal thin film may be a very thin film comprising aluminum (Al), magnesium (Mg), silver (Ag), gold (Au), their alloys, or combinations thereof.

[0106] One of the first electrode 10 and the second electrode 20 may be a reflective electrode. Here, the reflective electrode may have, for example, a light transmittance of less than about 10% or a high reflectance of greater than or equal to about 5%. The reflective electrode may include a reflective conductor, such as a metal, and may include, for example, aluminum (Al), silver (Ag), gold (Au), or alloys thereof.

[0107] For example, the first electrode 10 and the second electrode 20 may each be a transparent electrode, and one of the first electrode 10 and the second electrode 20 may be a light receiving electrode.

[0108] For example, the first electrode 10 can be a transparent electrode, the second electrode 20 can be a reflective electrode, and the first electrode 10 can be a light-receiving electrode.

[0109] For example, the first electrode 10 can be a reflective electrode, the second electrode 20 can be a transparent electrode, and the second electrode 20 can be a light receiving electrode.

[0110] The photoelectric conversion layer 30 can be disposed between the first electrode 10 and the second electrode 20. The second electrode 20 can be disposed on the first electrode 10.

[0111] The photoelectric conversion layer 30 can be configured to absorb light in at least a portion of the wavelength region and can be configured to convert the absorbed light into an electrical signal. The photoelectric conversion layer 30 can be configured to convert a portion of light in, for example, the blue wavelength region (hereinafter referred to as "blue light"), the green wavelength region (hereinafter referred to as "green light"), the red wavelength region (hereinafter referred to as "red light"), and / or the infrared wavelength region (hereinafter referred to as "infrared light") into an electrical signal.

[0112] For example, the photoelectric conversion layer 30 may be configured to selectively absorb at least one of blue light, green light, red light, and infrared light and convert the absorbed light into an electrical signal. Here, selective absorption of at least one of blue light, green light, red light, and infrared light may mean that the absorption spectrum has a maximum absorption wavelength (λ) in one of the wavelength regions. 最大 ( ): Greater than or equal to about 380 nm and less than about 500 nm, about 500 nm to about 600 nm, greater than about 600 nm and less than or equal to about 700 nm, and greater than about 700 nm and less than or equal to about 3000 nm, and the absorption spectrum in the corresponding wavelength regions may be significantly higher than those in other wavelength regions. Here, "significantly higher" may mean that about 70% to about 100%, about 75% to about 100%, about 80% to about 100%, about 85% to about 100%, about 90% to about 100%, or about 95% to about 100% of the total area of ​​the absorption spectrum belongs to the corresponding wavelength region.

[0113] The photoelectric conversion layer 30 may include a first material and a second material forming a pn junction, and the first material and the second material may receive light from the outside to generate excitons. The generated excitons may be separated into holes and electrons. For example, the first material may be a p-type material and the second material may be an n-type material.

[0114] For example, the first material and the second material may each be a light-absorbing material, and for example, at least one of the first material and the second material may be an organic light-absorbing material. For example, at least one of the first material and the second material may be a wavelength-selective light-absorbing material configured to selectively absorb light in a desired (and / or alternatively predetermined) wavelength region. For example, at least one of the first material and the second material may be a wavelength-selective organic light-absorbing material. The absorption spectra of the first material and the second material may have a maximum absorption wavelength (λ) in the same or different wavelength regions. 最大 ).

[0115] For example, the first material and the second material can be configured to independently and selectively absorb one of blue light, green light, red light, and infrared light. The maximum absorption wavelength (λ) of the absorption spectra of the first material and the second material... 最大 It can exist in one of the following wavelength regions: greater than or equal to about 380 nm and less than about 500 nm, about 500 nm to about 600 nm, greater than about 600 nm and less than or equal to about 700 nm, and greater than about 700 nm and less than or equal to about 3000 nm.

[0116] For example, the first material and / or the second material may be organic materials.

[0117] For example, the first material and / or the second material may be small molecule compounds.

[0118] For example, the first material and / or the second material may be a depositable compound.

[0119] For example, the first material may be an organic material having a core structure including an electron-donating part (EDM), a π-conjugated connection part, and an electron-receiving part (EMA).

[0120] The first material may be represented, for example, by chemical formula A, but is not limited thereto.

[0121] [Chemical Formula A]

[0122] EDM1-HA1-EAM1

[0123] In chemical formula A,

[0124] HA1, which serves as the π-conjugated linker, can be a substituted or unsubstituted C2-C30 heterocyclic group.

[0125] EDM1 can be a donor section, and

[0126] EAM1 can be the electron-receiving part.

[0127] For example, the first material represented by chemical formula A can be represented by chemical formula A-1, but is not limited thereto.

[0128] [Chemical Formula A-1]

[0129]

[0130] In chemical formula A-1,

[0131] X 1 It can be O, S, Se, Te, SO, SO2, SiR a R b , or GeR c R d ,

[0132] Ar 1 It may be a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heterocyclic group, or two or more of the aforementioned fused rings (e.g., fused rings including combinations thereof).

[0133] Ar 1a and Ar 2a It can be independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl.

[0134] Ar 1a and Ar 2a They can exist independently or connect with each other to form fused rings, and

[0135] R 1 -R 3 and R a -R d It can be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano.

[0136] For example, in chemical formula A-1, Ar 1a and Ar 2aIt may independently be one of the following: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthraquinyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted naphridinyl, substituted or unsubstituted cyclolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted phthalazinyl, substituted or unsubstituted benzotriazinyl, substituted or unsubstituted pyridopyrazinyl, substituted or unsubstituted pyridopyrimidinyl, or substituted or unsubstituted pyridopyridinyl.

[0137] For example, Ar with chemical formula A-1 1a and Ar 2a They can be connected to each other to form a ring, and for example, Ar 1a and Ar 2a A ring can be formed by connecting the following to each other: single bond, -O-, -S-, -Se-, -Te-, -N=, -NR e -、-(CR f R g ) n2 -(where n2 is 1 or 2), -SiR h R i -、-GeR j R k -、-(C(R 1 )=C(R m ))-、or SnR n R o Here, R e -R o It can independently be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano. Furthermore, R f and R g R h and R i R j and R k R l and R m and R n and R o They can exist independently or be connected to each other to form a ring. For example, R f and R g They can be connected to form a loop, R h and R i They can be connected to form a loop, R j and R k They can be connected to form a loop, R1 and R m They can be connected to each other to form a loop, and / or R n and R o They can be connected to each other to form a ring.

[0138] For example, the first material represented by chemical formula A-1 may be represented by chemical formulas A-2 to A-5, but is not limited thereto.

[0139]

[0140]

[0141] In chemical formulas A-2 to A-5,

[0142] X 1 and R 1 -R 3 The description is the same as that for chemical formula A-1 above.

[0143] Ar 3 It may be a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heterocyclic group, or two or more of the aforementioned fused rings (e.g., fused rings including combinations thereof).

[0144] G can be one of the following: single bond, -O-, -S-, -Se-, -Te-, -N=, -NR e -、-(CR f R g ) n2 -(where n2 is 1 or 2), -SiR h R i -、-GeR j R k -、-(C(R 1 )=C(R m ))-、or SnR n R o , where R e -R o It can be independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano, and R f and R g R h and R i R j and R k R l and R m and R n and R oThey can exist independently or be connected to each other to form a ring.

[0145] Y 2 It can be O, S, Se, Te, or C(R) p (CN)(where R) p It can be hydrogen, cyano (-CN), or C1-C10 alkyl.

[0146] R 6a -R 6e R 7a -R 7e R 16 and R 17 It can be independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano.

[0147] R 6a -R 6e It can exist independently or two adjacent ones can be connected to each other to provide a fused ring, and

[0148] R 7a -R 7e It can exist independently or two adjacent ones can be connected to each other to provide a fused ring.

[0149] For example, Ar with chemical formula A-2 or A-4 3 It can be a phenyl group, naphthyl group, anthracene group, thiophene group, selenophenol group, tellurene group, pyridine group, pyrimidine group, or two or more of the aforementioned fused rings.

[0150] The second material may include, for example, organic materials, inorganic materials, and / or organic / inorganic materials, and may be, for example, thiophene or thiophene derivatives, fullerenes or fullerene derivatives, but is not limited thereto. Thiophene derivatives or fullerene derivatives may be those commonly used in the art and may refer to thiophene or fullerene compounds having substituents. The substituents may include, for example, C1-C30 alkyl (e.g., C1-C20 alkyl, or C1-C10 alkyl), C6-C30 aryl (e.g., C6-C20 aryl, or C6-C12 aryl), etc.

[0151] The photoelectric conversion layer 30 further includes a third material. The third material may be a material different from the first material and the second material, and may be a dopant in the photoelectric conversion layer 30 used to adjust the physical properties of the first material and / or the second material.

[0152] The third material can be mixed with the first and second materials, and therefore the third material can contact the first and / or second materials at the atomic scale to adjust the morphology or molecular conformation of the first and / or second materials. Therefore, the morphological and molecular conformational diversity of the photoelectric conversion layer 30 comprising the first, second, and third materials can differ from the morphological and molecular conformational diversity of a thin film made of the first and second materials (without the third material).

[0153] According to quantum computing based on this morphology, the third material with a high dipole moment can be configured to adjust the energy level distribution of the first material and / or the second material. For example, the third material with a high dipole moment can be configured to adjust the HOMO or LUMO energy level distribution of the first or second material. Therefore, the HOMO or LUMO energy level distribution of the photoelectric conversion layer 30, which includes the first material, the second material, and the third material, may differ from the HOMO or LUMO energy level distribution of a thin film composed of the first and second materials (but without the third material).

[0154] The dipole moment of the third material may be, for example, greater than or equal to about 5.5 dbill, greater than or equal to about 6 dbill, greater than or equal to about 8 dbill, greater than or equal to about 10 dbill, or greater than or equal to about 12 dbill, or within the range of about 5.5 dbill to about 15 dbill, about 6 dbill to about 15 dbill, about 8 dbill to about 15 dbill, about 10 dbill to about 15 dbill, or about 12 dbill to about 15 dbill, but is not limited thereto.

[0155] The photoelectric conversion layer 30 includes the third material having a high dipole moment as a dopant and can therefore be tuned such that the first material or the second material may have a distribution of HOMO or LUMO energy levels in a desired region or may not have a distribution of HOMO or LUMO energy levels in an undesired region.

[0156] For example, when the first material is a p-type material and the second material is an n-type material, the third material can be a p-type material that adjusts the HOMO level distribution of the first material. For example, the HOMO level distribution of the first material adjusted by the third material can be shifted towards a deeper HOMO level direction compared to the original HOMO level distribution of the first material.

[0157] Thus, due to the shift in the HOMO level distribution of the first material as a p-type material, the desired region of the HOMO level distribution can be increased, or the undesirable region of the HOMO level distribution can be reduced or eliminated. For example, regions of shallow HOMO levels in the HOMO level distribution of the p-type material where a relatively large number of charge carrier (e.g., hole) trapping sites can be reduced or eliminated. For example, regions of HOMO levels shallower than approximately 5.2 eV in the HOMO level distribution of the p-type material can be reduced or eliminated.

[0158] For example, the HOMO level distribution of the first material, adjusted by the third material, can be shifted towards deeper HOMO levels. Here, the third material may have deeper or shallower HOMO levels compared to the HOMO levels of the first material. For example, the HOMO levels of the third material may be deeper than the HOMO levels of the first material, or the HOMO levels of the third material may be shallower than the HOMO levels of the first material by a value less than or equal to about 0.3 eV. For example, the HOMO levels of the third material may be in the range of about -0.3 eV to about 1.2 eV, excluding 0 eV, compared to the HOMO levels of the first material. For example, the original HOMO levels of the first material may be in the range of about 5.0 eV to about 5.8 eV, and the HOMO levels of the third material may be in the range of about 4.7 eV to about 6.2 eV. For example, the HOMO level of the third material may be deeper than the original HOMO level of the first material. For instance, the original HOMO level of the first material may be in the range of about 5.0 eV to about 5.8 eV, and the HOMO level of the third material may be in the range of about 5.1 eV to about 6.2 eV. The HOMO level of the first material adjusted by the third material may be deeper than the original HOMO level of the first material. The HOMO level of the first material adjusted by the third material may, for example, be deeper than or equal to about 0.001 eV than the original HOMO level of the first material, for example, about 0.001 eV to about 1.2 eV, about 0.002 eV to about 0.8 eV, about 0.003 eV to about 0.4 eV, about 0.004 eV to about 0.1 eV, about 0.005 eV to about 0.08 eV, about 0.005 eV to about 0.04 eV, about 0.005 eV to about 0.03 eV, about 0.005 eV to about 0.02 eV, or about 0.005 eV to about 0.018 eV.

[0159] For example, the HOMO level of the second material, as an n-type material, may be deeper than about 6.2 eV, and the HOMO level of the third material may be between the HOMO levels of the first material and the second material. For example, the difference between the HOMO level of the third material and the HOMO level of the second material may be smaller than the difference between the HOMO levels of the first material and the second material. For example, the original HOMO level of the first material may be in the range of about 5.0 eV to about 5.8 eV, the HOMO level of the second material may be in the range of about 6.3 eV to about 7.2 eV, and the HOMO level of the third material may be in the range of about 5.1 eV to about 6.2 eV.

[0160] Therefore, the HOMO energy level of the photoelectric conversion layer 30, which includes the first, second, and third materials, may be deeper than the HOMO energy level of the thin film formed from the first and second materials (without the third material), for example, deeper than the HOMO energy level of the thin film formed from the first and second materials (without the third material) by about 0.001 eV, for example, about 0.001 eV to about 1.2 eV, about 0.002 eV to about 0.8 eV, about 0.003 eV to about 0.4 eV, about 0.004 eV to about 0.1 eV, about 0.005 eV to about 0.08 eV, about 0.005 eV to about 0.04 eV, about 0.005 eV to about 0.03 eV, about 0.005 eV to about 0.02 eV, or about 0.005 eV to about 0.018 eV.

[0161] The third material can be an organic material, an inorganic material, and / or an organic / inorganic material having the above-mentioned properties. The third material can be, for example, an organic material, a small molecule compound, or a depositable organic compound. For example, the photoelectric conversion layer 30 can be a co-deposited thin film of the first material, the second material, and the third material.

[0162] The third material may be, for example, a light-absorbing material, and may be, for example, a light-absorbing material configured to selectively absorb light in one of the blue wavelength region, the green wavelength region, the red wavelength region, and the infrared wavelength region.

[0163] For example, the absorption spectra of the first material and the third material may have a maximum absorption wavelength (λ) that commonly belongs to one of the blue wavelength region, green wavelength region, red wavelength region, and infrared wavelength region. 最大 For example, the absorption spectra of the first material and the third material may each have a maximum absorption wavelength (λ) in the blue wavelength region greater than or equal to about 380 nm and less than about 500 nm. 最大For example, the absorption spectra of the first material and the third material may each have a maximum absorption wavelength (λ) in the green wavelength region of about 500 nm to about 600 nm. 最大 For example, the absorption spectra of the first material and the third material may each have a maximum absorption wavelength (λ) in the red wavelength region greater than about 600 nm and less than or equal to about 700 nm. 最大 For example, the absorption spectra of the first material and the third material may each have a maximum absorption wavelength (λ) in the infrared wavelength region greater than about 700 nm and less than or equal to about 3000 nm. 最大 ).

[0164] The third material may be represented, for example, by chemical formula 1, but is not limited thereto.

[0165] [Chemical Formula 1]

[0166] EDM3-HA3-EAM3

[0167] In chemical formula 1,

[0168] HA3, which serves as the π-conjugated linker, can be a substituted or unsubstituted C2-C30 heterocyclic group.

[0169] EDM3 can be used for the electron-donating section, and

[0170] EAM3 can be the electron-receiving part.

[0171] For example, HA3 may be the same as or different from HA1 described above, EDM3 may be the same as or different from EDM1 described above, and EAM3 may be the same as or different from EAM1 described above. However, at least one of HA3, EDM3, and EAM3 may be different from the corresponding HA1, EDM1, or EAM1.

[0172] For example, a third material represented by chemical formula 1 may be represented by chemical formula 1-1, but is not limited thereto.

[0173] [Chemical Formula 1-1]

[0174]

[0175] In chemical formula 1-1,

[0176] X 2 It can be O, S, Se, Te, SO, SO2, SiR a R b , or GeR c R d ,

[0177] Ar 2It can be a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heterocyclic group, or two or more of the aforementioned fused rings.

[0178] Ar 1b and Ar 2b It can be independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl.

[0179] Ar 1b and Ar 2b They can exist independently or connect with each other to form fused rings, and

[0180] R 4 -R 6 and R a -R d It can be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano.

[0181] For example, in chemical formula 1-1, Ar 1b and Ar 2b It may independently be a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthraquinyl, a substituted or unsubstituted phenanthryl, a substituted or unsubstituted pyridinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted quinolinyl, a substituted or unsubstituted isoquinolinyl, a substituted or unsubstituted naphthidyl, a substituted or unsubstituted cyclolinyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted phthalazinyl, a substituted or unsubstituted benzotriazinyl, a substituted or unsubstituted pyridopyrazinyl, a substituted or unsubstituted pyridopyrimidinyl, and a substituted or unsubstituted pyridopyridinyl.

[0182] For example, Ar with chemical formula 1-1 1b and Ar 2b They can be connected to each other to form a ring, or, for example, Ar 1b and Ar 2b They can be connected to each other using one of the following: single key, -O-, -S-, -Se-, -Te-, -N=, -NR e -、-(CR f R g ) n2 -(where n2 is 1 or 2), -SiR h R i -、-GeR j R k-、-(C(R 1 )=C(R m ))-、or SnR n R o Here, R e -R o Each of these can be independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano. Furthermore, R f and R g R h and R i R j and R k R l and R m and R n and R o They can exist independently or be connected to each other to form a ring.

[0183] For example, a third material represented by chemical formula 1-1 may be represented by chemical formulas 1-2 to 1-7, but is not limited thereto.

[0184]

[0185]

[0186] In chemical formulas 1-2 to 1-7,

[0187] X 2 and R 4 -R 6 As described above for chemical formula 1-1,

[0188] Ar 4 It can be a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heterocyclic group, or two or more of the aforementioned fused rings.

[0189] Ar 5 It can be a substituted or unsubstituted C3-C30 cycloalkyl group.

[0190] Z can be a single bond, -O-, -S-, -Se-, -Te-, -N=, -NR e -、-(CR f R g ) n2 -(where n2 is 1 or 2), -SiR h R i -、-GeR j R k -、-(C(R l)=C(R m ))-、or SnR n R o , where R e -R o It can be independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano, and R f and R g R h and R i R j and R k R l and R m and R n and R o They can exist independently or be connected to each other to form a ring.

[0191] Y 3 It can be O, S, Se, Te, or C(R) p (CN)(where R) p It can be hydrogen, cyano (-CN), or C1-C10 alkyl.

[0192] R 6f -R 6j R 7f -R 7j R 18 and R 19 It can be independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano.

[0193] R 6f -R 6j It can exist independently or two adjacent ones can be connected to each other to provide a fused ring, and

[0194] R 7f -R 7j It can exist independently or two adjacent ones can be connected to each other to provide a fused ring.

[0195] For example, Ar with chemical formulas 1-2, 1-4, or 1-6 4 It can be a phenyl group, naphthyl group, anthracene group, thiophene group, selenophenol group, tellurene group, pyridine group, pyrimidine group, or two or more of the aforementioned fused rings.

[0196] The photoelectric conversion layer 30 may be an intrinsic layer in which the first, second and third materials mentioned above are mixed in the form of a bulk heterojunction.

[0197] The first material and the second material can be mixed in a volume ratio of about 1:9 to about 9:1, for example, about 2:8 to about 8:2, about 3:7 to about 7:3, about 4:6 to about 6:4, or about 5:5.

[0198] The third material may be included in an amount such that, apart from adjusting the physical properties of the first and / or second materials, it does not affect the molecular stability of the first and second materials or other properties required in the photoelectric conversion layer 30. The third material may be included in an amount smaller than that of the first or second material. For example, based on the total volume of the first and third materials, the third material may be included in an amount less than or equal to about 30% of the volume, for example, about 1% to about 30% of the volume, about 1% to about 25% of the volume, about 1% to about 20% of the volume, about 1% to about 15% of the volume, or about 1% to about 10% of the volume.

[0199] For example, the photoelectric conversion layer 30 may be a ternary system composed of the first material, the second material, and the third material.

[0200] The photoelectric conversion device 100 may further include an anti-reflective layer (not shown) on the first electrode 10 or below the second electrode 20. The anti-reflective layer may be disposed on the light incident side and reduce the light reflectivity of the incident light, thereby further improving the light absorption. For example, the anti-reflective layer may be disposed on the first electrode 10 when light is incident on the first electrode 10, and below the second electrode 20 when light is incident on the second electrode 20.

[0201] The antireflective layer may include, for example, a material having a refractive index of about 1.6 to about 2.5, and may include at least one of a metal oxide, a metal sulfide, and an organic material having a refractive index within the range. The antireflective layer may include, for example, 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 organic materials such as amine derivatives, but is not limited thereto.

[0202] In the photoelectric conversion device 100, excitons can be generated within the photoelectric conversion layer 30 when light enters from the first electrode 10 or the second electrode 20 and the photoelectric conversion layer 30 is configured to absorb light in a desired (and / or alternatively predetermined) wavelength region. The excitons are separated into holes and electrons in the photoelectric conversion layer 30, and the separated holes are transported to the anode, which is one of the first electrode 10 and the second electrode 20, while the separated electrons are transported to the cathode, which is the other of the first electrode 10 and the second electrode 20, to allow current to flow.

[0203] Here, as described above, in addition to the first and second materials forming the pn junction, the photoelectric conversion layer 30 further includes the third material capable of adjusting the properties of the first and / or second materials, and thus achieving desired properties or eliminating undesirable properties. Therefore, the photoelectric characteristics of the photoelectric conversion device 100 can be improved. For example, as described above, the energy level distribution of the first or second material can be reduced or adjusted such that energy level regions in the photoelectric conversion layer 30 where a relatively large number of charge carrier trapping sites exist (e.g., regions with shallow HOMO energy levels) can be reduced or eliminated, and thus, among the charge carriers moving from the photoelectric conversion layer 30 to the first electrode 10 and / or the second electrode 20, residual charge carriers remaining or being trapped at the trapping sites can be reduced or prevented. Therefore, residual images (image retention) caused by residual charge carriers accumulating in the photoelectric conversion layer 30 can be reduced or prevented, resulting in improved electrical performance of the photoelectric conversion device 100.

[0204] Figure 2 A cross-sectional view showing another example of a photoelectric conversion device according to an exemplary embodiment.

[0205] Reference Figure 2 As in the embodiments described above, the photoelectric conversion device 100 according to this embodiment includes a first electrode 10, a second electrode 20, and a photoelectric conversion layer 30. However, unlike the embodiments described above, the photoelectric conversion device 100 according to this embodiment may further include auxiliary layers 40 and 50 between the first electrode 10 and the photoelectric conversion layer 30, and between the second electrode 20 and the photoelectric conversion layer 30.

[0206] The auxiliary layers 40 and 50 may include, but are not limited to, a hole injection layer (HIL) for promoting hole injection, a hole transport layer (HTL) for promoting hole transport, an electron blocking layer (EBL) for blocking electron movement, an electron injection layer (EIL) for promoting electron injection, an electron transport layer (ETL) for promoting electron transport, and / or a hole blocking layer (HBL) for blocking hole movement.

[0207] The auxiliary layers 40 and 50 may independently include organic materials, inorganic materials, and / or organic / inorganic materials.

[0208] For example, one of the auxiliary layers 40 and 50 may include an inorganic auxiliary layer. The inorganic auxiliary layer may include, for example, lanthanides, calcium (Ca), potassium (K), aluminum (Al), or alloys thereof, and the lanthanides may include, for example, ytterbium (Yb). The inorganic auxiliary layer may have a thickness of less than or equal to about 5 nm.

[0209] For example, one of the auxiliary layers 40 and 50 may include an organic auxiliary layer. The organic auxiliary layer may include, for example, a compound represented by chemical formula 2A or 2B, but is not limited thereto.

[0210] [Chemical Formula 2A]

[0211]

[0212] [Chemical Formula 2B]

[0213]

[0214] In chemical formula 2A or 2B,

[0215] M 1 and M 2 It can be independently O, S, Se, Te, CR q R r SiR s R t , or NR u ,

[0216] Ar 1c Ar 2c Ar 3c And Ar 4c It can be independently a substituted or unsubstituted C6-C30 aryl or a substituted or unsubstituted C3-C30 heteroaryl.

[0217] G 2 and G 3 Can be independently a single bond, -(CR) v R w ) n3 -, -O-, -S-, -Se-, -Te, -N=, -NR x - or -SiR y R z -, where n3 is 1 or 2, and

[0218] R 30 -R 37 and R q -R zIt can be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heterocyclic group, halogen, or cyano.

[0219] For example, the organic auxiliary layer may include, but is not limited to, compounds represented by chemical formula 2A-1 or 2B-1.

[0220] [Chemical Formula 2A-1]

[0221]

[0222] [Chemical Formula 2B-1]

[0223]

[0224] In chemical formula 2A-1 or 2B-1,

[0225] M 1 M 2 G 2 G 3 and R 30 -R 37 Same as described above,

[0226] R 38 -R 45 It can be hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano.

[0227] For example, the organic auxiliary layer may include, but is not limited to, compounds represented by chemical formula 2A-1a or 2B-1a.

[0228] [Chemical formula 2A-1a]

[0229]

[0230] [Chemical Formula 2B-1a]

[0231]

[0232] In chemical formulas 2A-1a and 2B-1a,

[0233] R 38 -R 45 Same as described in chemical formulas 2A-1 and 2B-1, and

[0234] R n and R oRegarding R in chemical formulas 2A and 2B q and R r The descriptions are the same.

[0235] For example, one of the auxiliary layers 40 and 50 may be an inorganic auxiliary layer, and the other of the auxiliary layers 40 and 50 may be an organic auxiliary layer.

[0236] For example, one of auxiliary layers 40 and 50 can be omitted.

[0237] The aforementioned photoelectric conversion device 100 can be applied to, for example, a sensor, and the sensor can be, for example, an image sensor. By reducing afterimages caused by residual charge carriers, the image sensor to which the aforementioned photoelectric conversion device 100 is applied is suitable for high-speed photography.

[0238] Hereinafter, examples of image sensors in which the above-described devices are applied are described with reference to the accompanying drawings. An organic CMOS image sensor is described as an example of the image sensor.

[0239] Figure 3 A cross-sectional view is shown to illustrate an example of an image sensor according to an exemplary implementation.

[0240] Reference Figure 3 The image sensor 300 according to an example embodiment includes a semiconductor substrate 110, an insulating layer 80, a photoelectric conversion device 100, and a color filter layer 70.

[0241] The semiconductor substrate 110 may be a silicon substrate and integrates a transfer transistor (not shown) and a charge memory 155. The transfer transistor and / or charge memory 155 may be integrated in each pixel. The charge memory 155 is electrically connected to the photoelectric conversion device 100.

[0242] Metal lines (not shown) and pads (not shown) are formed on the semiconductor substrate 110. To reduce signal delay, the metal lines and pads may be made of metals with low resistivity, such as aluminum (Al), copper (Cu), silver (Ag), and their alloys, but are not limited thereto.

[0243] An insulating layer 80 is formed on the metal lines and pads. The insulating layer 80 may be made of inorganic insulating materials such as silicon oxide and / or silicon nitride, or low dielectric constant (low K) materials such as SiC, SiCOH, SiCO, and SiOF. The insulating layer 80 has trenches 85 that expose the charge storage device 155. The trenches 85 may be filled with a filler.

[0244] The aforementioned photoelectric conversion device 100 is formed on the insulating layer 80. The photoelectric conversion device 100 may have... Figure 1The structure shown in Figure 2 is identical in detail to that described above. One of the first electrode 10 and the second electrode 20 of the photoelectric conversion device 100 may be a light receiving electrode, and the other of the first electrode 10 and the second electrode 20 of the photoelectric conversion device 100 may be connected to the charge memory 155.

[0245] A color filter layer 70 is formed on the photoelectric conversion device 100. The color filter layer 70 includes a blue filter 70a formed in the blue pixels, a red filter 70b formed in the red pixels, and a green filter 70c formed in the green pixels. However, the color filter layer 70 may include a cyan filter, a magenta filter, and / or a yellow filter in place of the above filters, or may further include them in addition to the above filters.

[0246] An insulating layer 180 is formed between the photoelectric conversion device 100 and the color filter layer 70. The insulating layer 180 may be omitted.

[0247] A focusing lens (not shown) may be further formed on the color filter layer 70. The focusing lens can control the direction of the incident light and focus the light into a region. The focusing lens may have, for example, a cylindrical or hemispherical shape, but is not limited thereto.

[0248] Figure 4 To show a top view of an example of an image sensor according to an exemplary implementation, and Figure 5 To display Figure 4 A cross-sectional view of an example of an image sensor.

[0249] Reference Figure 4 and 5 The image sensor 400 according to an example embodiment includes a semiconductor substrate 110 integrating light sensing devices 150a and 150b, a transmission transistor (not shown), and a charge storage device 155, a lower insulating layer 60, a color filter layer 70, an upper insulating layer 80, and the aforementioned photoelectric conversion device 100.

[0250] The semiconductor substrate 110 may be a silicon substrate and integrates photosensing devices 150a and 150b, a transfer transistor (not shown), and a charge storage device 155. The photosensing devices 150a and 150b may be photodiodes.

[0251] Light sensing devices 150a and 150b, a transfer transistor, and / or a charge memory 155 may be integrated in each pixel, and as shown in the figure, light sensing devices 150a and 150b may be included in the blue pixel and the red pixel, respectively, and the charge memory 155 may be included in the green pixel.

[0252] Light sensing devices 150a and 150b sense light. Information sensed by the light sensing devices can be transmitted via the transmission transistor. Charge memory 155 is electrically connected to photoelectric conversion device 100, which will be described later, and information from charge memory 155 can be transmitted via the transmission transistor.

[0253] Metal lines (not shown) and pads (not shown) are formed on the semiconductor substrate 110. To reduce signal delay, the metal lines and pads may be made of metals with low resistivity, such as aluminum (Al), copper (Cu), silver (Ag), and alloys thereof, but are not limited thereto. However, the structure is not limited to this, and the metal lines and pads may be disposed below the photosensitive devices 150a and 150b.

[0254] A lower insulating layer 60 is formed on the metal lines and pads. The lower insulating layer 60 may be made of inorganic insulating materials such as silicon oxide and / or silicon nitride, or low dielectric constant (low K) materials such as SiC, SiCOH, SiCO, and SiOF. The lower insulating layer 60 has trenches 85 that expose the charge storage device 155. The trenches 85 may be filled with a filler.

[0255] A color filter layer 70 is formed on the lower insulating layer 60. The color filter layer 70 includes a blue filter 70a formed in the blue pixels and a red filter 70b formed in the red pixels. However, this disclosure is not limited thereto and may alternatively include a cyan filter, a magenta filter, and / or a yellow filter. In this embodiment, a green filter is not included, but may be further included.

[0256] An upper insulating layer 80 is formed on the color filter layer 70. The upper insulating layer 80 eliminates the steps caused by the color filter layer 70 and smooths the surface. The upper insulating layer 80 and the lower insulating layer 60 may include contact holes (not shown) that expose pads and trenches 85 that expose the charge memory 155 of the green pixel.

[0257] The aforementioned photoelectric conversion device 100 is formed on the upper insulating layer 80. The photoelectric conversion device 100 may have... Figure 1 The structure shown in Figure 2 is identical in detail to that described above. One of the first electrode 10 and the second electrode 20 of the photoelectric conversion device 100 may be a light receiving electrode, and the other of the first electrode 10 and the second electrode 20 of the photoelectric conversion device 100 may be connected to the charge memory 155.

[0258] An insulating layer 180 is formed on the photoelectric conversion device 100. The insulating layer 180 may be omitted.

[0259] A focusing lens (not shown) may be further formed on the photoelectric conversion device 100. The focusing lens can control the direction of the incident light and focus the light into a region. The focusing lens may have, for example, a cylindrical or hemispherical shape, but is not limited thereto.

[0260] Figure 6 To display Figure 4 A cross-sectional view of another example of an image sensor.

[0261] Reference Figure 6 The image sensor 500 according to this embodiment includes a semiconductor substrate 110 integrating light sensing devices 150a and 150b, a transmission transistor (not shown), and a charge storage device 155, an upper insulating layer 80, and a photoelectric conversion device 100.

[0262] However, in the image sensor 500 according to this embodiment, unlike the embodiment described above, the photosensitive devices 150a and 150b are stacked vertically, and the lower insulating layer 60 and the color filter layer 70 are omitted. The photosensitive devices 150a and 150b are electrically connected to a transmission transistor (not shown), and their information can be transmitted through the transmission transistor. Depending on the stacking depth, the photosensitive devices 150a and 150b can be configured to selectively absorb light in various wavelength regions.

[0263] The photoelectric conversion device 100 may have Figure 1 The structure shown in Figure 2 is identical in detail to that described above. One of the first electrode 10 and the second electrode 20 of the photoelectric conversion device 100 may be a light receiving electrode, and the other of the first electrode 10 and the second electrode 20 of the photoelectric conversion device 100 may be connected to the charge memory 155.

[0264] An insulating layer 180 is formed on the photoelectric conversion device 100. The insulating layer 180 may be omitted.

[0265] Figure 7 To show a top view of another example of an image sensor according to an exemplary implementation, and Figure 8 To display Figure 7 A cross-sectional view of an example of an image sensor.

[0266] The image sensor 600 according to this embodiment has a structure in which a green photoelectric device configured to selectively absorb light in the green wavelength region, a blue photoelectric device configured to selectively absorb light in the blue wavelength region, and a red photoelectric device configured to selectively absorb light in the red wavelength region are stacked.

[0267] The image sensor 600 according to this embodiment includes a semiconductor substrate 110, a lower insulating layer 60, a middle insulating layer 65, an upper insulating layer 80, a first photoelectric conversion device 100a, a second photoelectric conversion device 100b, and a third photoelectric conversion device 100c.

[0268] The semiconductor substrate 110 may be a silicon substrate and integrates a transfer transistor (not shown) and charge storage devices 155a, 155b, and 155c.

[0269] Metal lines (not shown) and pads (not shown) are formed on the semiconductor substrate 110, and a lower insulating layer 60 is formed on the metal lines and pads.

[0270] The first photoelectric conversion device 100a, the second photoelectric conversion device 100b, and the third photoelectric conversion device 100c are sequentially formed on the lower insulating layer 60.

[0271] The first, second, and third photoelectric conversion devices 100a, 100b, and 100c can each independently possess... Figure 1 The structure shown in Figure 2 is described in the same way as described above. One of the first electrode 10 and the second electrode 20 of the first, second, and third photoelectric conversion devices 100a, 100b, and 100c may be a light receiving electrode, and the other of the first electrode 10 and the second electrode 20 of the first, second, and third photoelectric conversion devices 100a, 100b, and 100c may be connected to the charge storage devices 155a, 155b, and 155c.

[0272] The first photoelectric conversion device 100a can be configured to selectively absorb light in one of the red, blue, and green wavelength regions and can be configured to photoelectrically convert the absorbed light. For example, the first photoelectric conversion device 100a can be a red photoelectric conversion device. An intermediate insulating layer 65 is formed on the first photoelectric conversion device 100a.

[0273] The second photoelectric conversion device 100b is formed on the intermediate insulating layer 65.

[0274] The second photoelectric conversion device 100b can be configured to selectively absorb light in one of the red, blue, and green wavelength regions and can be configured to photoelectrically convert the absorbed light. For example, the second photoelectric conversion device 100b can be a blue photoelectric conversion device.

[0275] An upper insulating layer 80 is formed on the second photoelectric conversion device 100b. The lower insulating layer 60, the middle insulating layer 65, and the upper insulating layer 80 have a plurality of trenches 85a, 85b, and 85c that expose charge storage devices 155a, 155b, and 155c.

[0276] A third photoelectric conversion device 100c is formed on the upper insulating layer 80. The third photoelectric conversion device 100c can be configured to selectively absorb light in one of the red, blue, and green wavelength regions and to photoelectrically convert the absorbed light. For example, the third photoelectric conversion device 100c can be a green photoelectric conversion device.

[0277] A focusing lens (not shown) may be further formed on the third photoelectric conversion device 100c. The focusing lens can control the direction of the incident light and focus the light into a region. The focusing lens may have, for example, a cylindrical or hemispherical shape, but is not limited thereto.

[0278] In this figure, the first photoelectric conversion device 100a, the second photoelectric conversion device 100b, and the third photoelectric conversion device 100c are stacked sequentially, but this disclosure is not limited thereto, and they may be stacked in different orders.

[0279] As described above, the first photoelectric conversion device 100a, the second photoelectric conversion device 100b, and the third photoelectric conversion device 100c are stacked, and thus the size of the image sensor can be reduced to achieve a miniaturized image sensor.

[0280] Figure 9 To show a top view of another example of an image sensor according to an exemplary implementation, and Figure 10 To display Figure 9 A cross-sectional view of an example of an image sensor.

[0281] Reference Figure 9 and 10 The image sensor 1100 includes a photoelectric conversion device 90 disposed on a semiconductor substrate 110, and the photoelectric conversion device 90 includes a plurality of photoelectric conversion devices 90-1, 90-2, and 90-3. The plurality of photoelectric conversion devices 90-1, 90-2, and 90-3 can convert light in different wavelength regions (e.g., blue light, green light, or red light) into electrical signals. (See reference...) Figure 10 Multiple photoelectric conversion devices 90-1, 90-2, and 90-3 can be arranged horizontally on the semiconductor substrate 110, such that the photoelectric conversion devices 90-1, 90-2, and 90-3 can partially or completely overlap each other in a direction extending parallel to the surface 110a of the semiconductor substrate 110. Each photoelectric conversion device 90-1, 90-2, and 90-3 is connected to a charge storage device 155 integrated in the semiconductor substrate 110 via a trench 85.

[0282] Each photoelectric conversion device 90-1, 90-2, and 90-3 may be one of the aforementioned photoelectric conversion devices 100 and 200. For example, two or more photoelectric conversion devices 90-1, 90-2, and 90-3 may include different portions of a common continuous layer extending continuously between photoelectric conversion devices 90-1, 90-2, and 90-3. For example, multiple photoelectric conversion devices 90-1, 90-2, and 90-3 may share a common first electrode 10 and / or a common second electrode 20. For example, two or more photoelectric conversion devices 90-1, 90-2, and 90-3 may have different photoelectric conversion layers 30 configured to absorb different wavelength regions of incident light. Other configurations of the image sensor 1100 may be referenced. Figures 3 to 8 The image sensor described is one or more of the same.

[0283] Figure 11 A cross-sectional view is shown to illustrate an example of an image sensor according to an exemplary implementation.

[0284] Reference Figure 11 The image sensor 1200 includes a semiconductor substrate 110 and photoelectric conversion devices 90-1 and 91 stacked on the semiconductor substrate 110. Photoelectric conversion device 91 includes a plurality of photoelectric conversion devices 90-2 and 90-3, and the plurality of photoelectric conversion devices 90-2 and 90-3 can be arranged to overlap each other in a direction extending parallel to the surface 110a of the semiconductor substrate 110. The plurality of photoelectric conversion devices 90-1, 90-2, and 90-3 can convert light in different wavelength regions (e.g., blue light, green light, or red light) into electrical signals.

[0285] As an example, photoelectric conversion device 90-1 may include a plurality of horizontally arranged photoelectric conversion devices configured to absorb light in different wavelength regions. As an example, photoelectric conversion device 91 may photoelectricly convert light selected from a wavelength region of blue, green, and red light. As an example, photoelectric conversion device 91 may partially or completely overlap with photoelectric conversion device 90-1. Other configurations of image sensor 1200 may be referenced. Figures 3 to 8 The image sensor described is one or more of the same.

[0286] Figure 12 A cross-sectional view is shown to illustrate another example of an image sensor according to an exemplary implementation.

[0287] Reference Figure 12The image sensor 1300 includes a semiconductor substrate 110 integrating light sensing devices 150a and 150b, a transfer transistor (not shown), and a charge storage device 155; an upper insulating layer 80 and a color filter layer 70 disposed on the semiconductor substrate 110; and a lower insulating layer 60 and a photoelectric conversion device 90 disposed below the semiconductor substrate 110. The photoelectric conversion device 90 may be the aforementioned photoelectric conversion devices 100 and 200. Figure 12 As shown, the photoelectric conversion device 90 is disposed below the semiconductor substrate 110, and thus, the photoelectric conversion device 90 and the color filter layer 70 are spaced apart relative to the photosensing devices 150a and 150b. Other configurations of the image sensor 1300 can be referenced. Figures 3 to 8 The image sensor described is one or more of the same.

[0288] The aforementioned photoelectric conversion devices and sensors can be applied to a variety of electronic devices, such as mobile phones and cameras (e.g.) Figure 17 The invention includes, but is not limited to, the biometric devices and / or automotive electronic components depicted in the invention.

[0289] Figure 13 A schematic diagram illustrating an electronic device according to an example implementation.

[0290] Reference Figure 13 The electronic device 1700 may include a processor 1720, a memory 1730, and an image sensor 1740, which are electrically connected (coupled) together via a bus 1710. The image sensor 1740 may be an image sensor according to one of the embodiments described above. The memory 1730, which may be a non-transitory computer-readable medium, may store instruction programs. The memory 1730 may be non-volatile memory such as flash memory, phase-change random access memory (PRAM), magnetoresistive RAM (MRAM), resistive RAM (ReRAM), or ferroelectric RAM (FRAM), or volatile memory such as static RAM (SRAM), dynamic RAM (DRAM), or synchronous DRAM (SDRAM). The processor 1720 may execute the stored instruction programs to perform one or more functions. For example, the processor 1720 may be configured to process electrical signals generated by the image sensor 1740. The processor 1720 may be configured to generate output (e.g., an image to be displayed on a display interface) based on, for example, processing.

[0291] Figure 17 A block diagram of a digital camera including an image sensor according to an embodiment.

[0292] Reference Figure 17The digital camera 1800 includes a lens 1810, an image sensor 1820, a motor 1830, and an engine 1840. The image sensor 1820 may be an image sensor according to one of the above embodiments.

[0293] Lens 1810 focuses incident light onto image sensor 1820. Image sensor 1820 generates RGB data for the light received through lens 1810. In some embodiments, image sensor 1820 may interface with engine 1840. Motor 1830 may adjust the focal length of lens 1810 or perform shutter release in response to control signals received from engine 1840. Engine 1840 may control image sensor 1820 and motor 1830. Engine 1840 may be connected to host / application 1050.

[0294] In the example implementation, Figure 13 The processor 1720 and Figure 17 The motor 1830, engine 1840, and host / application 1050 may include processing circuitry systems, such as hardware including logic circuitry; hardware / software combinations, such as a processor executing software; or combinations thereof. For example, the processing circuitry systems may more specifically include, but are not limited to, central processing units (CPUs), arithmetic logic units (ALUs), digital signal processors, microcomputers, field-programmable gate arrays (FPGAs), system-on-a-chip (SoCs), programmable logic units, microprocessors, application-specific integrated circuits (ASICs), etc.

[0295] The embodiments are described in more detail below with reference to examples. However, these examples are non-limiting and the inventive concept is not limited thereto.

[0296] Simulation Evaluation

[0297] (1) Examples and Comparative Examples

[0298] The simulation evaluation was conducted as follows: Compound B was used as the first material, and fullerene C was used as the second material. 60 As a second material and one of compounds C-1 to C-5 as a third material, atomic morphologies are predicted in a molecular dynamics manner based on the molecular structures of the first, second, and third materials in each thin film comprising the first, second, and third materials according to Table 1, and quantum calculations are performed for all molecules included in said morphologies to obtain energy level distributions. Here, the first material and the second material are included in a 1:1 volume ratio, and the third material is included in 5% by volume based on the total volume of the first and third materials.

[0299] The quantum computing is performed by considering the conformation of each molecule in the described form and its surrounding environment. Therefore, the energy level distribution can be evaluated by taking into account the conformational changes of the first material, which depend on the influence of the third material or changes in the molecular environment.

[0300] Table 1

[0301]

[0302] [Compound B]

[0303]

[0304] [Compound C-1]

[0305]

[0306] [Compound C-2]

[0307]

[0308] [Compound C-3]

[0309]

[0310] [Compound C-4]

[0311]

[0312] [Compound C-5]

[0313]

[0314] (2) Evaluation of material properties

[0315] The properties of the first material, the second material, and the third material are shown in Table 2.

[0316] Simulations of the HOMO energy level distribution were performed using Quantum Patch software (Nanomatch GmbH), and simulations of the molecular dipole moments were performed using Jaguar software (Schrodinger, LLC. Materialsscience suite). However, density functional theory (DFT) calculations were performed using Quantum Patch software for B3LPY / def2-SVP and Jaguar software for the LACV3P** basis set.

[0317] Table 2

[0318]

[0319] (3) Simulation Results I

[0320] The variation of residual charge carriers, which depends on the variation of the HOMO energy level distribution of the first material, is evaluated by simulation.

[0321] Figure 14 A graph showing the changes in the HOMO energy level distribution of the first material, and Figure 15 and 16 A graph showing the change in residual charge carriers depending on the variation of the HOMO energy level distribution of the first material.

[0322] Reference Figure 15 and 16 As the HOMO energy level distribution of the first material shifts towards a deeper direction, the residual charge carrier characteristics can be improved.

[0323] (4) Simulation Results II

[0324] Evaluate the energy level changes of the first material and the changes in residual charge carriers that depend on the energy level changes.

[0325] The results are shown in Table 3.

[0326] Table 3

[0327]

[0328] Referring to Table 3, as the HOMO energy level of the first material becomes deeper, the residual charge carrier characteristics can be improved, and as the HOMO energy level of the first material changes more significantly, the residual charge carrier characteristics can be further improved.

[0329] Device Evaluation

[0330] (1) Manufacturing of the device

[0331] The photoelectric conversion device was manufactured to experimentally verify the simulation evaluation.

[0332] Device Example 1

[0333] ITO was sputtered onto a glass substrate to form a 150 nm thick anode. Compound A was deposited on the anode to form a 5 nm thick charge-blocking layer. Compound B (the first material) (λ) was then deposited on the charge-blocking layer. 最大 : 545nm), fullerene (C 60 The second material), and compound C-1 (the third material) (λ) 最大A 100 nm thick photoelectric conversion layer is formed by co-depositing the first and second materials at a 1:1 volume ratio, and the third material at 5% volume of the total volume of the first and third materials. The adjusted HOMO level of the first material in the photoelectric conversion layer is 5.495 eV, and the LUMO level of the fullerene is 3.563 eV. Yb is thermally deposited on the photoelectric conversion layer to form a 1.5 nm thick electron buffer layer (work function: 2.6 eV). ITO is sputtered on the electron buffer layer to form a 7 nm thick cathode. Subsequently, alumina (Al₂O₃) is deposited on the cathode to form a 50 nm thick antireflective layer, which is then sealed with a glass plate, thereby fabricating the photoelectric conversion device.

[0334] [Compound A]

[0335]

[0336] Device Example 2

[0337] The photoelectric conversion device is manufactured according to the same method as in Device Example 1, except that: compound C-2(λ) is used. 最大 A photoelectric conversion layer is formed by replacing compound C-1 with a material at 538 nm. The adjusted HOMO level of the first material in the photoelectric conversion layer is 5.502 eV.

[0338] Device Example 3

[0339] The photoelectric conversion device is manufactured according to the same method as in Device Example 1, except that: compound C-3(λ) is used. 最大 A photoelectric conversion layer is formed by replacing compound C-1 with a material at 538 nm. The adjusted HOMO level of the first material in the photoelectric conversion layer is 5.508 eV.

[0340] Device Comparison Example 1

[0341] The photoelectric conversion device is manufactured according to the same method as in Device Example 1, except that: a photoelectric conversion layer is formed by co-depositing the first and second materials in the absence of the third material. The HOMO level of the first material in the photoelectric conversion layer is 5.490 eV.

[0342] Device Comparison Example 2

[0343] The photoelectric conversion device is manufactured according to the same method as in Device Example 1, except that: compound C-4(λ) is used. 最大A photoelectric conversion layer is formed by replacing compound C-1 with a material at 534 nm. The adjusted HOMO level of the first material in the photoelectric conversion layer is 5.479 eV.

[0344] Device Comparison Example 3

[0345] The photoelectric conversion device is manufactured according to the same method as in Device Example 1, except that: a photoelectric conversion layer is formed by using compound C-5 instead of compound C-1 as a third material. The adjusted HOMO level of the first material in the photoelectric conversion layer is 5.482 eV.

[0346] (2) Evaluation

[0347] The residual charge carrier characteristics of photoelectric conversion devices were evaluated based on the device embodiments and device comparison examples.

[0348] The residual charge carrier characteristics were evaluated by measuring the amount of charge carriers that were not used in signal processing within one frame of photoelectrically converted charge carriers but were still read in the next frame. Specifically, the devices of the embodiments and comparative examples were illuminated with photoelectrically convertible light in the green wavelength region for 33 milliseconds, and then measured at 10000 wavelengths using a Keithley 2400 device. -6 Current measured in seconds. At 5000 lux, measured in h... + / s / μm 2 The amount of residual electrons is evaluated in units.

[0349] The results are shown in Table 4.

[0350] Table 4

[0351] <![CDATA[Residual electrons (h + / s / μm 2 )]]> Device Example 1 114 Device Example 2 108 Device Example 3 67 Device Comparison Example 1 124 Device Comparison Example 2 154 Device Comparison Example 3 134

[0352] Referring to Table 4, the devices in the device embodiments exhibit improved residual electronic characteristics compared to those in the device comparison examples. Furthermore, the device embodiments show results that are substantially equivalent to the simulation results.

[0353] While some exemplary embodiments have been described, it will be understood that the inventive concept is not limited to the disclosed embodiments, but rather is intended to cover various variations and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A photoelectric conversion device, comprising: First electrode and second electrode; and A photoelectric conversion layer between the first electrode and the second electrode The photoelectric conversion layer comprises a first material, a second material, and a third material. The first material and the second material form a pn junction, and The third material is different from the first material and the second material, and The third material is configured to adjust the energy level distribution of the first material or the second material, wherein The dipole moment of the third material is greater than or equal to 5.5 Debye. The first material and the third material are p-type materials, and the second material is an n-type material. The third material causes the HOMO level distribution of the first material to shift towards deeper HOMO levels.

2. The photoelectric conversion device as described in claim 1, wherein... The absorption spectrum of the photoelectric conversion layer has a maximum absorption wavelength in the first wavelength region. The first wavelength region is one of the blue wavelength region, the green wavelength region, the red wavelength region, and the infrared wavelength region. The first material and the third material are each light-absorbing materials having the maximum absorption wavelength in the first wavelength region.

3. The photoelectric conversion device of claim 1, wherein the third material is included in an amount less than or equal to 30% of the total volume of the first material and the third material.

4. A photoelectric conversion device, including First electrode and second electrode; and A photoelectric conversion layer between the first electrode and the second electrode The photoelectric conversion layer comprises a mixture of a first material, a second material, and a third material. The first material, the second material, and the third material are different from each other. The first material and the third material are light-absorbing materials having the maximum absorption wavelength in the first wavelength region. The first wavelength region is one of the blue wavelength region, the green wavelength region, the red wavelength region, and the infrared wavelength region. The dipole moment of the third material is greater than or equal to 5.5 Debye, and Based on the total volume of the first material and the third material, the third material is included in an amount less than or equal to 30% by volume. The first material and the third material are p-type materials, and the second material is an n-type material. The third material causes the HOMO level distribution of the first material to shift towards deeper HOMO levels.

5. The photoelectric conversion device as described in claim 1 or 4, wherein... The HOMO level of the third material is deeper than or shallower than the HOMO level of the first material by a value less than or equal to 0.3 eV.

6. The photoelectric conversion device as claimed in claim 5, wherein... The HOMO energy levels of the third material are 4.7 eV-6.2 eV, and The HOMO energy level of the first material is 5.0 eV-5.8 eV.

7. The photoelectric conversion device as claimed in claim 5, wherein... The HOMO energy level of the third material is 5.1 eV-6.0 eV, and The HOMO energy level of the first material is 5.0 eV-5.8 eV.

8. The photoelectric conversion device of claim 1 or 4, wherein the third material provides an adjusted HOMO level of the first material, and the adjusted HOMO level of the first material is between the HOMO level of the first material and the HOMO level of the second material.

9. The photoelectric conversion device as described in claim 1 or 4, wherein... The dipole moment of the third material is in the range of 5.5 Debye to 15 Debye.

10. The photoelectric conversion device as claimed in claim 1 or 4, wherein... The dipole moment of the third material is in the range of 10 Debye to 15 Debye.

11. The photoelectric conversion device of claim 1 or 4, wherein the photoelectric conversion layer comprises a mixture of the first material, the second material, and the third material.

12. The photoelectric conversion device of claim 3 or 4, wherein the third material is included in an amount of 1% to 10% of the total volume of the first material and the third material.

13. The photoelectric conversion device of claim 3 or 4, wherein the HOMO energy level distribution of the photoelectric conversion layer is different from the HOMO energy level distribution of the thin film formed from the first material and the second material.

14. The photoelectric conversion device of claim 13, wherein the HOMO level of the photoelectric conversion layer is deeper than the HOMO level of the thin film formed from the first material and the second material.

15. The photoelectric conversion device of claim 14, wherein the HOMO level of the photoelectric conversion layer is 0.001 eV-1.2 eV deeper than the HOMO level of the thin film formed from the first material and the second material.

16. The photoelectric conversion device as claimed in claim 1 or 4, wherein the third material is an organic material.

17. The photoelectric conversion device of claim 16, wherein at least one of the first material and the second material is an organic material.

18. The photoelectric conversion device as claimed in claim 1 or 4, wherein... The first material is represented by the chemical formula A-1. [Chemical Formula A-1] in, In chemical formula A-1, X 1 For O, S, Se, Te, SO, SO2, SiR a R b or GeR c R d , Ar 1 The substituted or unsubstituted C6-C30 arylene group, the substituted or unsubstituted C3-C30 heterocyclic group, or a fused ring including combinations thereof, Ar 1a and Ar 2a Independently, it is hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl. Ar 1a and Ar 2a They exist independently or are connected to each other to form fused rings, and R 1 -R 3 and R a -R d It is independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano.

19. The photoelectric conversion device of claim 18, wherein the second material comprises an inorganic material, thiophene or a thiophene derivative, a fullerene or a fullerene derivative, or a combination thereof.

20. The photoelectric conversion device of claim 19, wherein... The third material is represented by chemical formula 1-1. [Chemical Formula 1-1] in, In chemical formula 1-1, X 2 For O, S, Se, Te, SO, SO2, SiR a R b or GeR c R d , Ar 2 The substituted or unsubstituted C6-C30 arylene group, the substituted or unsubstituted C3-C30 heterocyclic group, or a fused ring including combinations thereof, Ar 1b and Ar 2b Independently, it is hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl. Ar 1b and Ar 2b They exist independently or are connected to each other to form fused rings, and R 4 -R 6 and R a -R d It is independently hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, halogen, or cyano.

21. The photoelectric conversion device as claimed in claim 1 or 4, wherein the photoelectric conversion layer is a ternary system composed of the first material, the second material, and the third material.

22. A sensor, comprising: The photoelectric conversion device as described in any one of claims 1-21.

23. Electronic devices, including: The sensor as described in claim 22 or The photoelectric conversion device as described in any one of claims 1-21.

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