Sensor, method of operating the same, camera, and electronic device

Abstract

The present invention relates to a sensor, a method of operating the same, a camera, and an electronic device. The sensor includes a first electrode and a second electrode, and a photoactive layer between the first electrode and the second electrode. The photoactive layer includes a light-absorbing semiconductor configured to form a Schottky junction with the first electrode. The photoactive layer has a carrier-trapping site configured to trap photo-generated carriers generated based on absorption of incident light into the photoactive layer at least at a location adjacent to the first electrode. The sensor is configured to have an external quantum efficiency (EQE) that is adjusted based on a voltage bias applied between the first electrode and the second electrode.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2020-0056122, filed with the Korean Intellectual Property Office on May 11, 2020, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The sensors and electronic devices were disclosed. Background Technology

[0004] An imaging device generates an image and can store it as an electrical signal. The imaging device includes an image sensor that decomposes incident light into individual components based on the wavelength of the incident light and converts each component into an electrical signal. Summary of the Invention

[0005] Some exemplary implementations provide one or more sensors that can improve efficiency and sensitivity.

[0006] Some exemplary implementations provide one or more electronic devices that include the one or more sensors.

[0007] According to some exemplary embodiments, the sensor may include a first electrode and a second electrode, and a photoactive layer between the first and second electrodes, the photoactive layer including a light-absorbing semiconductor configured to form a Schottky junction with the first electrode. The photoactive layer may have carrier trapping sites (trapping sites, trapping positions) configured to trap photogenerated carriers generated by the light-absorbing semiconductor based on the absorption of incident light entering the photoactive layer at least at a location adjacent to the first electrode. The sensor may be configured to have an external quantum efficiency (EQE) adjustable based on a voltage bias (bias voltage) applied between the first and second electrodes.

[0008] As the voltage bias between the first and second electrodes increases, the external quantum efficiency (EQE) of the sensor can become higher, so that the magnitude of the external quantum efficiency (EQE) of the sensor can be proportional to the magnitude of the voltage bias between the first and second electrodes.

[0009] The electric field applied between the first and second electrodes can be greater than about 0 MV / cm and less than or equal to about 0.5 MV / cm.

[0010] The external quantum efficiency (EQE) of the sensor can exceed approximately 100%.

[0011] The light-absorbing semiconductor may include either a p-type non-polymer (non-polymer) semiconductor or an n-type non-polymer semiconductor.

[0012] The photoactive layer may at least partially define a mono-continuous phase comprising either a p-type nonpolymer semiconductor or an n-type nonpolymer semiconductor.

[0013] p-type nonpolymer semiconductors may be p-type monomers having a molecular weight of less than or equal to about 5,000 Daltons and greater than 0 Daltons, and n-type nonpolymer semiconductors may be n-type monomers having a molecular weight of less than or equal to about 5,000 Daltons and greater than 0 Daltons.

[0014] p-type monomers can be organic semiconductors that include an electron-donating portion, a π-conjugated portion, and an electron-accepting portion.

[0015] The light-absorbing semiconductor can be configured to absorb light in at least one of the blue wavelength spectrum, green wavelength spectrum, red wavelength spectrum, or infrared wavelength spectrum.

[0016] Based on the total volume of the photoactive layer, approximately 90% to approximately 100% may comprise light-absorbing semiconductors, such that approximately 90% to approximately 100% of the total volume of the photoactive layer is light-absorbing semiconductor.

[0017] The thickness of the photoactive layer can be equal to or greater than about 100 nm and less than or equal to about 3 μm.

[0018] The photoactive layer may have a first surface near the first electrode and a second surface opposite to the first surface and near the second electrode, such that the first surface and the second surface are opposite surfaces of the photoactive layer, wherein the surface roughness of the first surface of the photoactive layer may be between about 0 nm and about 10 nm.

[0019] The carrier trapping sites in the photoactive layer can be located within approximately 50% of the total thickness of the photoactive layer from the first surface of the photoactive layer, in a direction extending perpendicular to the first surface of the photoactive layer.

[0020] Photogenerated carriers can be configured as a switch to induce interfacial bandbending in a Schottky junction. Carriers can be transferred from a first electrode to a second electrode by a voltage bias, and the amount of carriers transferred from the first electrode to the second electrode can be greater than the amount of photogenerated carriers generated by a light-absorbing semiconductor that absorbs incident light entering the photoactive layer at least at a location adjacent to the first electrode.

[0021] The sensor may further include a buffer layer between the photoactive layer and the second electrode.

[0022] The sensor may further include a semiconductor substrate, and the semiconductor substrate may include a charge memory electrically connected to the second electrode.

[0023] The sensor may further include a color filter layer on a semiconductor substrate and at least partially overlap with a photoactive layer in a direction extending perpendicular to the upper surface of the semiconductor substrate.

[0024] The semiconductor substrate may further include a photodiode.

[0025] The light-absorbing semiconductor may be configured to absorb light in a first wavelength spectrum, which is one of a blue wavelength spectrum, a green wavelength spectrum, or a red wavelength spectrum. The photodiode may include a first photodiode configured to sense light in a second wavelength spectrum, which is another of a blue wavelength spectrum, a green wavelength spectrum, or a red wavelength spectrum. The first wavelength spectrum and the second wavelength spectrum may be different from each other.

[0026] The photodiode may further include a second photodiode stacked in the semiconductor substrate with the first photodiode in a direction extending perpendicular to or parallel to the upper surface of the semiconductor substrate. The second photodiode may be configured to sense light in a third wavelength spectrum, which is another of a blue wavelength spectrum, a green wavelength spectrum, or a red wavelength spectrum, and the third wavelength spectrum may be different from both the first wavelength spectrum and the second wavelength spectrum.

[0027] According to some exemplary embodiments, a method for operating a sensor, the sensor including a first electrode, a second electrode, and a photoactive layer between the first electrode and the second electrode, the photoactive layer including a light-absorbing semiconductor, the method comprising: generating photogenerated carriers at the photoactive layer based on the photoactive layer absorbing incident light; trapping the photogenerated carriers at carrier trapping sites in the photoactive layer; causing the trapped photogenerated carriers to cause band bending at the interface of the Schottky junction between the first electrode and the photoactive layer; applying a voltage bias between the first electrode and the second electrode causing the sensor to transfer carriers through the photoactive layer from the first electrode to the second electrode; and generating an electrical signal output from the sensor based on the carriers transferred to the second electrode.

[0028] Photogenerated carriers can be used as switches to cause interfacial band bending in Schottky junctions, and the amount of carriers transferred to the second electrode is greater than the amount of photogenerated carriers generated by the photoactive layer based on the absorption of incident light.

[0029] The electrical signal transmitted to the second electrode may not include a separate electrical signal generated by photogenerated carriers.

[0030] The voltage bias applied between the first electrode and the second electrode can be greater than about 0 MV / cm and less than or equal to about 0.5 MV / cm.

[0031] The external quantum efficiency (EQE) of the sensor can exceed approximately 100%.

[0032] According to some exemplary implementations, a camera including the sensor is provided.

[0033] According to some exemplary embodiments, an electronic device including the sensor or the camera is provided.

[0034] According to some exemplary embodiments, the sensor may include a first electrode and a second electrode, and a photoactive layer between the first and second electrodes, the photoactive layer including a light-absorbing semiconductor configured to form a Schottky junction with at least one of the first or second electrodes. The photoactive layer may have carrier trapping sites configured to trap photogenerated carriers generated based on the light-absorbing semiconductor absorbing incident light entering at least the photoactive layer. The sensor may be configured to have an external quantum efficiency (EQE) adjustable based on a voltage bias applied between the first and second electrodes.

[0035] Carrier trapping sites can be configured to capture photogenerated carriers generated by a light-absorbing semiconductor that absorbs incident light entering the photoactive layer at a location at least closer to the first electrode than the second electrode.

[0036] The external quantum efficiency (EQE) of the sensor can exceed approximately 100%.

[0037] The light-absorbing semiconductor may include either a p-type nonpolymer semiconductor or an n-type nonpolymer semiconductor.

[0038] The photoactive layer may have a first surface near the first electrode and a second surface near the second electrode, the second surface being opposite to the first surface, such that the first surface and the second surface are opposite surfaces of the photoactive layer. The surface roughness of the first surface of the photoactive layer may be between about 0 nm and about 10 nm.

[0039] The carrier trapping sites in the photoactive layer can be located within approximately 50% of the total thickness of the photoactive layer from the first surface of the photoactive layer, in a direction extending perpendicular to the first surface of the photoactive layer.

[0040] Photogenerated carriers can be configured as switches to cause interfacial band bending in a Schottky junction. Carriers can be transferred from a first electrode to a second electrode by a voltage bias, and the amount of carriers transferred from the first electrode to the second electrode can be greater than the amount of photogenerated carriers generated by a light-absorbing semiconductor that absorbs incident light entering the photoactive layer at least at a location adjacent to the first electrode.

[0041] The sensor may further include a buffer layer between the photoactive layer and the second electrode.

[0042] Electronic devices may include the sensor.

[0043] The efficiency and sensitivity of the sensor can be improved. Attached Figure Description

[0044] Figure 1 This is a schematic cross-sectional view illustrating one example of a device according to some exemplary embodiments.

[0045] Figure 2 It is implemented according to some examples. Figure 1 Energy diagrams of examples of the devices.

[0046] Figure 3 This is a cross-sectional view showing another example of a device according to some exemplary embodiments.

[0047] Figure 4 This is a cross-sectional view illustrating one example of an image sensor according to some exemplary implementations.

[0048] Figure 5 This is a top view of one example of an image sensor implemented according to some exemplary methods.

[0049] Figure 6 It is shown Figure 5 A cross-sectional view of an example of an image sensor.

[0050] Figure 7 This illustrates implementations according to some examples. Figure 5 A cross-sectional view of another example of an image sensor.

[0051] Figure 8 This is a top view of another example of an image sensor implemented according to some exemplary methods.

[0052] Figure 9 This illustrates implementation methods based on some examples. Figure 8 A cross-sectional view of an example of an image sensor.

[0053] Figure 10 This is a top view of another example of an image sensor implemented according to some exemplary methods.

[0054] Figure 11 This illustrates implementation methods based on some examples. Figure 10 A cross-sectional view of an example of an image sensor.

[0055] Figure 12 This is a cross-sectional view illustrating one example of an image sensor according to some exemplary implementations.

[0056] Figure 13 This is a cross-sectional view illustrating another example of an image sensor implemented according to some exemplary methods.

[0057] Figure 14These are schematic diagrams of electronic devices implemented according to some examples.

[0058] Figure 15 This is a graph showing the variation of the external quantum efficiency (EQE) of the devices according to Example 1 and Reference Example 1 with respect to the electric field.

[0059] Figure 16 This is a graph showing the variation of the external quantum efficiency (EQE) of the device according to Embodiment 2 and Reference 2 according to some exemplary embodiments.

[0060] Figure 17 This is a graph showing the external quantum efficiency (EQE) of the device according to Embodiment 1 according to some exemplary embodiments, and

[0061] Figure 18 This is a flowchart illustrating a method for operating a sensor according to some example implementations. Detailed Implementation

[0062] The following sections will describe some exemplary implementations in detail, enabling those skilled in the art to readily implement them. However, practical applications can be implemented in a wide variety of different forms and are not limited to the implementations described herein.

[0063] In the accompanying drawings, the thicknesses of layers, films, panels, regions, etc., are enlarged for clarity. 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 the other element, or there may be intermediate elements such that the one element and the other element are separated from each other by one or more insertion spaces and / or structures to prevent direct contact. Conversely, when an element is referred to as being "directly on" another element, there are no intermediate elements such that the one element and the other element are in direct contact. As described herein, an element "on" another element may be above, below, and / or horizontally adjacent to the other element.

[0064] It will be understood that an element and / or its properties may be stated herein as “identical” or “equal” to other elements, and it will be further understood that an element and / or its properties stated herein as “identical” or “equal” to other elements may be “identical” or “equal” to other elements or its properties, or “substantially identical” or “substantially equal” to other elements and / or its properties. Element and / or its properties being “substantially identical” or “substantially equal” to other elements and / or its properties will be understood to include elements and / or its properties being identical or equal to other elements and / or its properties within manufacturing tolerances and / or material tolerances. Element and / or its properties being identical or substantially identical to other elements and / or its properties may be identical or substantially identical in structure, identical or substantially identical in function, and / or identical or substantially identical in composition.

[0065] It will be understood that elements and / or properties described herein as “substantially” identical encompass elements and / or properties having a relative difference in size equal to or less than 10%. Furthermore, regardless of whether an element and / or property is modified to “substantially,” it will be understood that such elements and / or properties should be interpreted as including manufacturing or operational tolerances (e.g., ±10%) near the stated elements and / or properties.

[0066] When the terms “about” or “substantially” are used in this specification with respect to numerical values, it is intended that the relevant numerical value includes a tolerance of ±10% around the stated value. When a range is specified, the range includes all values ​​within that range, such as an increment of 0.1%.

[0067] In the accompanying drawings, parts unrelated to the description are omitted for clarity of the embodiments, and throughout the specification, the same or similar constituent elements are indicated by the same reference numerals.

[0068] In the following text, the terms "lower (bottom)" and "upper (top)" are used for descriptive convenience and do not restrict the positional relationship. The term "metal" includes both metals and semi-metals.

[0069] In the following text, the upper part of the sensor will be described as a light-receiving surface, but this is for the sake of convenience and does not restrict the positional relationship.

[0070] As used herein, unless otherwise specifically defined, “substituted” means that the hydrogen atom of a compound or group is replaced by: a halogen atom, a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azide group, an amido group, a hydrazine group, a hydrazine group, a hydrazone group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a silyl group, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroaryl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C3 to C30 heterocycloalkyl group, or a combination thereof.

[0071] As used herein, unless otherwise specifically defined, the term "hybrid" refers to a mixture of 1 to 4 heteroatoms selected from N, O, S, Se, Te, Si, and P.

[0072] In the following text, "combination" refers to a mixture of two or more kinds and a stacked structure of two or more kinds.

[0073] In the following text, unless otherwise defined, an energy level is the highest occupied molecular orbital (HOMO) level and / or the lowest unoccupied molecular orbital (LUMO) level.

[0074] In the following text, unless otherwise defined, the work function or energy level is referred to as the absolute value of the distance from 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 of "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 of "0 eV."

[0075] The following describes devices according to some example implementations.

[0076] Devices according to some exemplary embodiments may include, for example, an electrode pair and a photoactive layer between the electrode pairs, and the photoactive layer may include, for example, a photoelectronic material. The photoelectronic material may include, for example, a material configured to absorb light and exhibit electrical properties, but is not limited thereto. Devices according to some exemplary embodiments may be, for example, photoelectric conversion devices, photoelectric sensors, or photodetectors, but are not limited thereto.

[0077] The device according to some example embodiments may be, for example, an organic device comprising at least one organic material, and may be, for example, an organic diode comprising at least one organic material as an optoelectronic material.

[0078] According to some example implementations, the device may be, for example, a Schottky diode configured to form a Schottky junction under bias.

[0079] Figure 1 It schematically shows a cross-sectional view of a device according to some exemplary embodiments, and Figure 2 It is implemented according to some examples. Figure 1 The energy diagram of an example of a device. A device as described herein, according to any example implementation, may be a sensor, and sensors as described herein can be interchangeably referred to as devices.

[0080] Reference Figure 1 According to some exemplary embodiments, the sensor 100 includes a first electrode 10 and a second electrode 20, and a photoactive layer 30 between the first electrode 10 and the second electrode 20. In some exemplary embodiments, the sensor 100 may be a sensor including an image sensor, a light sensor, etc.

[0081] One of the first electrode 10 or the second electrode 20 may be an anode, and the other may be a cathode. For example, the first electrode 10 may be an anode and the second electrode 20 may be a cathode.

[0082] At least one of the first electrode 10 or the second electrode 20 may be a transparent electrode. The transparent electrode may have a high transmittance of about 80%, for example, about 85%, about 88%, or about 90%. The transmittance may be equal to or less than about 100%, for example, equal to or less than about 99%. The transparent electrode may include at least one of, for example, an oxide conductor, a carbon conductor, or a metal thin film. The oxide conductor may include at least one selected from, for example, indium tin oxide (ITO), indium zinc oxide (IZO), zinc tin oxide (ZTO), aluminum tin oxide (ATO), and aluminum zinc oxide (AZO); the carbon conductor may be at least one selected from graphene and carbon nanostructures; and the metal thin film may be an ultrathin film including aluminum (Al), magnesium (Mg), silver (Ag), gold (Au), their alloys, or combinations thereof. The light-receiving electrode may be a transparent electrode.

[0083] One of the first electrode 10 or the second electrode 20 may be a reflective electrode. The reflective electrode may have, for example, a 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, such as aluminum (Al), silver (Ag), gold (Au), or an alloy thereof.

[0084] For example, the first electrode 10 and the second electrode 20 can each be a transparent electrode. One of the first electrode 10 or the second electrode 20 can be a light-receiving electrode.

[0085] For example, the first electrode 10 can be a transparent electrode and the second electrode 20 can be a reflective electrode. The first electrode 10 can be a light-receiving electrode.

[0086] For example, the first electrode 10 can be a reflective electrode and the second electrode 20 can be a transparent electrode. The second electrode 20 can be a light-receiving electrode.

[0087] The photoactive layer 30 can be located between the first electrode 10 and the second electrode 20.

[0088] The photoactive layer 30 may be configured to absorb light to generate photogenerated carriers. The light may be at least a subset of, for example, light in the blue wavelength spectrum (hereinafter referred to as "blue light"), light in the green wavelength spectrum (hereinafter referred to as "green light"), light in the red wavelength spectrum (hereinafter referred to as "red light"), and / or light in the infrared wavelength spectrum (hereinafter referred to as "infrared light").

[0089] For example, the photoactive layer 30 can be configured to selectively absorb one of blue light, green light, red light, or infrared light. In this document, selective absorption of one of blue light, green light, red light, or infrared light means that a peak absorption wavelength (λ) of the absorption spectrum exists in one of the following wavelength ranges: greater than or equal to about 380 nm and less than about 500 nm (blue light); about 500 nm to about 600 nm (green light); greater than about 600 nm and less than or equal to about 700 nm (red light); or greater than about 700 nm and less than about 3000 nm (infrared light). 最大 Furthermore, the absorption spectrum in the corresponding wavelength spectrum (e.g., the fraction of incident radiation absorbed by the photoactive layer 30) is significantly higher than the absorption spectrum in other wavelength spectra. In this document, "significantly higher" may mean about 70% or more, about 75% or more, about 80% or more, about 85% or more, about 90% or more, or about 95% or more, based on the total absorption spectrum.

[0090] For example, the photoactive layer 30 may be configured to absorb at least two of blue light, green light, red light, or infrared light, such as absorbing blue light, green light, and red light.

[0091] The photoactive layer 30 may include a light-absorbing semiconductor having the aforementioned light absorption characteristics. The light-absorbing semiconductor may be and / or include one of a p-type semiconductor or an n-type semiconductor having the aforementioned absorption characteristics, and the p-type semiconductor or n-type semiconductor may be configured to form a Schottky junction with the first electrode 10. Therefore, it will be understood that the photoactive layer 30 may include a light-absorbing semiconductor configured to form a Schottky junction with the first electrode 10. In some exemplary embodiments, instead of forming a Schottky junction with the first electrode 10, or in addition to forming a Schottky junction with the first electrode 10, the light-absorbing semiconductor may be configured to form a Schottky junction with the second electrode 20. Therefore, it will be understood that the photoactive layer 30 may include a light-absorbing semiconductor configured to form a Schottky junction with at least one of the first electrode 10 or the second electrode 20. Since the Schottky junction is formed between an electrode and a p-type semiconductor or between an electrode and an n-type semiconductor, unlike a pn junction, it does not include both p-type and n-type semiconductors together. The p-type semiconductor may include one or more types, and the n-type semiconductor may include one or more types.

[0092] The light-absorbing semiconductor can be, for example, a p-type or n-type nonpolymeric semiconductor having the aforementioned light-absorbing properties, and the p-type or n-type nonpolymeric semiconductor can be, for example, a p-type or n-type inorganic semiconductor, a p-type or n-type organic-inorganic semiconductor, a p-type or n-type nonpolymeric organic semiconductor (low molecular weight semiconductor), or a combination thereof. For example, the p-type or n-type inorganic semiconductor, the p-type or n-type organic-inorganic semiconductor, or the p-type or n-type nonpolymeric organic semiconductor (low molecular weight semiconductor) may include a wavelength-selective absorbing material configured to selectively absorb one of blue light, green light, red light, or infrared light. Therefore, the light-absorbing semiconductor can be configured to absorb light in at least one of the blue wavelength spectrum, the green wavelength spectrum, the red wavelength spectrum, or the infrared wavelength spectrum (e.g., at least some of the incident light 900).

[0093] p-type or n-type nonpolymer semiconductors may form (e.g., define) carrier trapping sites 30a, which are intentionally or unintentionally formed by the configuration of the molecules themselves, such as the arrangement, alignment, and / or stacking of the molecules. Carrier trapping sites 30a will be described later.

[0094] For example, light-absorbing semiconductors may include p-type inorganic semiconductors, p-type organic-inorganic semiconductors, p-type low molecular weight semiconductors, or combinations thereof. P-type low molecular weight semiconductors may be, for example, p-type monomers, such as p-type monomers having a molecular weight of less than or equal to about 5000, less than or equal to about 4000, or less than or equal to about 3000. The molecular weight of the p-type monomer may be equal to or greater than about 0, 0.01, 0.1, 1, etc. As described herein, molecular weight can be measured in Daltons, also known as uniform atomic mass units (e.g., a p-type low molecular weight semiconductor may be a p-type monomer having a molecular weight of less than or equal to about 5000 Daltons and greater than 0 Daltons).

[0095] For example, light-absorbing semiconductors may include n-type inorganic semiconductors, n-type organic-inorganic semiconductors, n-type low molecular weight semiconductors, or combinations thereof. The n-type low molecular weight semiconductor may be, for example, an n-type monomer having a molecular weight of less than or equal to about 5000, less than or equal to about 4000, or less than or equal to about 3000. The molecular weight of the n-type monomer may be equal to or greater than about 0, 0.01, 0.1, 1, etc. As described herein, molecular weight can be measured in Daltons, also known as uniform atomic mass units (e.g., an n-type low molecular weight semiconductor may be an n-type monomer having a molecular weight of less than or equal to about 5000 Daltons and greater than 0 Daltons).

[0096] For example, p-type monomers may have a core structure that includes an electron-donating moiety, a π-conjugated linking group, and an electron-accepting moiety.

[0097] For example, p-type low molecular weight semiconductors can be represented by the chemical formula A, but are not limited to this.

[0098] [Chemical Formula A]

[0099] EDM-LM–EAM

[0100] In chemical formula A,

[0101] LM is a π-conjugated linker group and can be a C2 to C30 heterocyclic group having at least one of O, S, Se, Te or Si.

[0102] EDM can be used for the electron-emitting part, and

[0103] EAM can be the electron-receiving part.

[0104] For example, a p-type monomer represented by chemical formula A can be configured to selectively absorb green light, and can be represented, for example, by chemical formula A-1.

[0105] [Chemical Formula A-1]

[0106]

[0107] In chemical formula A-1,

[0108] X can be O, S, Se, Te, SO, SO2, or SiR. a R b ,

[0109] Ar can be a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C3 to C30 heterocyclic group, or a fused ring of two or more of the aforementioned groups.

[0110] Ar 1a and Ar 2aIt can be independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C3-C30 heteroaryl group.

[0111] R 1a To R 3a R a and R b It may independently be hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heteroaryl, halogen, cyano, or a combination thereof, and

[0112] R 1a To R 3a And Ar 1a and Ar 2a It can exist independently, or two adjacent groups can combine with each other to form a fused ring.

[0113] For example, in chemical formula A-1, Ar 1a and Ar 2a It 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.

[0114] For example, Ar with chemical formula A-1 1a and Ar 2a They can be connected to each other to form a ring, or, for example, Ar 1a and Ar 2a They can be connected to each other to form a ring through one of the following: single bond, -(CR) g R h ) n2 -(n² is 1 or 2), -O-, -S-, -Se-, -N=, -NR i -、-SiR j R k -、or-GeR l R m - Here, R g To R mIt may independently be hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heteroaryl, substituted or unsubstituted C1 to C6 alkoxy, halogen, or a combination thereof.

[0115] For example, R in chemical formula A-1 1a and Ar 1a They can be connected to each other to form a ring, and for example, they can be connected to each other to form a ring by one of the following: single bonds, -(CR g R h ) n2 -(n² is 1 or 2), -O-, -S-, -Se-, -N=, -NR i -、-SiR j R k -、or-GeR l R m - Here, R g To R m Same as above.

[0116] For example, a p-type monomer represented by chemical formula A-1 can be represented by one of chemical formulas A-2 to A-7.

[0117]

[0118]

[0119] In chemical formulas A-2 to A-7,

[0120] X and R 1a To R 3a Same as above,

[0121] Ar 3 It can be a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C3 to C30 heterocyclic group, or a fused ring of two or more of the above.

[0122] G can be one of the following: a single bond, -(CR) g R h ) n2 -(n² is 1 or 2), -O-, -S-, -Se-, -N=, -NR i -、-SiR j R k -、or-GeR l R m -, where R g To R mIt may independently be hydrogen, a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C1 to C30 alkoxy, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C3 to C30 heteroaryl, a halogen, a cyano, or a combination thereof, wherein R g and R h R j and R k and R l and R m They can exist independently or be connected to form a ring.

[0123] Y 2 It can be O, S, Se, Te, or C(R) q (CN)(where R) q It can be hydrogen, cyano (-CN), or C1 to C10 alkyl.

[0124] R 6a To R 6e R 7a To R 7e R 16 R 17 R g and R h It may independently be hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heteroaryl, halogen, cyano, or a combination thereof, and

[0125] R 1a To R 3a R 6a To R 6e and R 7a To R 7e It can exist independently, or two adjacent groups can connect to each other to form a fused ring.

[0126] For example, Ar with chemical formulas A-2, A-4, and / or A-6 3 It can be a benzene ring, naphthalene ring, anthracene ring, thiophene ring, selenophene ring, tellurophene ring, pyridine ring, pyrimidine ring, or a fused ring selected from two or more of the aforementioned rings.

[0127] The light-absorbing semiconductor may occupy a large portion of the photoactive layer 30. For example, based on the total volume of the photoactive layer 30, it may comprise about 90% to about 100%, about 92% to about 100%, about 95% to about 100%, about 97% to about 100%, about 98% to about 100%, or about 99% to about 100% of the total volume of the photoactive layer 30. For example, about 90% to about 100% of the total volume of the photoactive layer 30 may be light-absorbing semiconductors.

[0128] For example, the photoactive layer 30 may be formed of one of the above-mentioned p-type nonpolymer semiconductors or n-type nonpolymer semiconductors (e.g., may partially or completely include it), and may form (e.g., define) a single continuous phase composed of one of the p-type nonpolymer semiconductors or n-type nonpolymer semiconductors (which may be the same as or different from one of the p-type nonpolymer semiconductors or n-type nonpolymer semiconductors that at least partially or completely constitute the photoactive layer 30) (e.g., at least partially or completely include it).

[0129] For example, in addition to the light-absorbing semiconductor, the photoactive layer 30 may optionally further include additives capable of improving absorption characteristics and / or electrical properties. The additives may be, for example, inorganic materials, organic materials, and / or organic-inorganic materials. For example, the additives may be non-light-absorbing materials or light-absorbing materials. The additives may be included in the photoactive layer 30 in small amounts, for example, in amounts less than about 10%, less than or equal to about 9%, less than or equal to about 5%, less than or equal to about 3%, less than or equal to about 2%, less than or equal to about 1%, or less than or equal to about 0.5%, based on the total volume of the photoactive layer 30.

[0130] The photoactive layer 30 may form a Schottky junction with the first electrode 10. For example, the photoactive layer 30 has a first surface 30-1 that is close to (e.g., near, adjacent to, etc.) the first electrode 10 and a second surface 30-2 that is opposite to the first surface 30-1 and close to (e.g., near, adjacent to, etc.) the second electrode 20, such that the first surface 30-1 and the second surface 30-2 may be opposite surfaces of the photoactive layer 30. In some embodiments, the first surface 30-1 may be in direct contact with the first electrode 10, or may be isolated from the first electrode 10 to avoid direct contact. In some embodiments, the second surface 30-2 may be in direct contact with the second electrode 20, or may be isolated from the second electrode 20 to avoid direct contact. The photoactive layer 30 may form a Schottky junction between the first electrode 10 and the first surface 30-1 of the photoactive layer 30 and / or between the second electrode 20 and the second surface 30-2 of the photoactive layer 30. The sensor 100 may be a Schottky diode.

[0131] Sensor 100 may have current-voltage (IV) characteristics, wherein current may flow at a specific (or alternatively predetermined) voltage or higher, and the current changes according to the voltage. For example, when a specific (or alternatively predetermined) voltage is applied between the first electrode 10 and the second electrode 20 (e.g., applying separate voltages to the first electrode 10 and the second electrode 20 to result in a voltage bias between the first and second electrodes 10 and 20), current may flow through the photoactive layer 30, and the amount (e.g., magnitude) of the current flowing through the photoactive layer 30 may increase linearly as the applied voltage (e.g., the magnitude of the voltage bias) increases.

[0132] The photoactive layer 30 may have carrier trapping sites 30a that are adjacent to the first electrode 10, i.e., close to the first surface 30-1 of the photoactive layer 30 (e.g., closer to the first surface 30-1 than to the second surface 30-2). However, it will be understood that the carrier trapping sites 30a, as described herein, may be located anywhere within the photoactive layer 30, such that the carrier trapping sites 30a may be closer to the second surface 30-2 than to the first surface 30-1, or equidistant between the first and second surfaces 30-1 and 30-2. The carrier trapping sites 30a may have multiple trapping states (trapped states) between the HOMO and LUMO energy levels of the photoactive layer 30, and these multiple trapping states may be intentionally or unintentionally formed by the molecular configuration, such as the arrangement, alignment, and / or stacking of p-type or n-type nonpolymer semiconductor molecules as described above. The multiple trapping states may be, for example, about 10 11 To about 10 15 (units), and can be approximately 10 12 To about 10 14 However, it is not limited to this.

[0133] When the photoactive layer 30 comprises a polymeric semiconductor, a separate process is required to form carrier trapping sites with multiple trapping states at the first surface 30-1 of the photoactive layer 30 in contact with the first electrode 10. However, according to some exemplary embodiments, the sensor 100 may include a p-type or n-type non-polymeric semiconductor in the photoactive layer 30 to form carrier trapping sites with multiple trapping states without additional processing. For example, a photoactive layer 30 comprising a polymeric semiconductor requires additional processing to form carrier trapping sites on the surface with a high surface roughness greater than or equal to about 10 nm (e.g., about 10 nm to about 1000 nm, etc.). However, according to some exemplary embodiments, the photoactive layer 30 of the sensor 100 may have a low surface roughness of less than about 10 nm (e.g., about 0 nm to less than about 10 nm, about 0.1 nm to less than about 10 nm, etc.) with a sufficient thickness of carrier trapping sites without additional processing. As described herein, the value for surface roughness (e.g., surface roughness less than about 10 nm) may refer to the average deviation of the surface from the average centerline extending parallel to the first electrode 10 and / or the second electrode (e.g., surface roughness less than about 10 nm).

[0134] For example, the location and thickness 30aT of the carrier trapping sites 30a can vary depending on the type of light-absorbing semiconductor. For instance, a majority may be present within approximately 50% of the total thickness 30T of the photoactive layer 30 extending from the first surface 30-1 of the photoactive layer 30. To reiterate, the thickness 30aT of the carrier trapping sites 30a in the direction perpendicular to the first surface 30-1 of the photoactive layer 30 can be approximately 50% or less of the total thickness 30T of the photoactive layer 30 extending from the first surface 30-1 of the photoactive layer 30 in said direction. It will be understood that “thickness” as used herein can refer to the thickness in the direction perpendicular to one or both of the first surface 30-1 and / or the second surface 30-2.

[0135] refer to Figure 1 When light (e.g., incident light 900) enters the sensor 100 (e.g., via one or both of the first electrode 10 and / or the second electrode 20 into the photoactive layer 30), photogenerated carriers can be generated in the photoactive layer 30 based on the light absorption of the aforementioned light-absorbing semiconductor (e.g., based on the light-absorbing semiconductor that absorbs at least a portion of the incident light entering the photoactive layer 30), and a plurality of capture states in carrier trapping sites 30a can be configured to trap these photogenerated carriers. To reiterate, at least one carrier trapping site 30a of the photoactive layer 30 can be configured to trap photogenerated carriers generated based on the light-absorbing semiconductor of the photoactive layer 30 that absorbs at least a portion of the incident light 900, which enters the photoactive layer 30 at least at locations within the photoactive layer 30 such that the location may be adjacent to the first electrode 10, adjacent to the second electrode 20, or at an equidistant location between the first electrode 10 and the second electrode 20, etc.

[0136] In some implementations, the photoactive layer 30 may include a plurality of carrier trapping sites 30a. At least one carrier trapping site 30a may be adjacent to (e.g., directly adjacent to, near, or indirectly adjacent to) the first electrode 10. At least another carrier trapping site 30a may be adjacent to (e.g., directly adjacent to, near, or indirectly adjacent to) the second electrode 20. The carrier trapping sites may be stacked in a direction extending through the photoactive layer 30 between the first electrode 10 and the second electrode 20.

[0137] The at least one carrier trapping site 30a may be located directly adjacent to the first surface 30-1, closer to the first surface 30-1 than to the second surface 30-2, at a specific distance from the first surface 30-1, said specific distance being equal to or less than about 10% of the distance between the first and second electrodes 10 and 20 (the carrier trapping site 30a may be located at a distance from the first surface 30-1, said specific distance being between 0% and about 10% of the distance between the first and second surfaces 30-1 and 30-2). In some exemplary embodiments, the at least one carrier trapping site 30a may include at least a portion of the photoactive layer 30 defined by the first surface 30-1, such that the at least one carrier trapping site 30a can be understood as being in direct contact with the first surface 30-1. The captured photogenerated carriers can be configured to cause the interface band bending of the Schottky junction between the first electrode 10 and the photoactive layer 30 (e.g., the sensor 100 can be configured to cause the captured photogenerated carriers to cause the interface band bending of the Schottky junction between the first electrode 10 and the photoactive layer 30), thereby reducing or eliminating the energy barrier (Δd1) between the first electrode 10 and the photoactive layer 30, and the carriers can be effectively injected from the first electrode 10 into the photoactive layer 30 by an external voltage (e.g., reverse bias) applied between the first electrode 10 and the second electrode 20.

[0138] In other words, photogenerated carriers in the photoactive layer 30, generated by light, can be configured as a switch to induce band bending at the interface of the Schottky junction. Carriers are effectively injected from the first electrode 10 into the photoactive layer 30 by applying an external voltage. The carriers injected into the photoactive layer 30 can be transferred to the second electrode 20 and read as an electrical signal by the sensor 100 (e.g., carriers can be transferred from the first electrode 10 to the second electrode 20 via the photoactive layer 30 by an applied external voltage as a bias voltage, and the transferred carriers reaching the second electrode can be read as an electrical signal by the sensor 100). Here, the amount of charge (current) transferred from the first electrode 10 to the second electrode 20 can be adjusted according to the intensity of the applied voltage, and the amount of current can increase as the intensity of the applied voltage increases. For example, the electric field applied between the first electrode 10 and the second electrode 20 may be greater than about 0 MV / cm and less than or equal to about 0.5 MV / cm (e.g., between about 0.001 MV / cm and about 0.5 MV / cm, between about 0.01 MV / cm and about 0.5 MV / cm, etc.), but is not limited thereto.

[0139] As described above, in the sensor 100 according to some exemplary embodiments, photogenerated carriers produced by light can be used as a switching function to induce band bending at the interface, and the amount of charge transferred from the first electrode 10 to the second electrode 20 can be adjusted by the intensity of an external bias voltage. It will be understood that the external bias voltage or bias voltage as described herein can be interchangeably referred to as the voltage bias applied between the first electrode 10 and the second electrode 20, for example, based on one or more voltages applied to one or more of the first and second electrodes 10 and 20 to result in an applied voltage or voltage difference between the first and second electrodes 10 and 20. As the external bias voltage increases, i.e., the voltage applied between the first electrode 10 and the second electrode 20 becomes higher, the amount of current flowing through the photoactive layer 30 can increase linearly. Reiterating, the sensor 100 can be configured to have an adjustable external quantum efficiency (EQE) that is proportional (e.g., directly proportional) to the magnitude of the bias voltage (e.g., the applied voltage difference) between the first and second electrodes. Therefore, unlike pn junction devices where the amount of current is determined based on the amount of light absorbed, the sensor 100 according to some exemplary embodiments can obtain a sufficient amount of current even in low light (low brightness) environments by adjusting the external bias voltage, thereby implementing a highly efficient device.

[0140] For example, in the case of a pn junction device, photogenerated carriers generated by light are transferred to the first electrode 10 and / or the second electrode 20 and read as the current value of the pn junction device, such that the external quantum efficiency (EQE) may not exceed 100%. However, in the case of the sensor 100 according to some exemplary embodiments, regardless of the amount of photogenerated carriers generated by light, the desired current value can be obtained according to the intensity of the external bias voltage, such that an external quantum efficiency exceeding 100% can be obtained. To reiterate, the external quantum efficiency (EQE) of the sensor 100 may exceed approximately 100%. That is, the number of carriers transferred from the first electrode 10 to the second electrode 20 according to the external bias voltage may be greater than the number of photogenerated carriers. For example, the amount of carriers transferred from the first electrode to the second electrode by the bias voltage (e.g., the applied external bias voltage, the voltage difference applied between the first and second electrodes 10 and 20, etc.) may be greater than the amount of photogenerated carriers generated by the light-absorbing semiconductor of the photoactive layer 30 based on the absorption of incident light 900 that enters at least the photoactive layer 30 at a location adjacent to the first electrode 10. For example, as the bias voltage between the first electrode 10 and the second electrode 20 (e.g., the difference between the voltages applied to the first and second electrodes 10 and 20, respectively) increases, the external quantum efficiency (EQE) of the sensor 100 can increase, and the external quantum efficiency (EQE) of the sensor 100 can be greater than about 100%, greater than about 1000%, or greater than about 10000%. Therefore, it will be understood that the sensor 100 can be configured to be related to (e.g., have) an external quantum efficiency (EQE) that is adjustable based on the bias voltage applied between the first and second electrodes 10 and 20 (e.g., an external bias voltage, a voltage bias voltage, etc.) (e.g., the magnitude of the external quantum efficiency (EQE) can be adjustable based on the magnitude of the applied bias voltage). For example, the sensor 100 can be configured to adjust the EQE of the sensor 100 based on and / or in response to the difference between a first voltage applied to the first electrode and a second voltage applied to the second electrode 20.

[0141] In some implementations, since the sensor 100 according to some implementations does not generate photogenerated carriers in a lightless (dark) environment, the aforementioned interface band bending of the Schottky junction does not occur, and therefore, the aforementioned mechanism does not operate to suppress the generation of dark current.

[0142] The total thickness 30T of the photoactive layer 30 may be equal to or greater than about 100 nm and less than or equal to about 3 μm (for example, it may be about 100 nm to about 3 μm), and within the above range, it may be about 200 nm to about 3 μm, about 300 nm to about 3 μm, or about 500 nm to about 3 μm.

[0143] The sensor 100 may further include an anti-reflective layer (not shown) on the first electrode 10 or under the second electrode 20. The anti-reflective layer may be on the side where light is incident and may further improve light absorption by reducing the reflectivity of the incident light. For example, the anti-reflective layer may be disposed on the first electrode 10 when light is incident through the first electrode 10, and under the second electrode 20 when light is incident through the second electrode 20.

[0144] 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 metal oxide, metal sulfide, or organic material having a refractive index within the said range. The antireflective layer may include, for example, metal oxides, such as 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 not limited thereto.

[0145] The aforementioned sensor 100 can be operated by supplying light to the photoactive layer 30 and applying a bias voltage between the first electrode 10 and the second electrode 20. Specifically, the aforementioned sensor 100 can operate as follows: absorbing light in the photoactive layer 30 to generate photogenerated carriers, trapping the photogenerated carriers in a trapped state at the carrier trapping sites in the photoactive layer 30, causing the interface band bending of the Schottky junction between the first electrode 10 and the photoactive layer 30 by the trapped photogenerated carriers, applying a bias voltage between the first electrode 10 and the second electrode 20 and transferring carriers from the first electrode 10 through the photoactive layer 30 to the second electrode 20 by (reverse) bias voltage, and reading the electrical signal transmitted to the second electrode 20.

[0146] Unlike pn junction devices, the sensor 100 according to some example implementations functions as a switch, wherein photogenerated carriers cause the interface band of the Schottky junction to bend, so that the electrical signal transmitted to the second electrode 20 can be determined according to the strength of the external bias voltage, and the electrical signal caused by photogenerated carriers can be ignored.

[0147] As described above, since the sensor 100 according to some exemplary embodiments uses a photogenerated carrier switch (conversion) and the current value can be adjusted with respect to the intensity of the external bias voltage, a sufficient amount of current can be obtained even in low-light (low-brightness) environments by adjusting the external bias voltage. Therefore, a highly efficient device can be implemented even in low-light (low-brightness) environments.

[0148] In the following text, another example of a device implemented according to some examples is described.

[0149] Figure 3 This is a cross-sectional view showing another example of a device according to some exemplary embodiments.

[0150] refer to Figure 3 According to some exemplary embodiments, the sensor 100 includes a first electrode 10, a second electrode 20, and a photoactive layer 30, such as in the case of at least Figure 1 As shown in some of the example implementations.

[0151] However, with including at least Figure 1 Some of the example implementations shown in the document differ from those in the example implementations, depending on whether they include at least Figure 3 The sensor 100 of some exemplary embodiments shown in the illustration further includes a buffer layer 40 between the second electrode 20 and the photoactive layer 30 (e.g., directly or indirectly between them). The buffer layer 40 can increase the carrier mobility from the photoactive layer 30 to the second electrode 20 while blocking the reverse movement of carriers from the second electrode 20 to the photoactive layer 30.

[0152] The buffer layer 40 may include, for example, organic materials, inorganic materials, and / or organic-inorganic materials.

[0153] The buffer layer 40 may include, for example, a compound represented by the chemical formula B-1 or B-2.

[0154] [Chemical Formula B-1]

[0155]

[0156] [Chemical formula B-2]

[0157]

[0158] In chemical formulas B-1 or B-2,

[0159] M 1 and M 2 Can be used independently for CR n R o SiR p R q NR r ,O,S,Se or Te,

[0160] Ar in chemical formula B-1 1b Ar 2b Ar 3b and Ar 4b It can be independently a substituted or unsubstituted C6 to C30 aryl or a substituted or unsubstituted C3 to C30 heteroaryl, and Ar in chemical formula B-2. 1b Ar 2bAr 3b and Ar 4b It can be independently a substituted or unsubstituted C6 to C30 arylene or a substituted or unsubstituted C3 to C30 heteroarylene.

[0161] G 2 and G 3 Can be independently a single bond, -(CR) s R t ) n3 -, -O-, -S-, -Se-, -N=, -NR u -、-SiR v R w -or-GeR x R y -, where n3 is 1 or 2, and

[0162] R 30 To R 37 and R n To R y It may be hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclic, substituted or unsubstituted C1 to C6 alkoxy, halogen or cyano, independently.

[0163] Compounds represented by chemical formula B-1 or B-2 may be, for example, compounds represented by chemical formula B-3 or B-4.

[0164] [Chemical Formula B-3]

[0165]

[0166] [Chemical Formula B-4]

[0167]

[0168] In chemical formulas B-3 or B-4,

[0169] M 1 M 2 G 2 G 3 R 30 To R 37 Same as above, and

[0170] R 38 To R 45 It may be hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heteroaryl, substituted or unsubstituted C1 to C6 alkoxy, halogen or cyano, independently.

[0171] Compounds represented by chemical formula B-3 or B-4 may be, for example, compounds represented by chemical formula B-5 or B-6.

[0172] [Chemical Formula B-5]

[0173]

[0174] [Chemical Formula B-6]

[0175]

[0176] In chemical formulas B-5 or B-6, R 38 To R 45 and R o and R n Same as above.

[0177] The aforementioned sensor 100 can be applied to, for example, a sensor, and the sensor can be, for example, an image sensor. As described above, an image sensor using the aforementioned sensor 100 can be configured to adjust electrical characteristics such as external quantum efficiency (EQE) based on an external bias voltage (e.g., a bias voltage applied between the first and second electrodes 10 and 20), even in low-light (low-brightness) environments, making it effectively applicable to image sensors used in low-brightness environments and / or image sensors requiring high efficiency.

[0178] In the following description, some exemplary embodiments of image sensors employing the above-described devices are described with reference to the accompanying drawings. Hereinafter, an organic CMOS image sensor is described as an example of an image sensor.

[0179] Figure 4 This is a cross-sectional view illustrating one example of an image sensor according to some exemplary implementations.

[0180] refer to Figure 4 According to some exemplary embodiments, the image sensor 300 includes a semiconductor substrate 110, an insulating layer 80, a sensor 100, and a color filter layer 70.

[0181] The semiconductor substrate 110 may be a silicon substrate, and a transfer transistor (not shown) and a charge memory 155 are integrated therein. The transfer transistor and / or charge memory 155 may be integrated for each pixel. The charge memory 155 is electrically connected to the sensor 100 (e.g., the charge memory 155 may be included in the semiconductor substrate 110 and may be electrically connected to the second electrode 20 of the sensor 100, for example, based on the charge memory 155 being in direct contact with a trench 85, which itself is in direct contact with the second electrode 20 of the sensor 100).

[0182] 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 / or alloys thereof, but are not limited thereto.

[0183] An insulating layer 80 is formed on the metal wires 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 charge storage 155. The trenches 85 may be filled with filler.

[0184] The aforementioned sensor 100 is formed on the insulating layer 80. The sensor 100 may have... Figure 1 Alternatively, the structure shown in Figure 3 may be described in the same manner as described above. One of the first electrode 10 or the second electrode 20 of the sensor 100 may be a light-receiving electrode, and the other of the first electrode 10 and the second electrode 20 of the sensor 100 may be connected (e.g., electrically connected) to the charge memory 155. For example, the first electrode 10 of the sensor 100 may be a light-receiving electrode, and the second electrode 20 of the sensor 100 may be connected to the charge memory 155. For example, the second electrode 20 of the sensor 100 may be a light-receiving electrode, and the first electrode 10 of the sensor 100 may be connected to the charge memory 155 via a conductive material (e.g., a metal with low resistivity, such as aluminum (Al), copper (Cu), silver (Ag), and / or alloys thereof) located within the trench 85.

[0185] A color filter layer 70 is formed on the sensor 100 and therefore on the semiconductor substrate 110. As in at least Figure 4 As shown (and as further in at least) Figure 6 and 13 As shown in the diagram, the color filter layer 70 may overlap, at least partially or completely, the photoactive layer 30 of the sensor 100 in a direction extending perpendicular to the upper surface 110a of the semiconductor substrate 110. The color filter layer 70 may include a blue filter 70a formed in blue pixels, a red filter 70b formed in red pixels, and a green filter 70c formed in green pixels. However, the inventive concept is not limited thereto, and may alternatively or additionally include cyan filters, magenta filters, and / or yellow filters.

[0186] An insulating layer 180 is formed between the sensor 100 and the color filter layer 70. The insulating layer 180 may be omitted.

[0187] A focusing lens (not shown) may be further formed on the color filter layer 70. The focusing lens controls the direction of the incident light and focuses the light into a region. The focusing lens may have, for example, a cylindrical or hemispherical shape, but is not limited thereto.

[0188] Figure 5 This is a top view of an example of an image sensor implemented according to some exemplary methods, and Figure 6 This illustrates implementation methods based on some examples. Figure 5 A cross-sectional view of an example of an image sensor.

[0189] Reference Figure 5 and 6 Image sensor 400 according to some exemplary embodiments includes a semiconductor substrate 110 in which photosensitive devices 150a and 150b, a transfer transistor (not shown) and a charge memory 155 are integrated; a lower insulating layer 60; a color filter layer 70; an upper insulating layer 80; and the aforementioned sensor 100.

[0190] The semiconductor substrate 110 may be a silicon substrate, and photosensitive devices 150a and 150b, a transfer transistor (not shown), and a charge storage device 155 are integrated therein. The photosensitive devices 150a and 150b may be photodiodes and can be understood as being stacked in the semiconductor substrate 110 in a direction extending parallel to the upper surface 110a of the semiconductor substrate 110. It will be understood that, according to the inclusion of at least... Figure 6 , 7 The semiconductor substrate 110 of some of the exemplary embodiments shown in 13 may include at least one photodiode (e.g., at least one of photosensing devices 150a and / or 150b).

[0191] Light sensing devices 150a and 150b, transfer transistors, and / or charge memory 155 can be integrated into each pixel. For example, as shown in the figure, light sensing devices 150a and 150b can be included in the blue and red pixels respectively, and charge memory 155 can be included in the green pixel.

[0192] The light sensing devices 150a and 150b can be configured to sense light and the sensed information can be transmitted by a transfer transistor. The charge memory 155 is electrically connected to the sensor 100 and the information in the charge memory 155 can be transmitted by the transfer transistor.

[0193] 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, this disclosure is not limited to the above structure, and the metal lines and pads may be disposed under the photosensitive devices 150a and 150b.

[0194] 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 that expose charge storage 155. The trenches may be filled with filler.

[0195] A color filter layer 70 is formed on the lower insulating layer 60. The color filter layer 70 includes a blue filter 70a in the blue pixels and a red filter 70b in the red pixels. However, this disclosure is not limited thereto, and may alternatively or additionally include a cyan filter, a magenta filter, and / or a yellow filter. Figure 5-6 Some of the exemplary embodiments shown are described in which a green filter is not provided, but in some cases a green filter may be provided.

[0196] An upper insulating layer 80 is formed on the color filter layer 70. The upper insulating layer 80 can remove and planarize the steps caused by the color filter layer 70. The upper insulating layer 80 and the lower insulating layer 60 have contact holes (not shown) that expose pads and trenches 85 that expose charge storage 155 of green pixels.

[0197] The aforementioned sensor 100 is formed on the upper insulating layer 80. The sensor 100 may have... Figure 1The structure is as shown in Figure 3, and described in detail above. One of the first electrode 10 or the second electrode 20 of the sensor 100 may be a light-receiving electrode, and the other of the first electrode 10 and the second electrode 20 of the sensor 100 may be connected to the charge memory 155. For example, the first electrode 10 of the sensor 100 may be a light-receiving electrode, and the second electrode 20 of the sensor 100 may be connected to the charge memory 155. For example, the second electrode 20 of the sensor 100 may be a light-receiving electrode, and the first electrode 10 of the sensor 100 may be connected to the charge memory 155. Sensor 100 may include a photoactive layer 30 comprising a light-absorbing semiconductor configured to absorb light in a first wavelength spectrum (e.g., at least a portion of incident light 900), the first wavelength spectrum being one of a blue wavelength spectrum, a green wavelength spectrum, or a red wavelength spectrum. At least one of a first photosensitive device 150a or a second photosensitive device 150b may be configured to sense light in a second wavelength spectrum (e.g., at least a portion of incident light 900), the second wavelength spectrum being one of a blue wavelength spectrum, a green wavelength spectrum, or a red wavelength spectrum, wherein the first wavelength spectrum and the second wavelength spectrum are different from each other. At least another of the first photosensitive device 150a or the second photosensitive device 150b may be configured to sense light in a third wavelength spectrum (e.g., at least a portion of incident light 900), the third wavelength spectrum being one of a blue wavelength spectrum, a green wavelength spectrum, or a red wavelength spectrum, wherein the third wavelength spectrum is different from both the first and second wavelength spectra. For example, sensor 100 may include a photoactive layer 30 comprising a light-absorbing semiconductor configured to absorb green light (e.g., green wavelength spectrum), a first photosensitive device 150a configured to absorb blue light (e.g., blue wavelength spectrum), and a second photosensitive device 150b configured to absorb red light (e.g., red wavelength spectrum). In some embodiments, a color filter layer 70 may not be present in sensor 400, and photosensitive devices 150a and 150b may each be configured to absorb a specific wavelength spectrum independently of color filter layer 70 (e.g., in the absence of color filter layer 70). In some embodiments, photosensitive devices 150a and 150b may be configured to absorb light passing through a specific color filter 70a or 70b, which overlaps with photosensitive device 150a or 150b in a direction perpendicular to the upper surface 110a of semiconductor substrate 110.

[0198] A focusing lens (not shown) may be further formed on the sensor 100. The focusing lens controls the direction of the incident light and focuses the light into a region. The focusing lens may have, for example, a cylindrical or hemispherical shape, but is not limited thereto.

[0199] Figure 7 This illustrates implementation methods based on some examples. Figure 5A cross-sectional view of another example of an image sensor.

[0200] refer to Figure 7 Image sensor 500 according to some exemplary embodiments includes a semiconductor substrate 110 in which light sensing devices 150a and 150b, a transfer transistor (not shown), and a charge memory 155 are integrated, an insulating layer 80, and a sensor 100, as included in at least Figure 5-6 As in some exemplary embodiments of the illustrated embodiments. Sensor 100 may include a photoactive layer 30 comprising a light-absorbing semiconductor configured to absorb light in a first wavelength spectrum (e.g., at least a portion of incident light 900), the first wavelength spectrum being one of a blue wavelength spectrum, a green wavelength spectrum, or a red wavelength spectrum, and at least one of a first photosensing device 150a or a second photosensing device 150b may be configured to sense light in a second wavelength spectrum (e.g., at least a portion of incident light 900), the second wavelength spectrum being one of a blue wavelength spectrum, a green wavelength spectrum, or a red wavelength spectrum, wherein the first wavelength spectrum and the second wavelength spectrum are different from each other. For example, sensor 100 may include a photoactive layer 30 comprising a light-absorbing semiconductor configured to absorb green light (e.g., green wavelength spectrum), a first photosensing device 150a configured to absorb blue light (e.g., blue wavelength spectrum), and a second photosensing device 150b configured to absorb red light (e.g., red wavelength spectrum).

[0201] However, with including at least Figure 5-6 Some of the example implementations shown differ from those in the example implementations, and are based on at least Figure 7 In some exemplary embodiments of the image sensor 500 shown, photosensitive devices 150a and 150b are stacked in a vertical direction (e.g., a direction perpendicular to the upper surface 110a of the semiconductor substrate 110), and the color filter layer 70 is omitted. Photosensitive devices 150a and 150b are electrically connected to a charge memory (not shown), and information sensed by photosensitive devices 150a and 150b can be transmitted by a transfer transistor. Photosensitive devices 150a and 150b can selectively absorb light in various wavelength spectra depending on the stacking depth.

[0202] Sensor 100 may have Figure 1The structure shown in Figure 3 is described in detail above. One of the first electrode 10 or the second electrode 20 of the sensor 100 may be a light-receiving electrode, and the other of the first electrode 10 and the second electrode 20 of the sensor 100 may be connected to the charge memory 155. For example, the first electrode 10 of the sensor 100 may be a light-receiving electrode, and the second electrode 20 of the sensor 100 may be connected to the charge memory 155. For example, the second electrode 20 of the sensor 100 may be a light-receiving electrode, and the first electrode 10 of the sensor 100 may be connected to the charge memory 155.

[0203] Figure 8 This is a top view of another example of an image sensor implemented according to some example methods, and Figure 9 It is shown Figure 8 A cross-sectional view of an example of an image sensor.

[0204] According to some exemplary embodiments, the image sensor 600 has a structure in which a green device configured to selectively absorb light in the green wavelength spectrum, a blue device configured to selectively absorb light in the blue wavelength spectrum, and a red device configured to selectively absorb light in the red wavelength spectrum are stacked.

[0205] Image sensor 600 according to some exemplary embodiments includes a semiconductor substrate 110, a lower insulating layer 60, a middle insulating layer 65, an upper insulating layer 80, a first sensor 100a, a second sensor 100b, and a third sensor 100c.

[0206] The semiconductor substrate 110 may be a silicon substrate, and a transfer transistor (not shown) and charge storage devices 155a, 155b and 155c are integrated therein.

[0207] 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.

[0208] The first sensor 100a, the second sensor 100b, and the third sensor 100c are sequentially formed on the lower insulating layer 60.

[0209] The first, second, and third sensors 100a, 100b, and 100c can each have independently... Figure 1The structure is as shown in Figure 3, and described in detail above. The first, second, and third sensors 100a, 100b, and 100c may have the same or different structures and / or material compositions. One of the first electrode 10 or the second electrode 20 of the first, second, and third sensors 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 sensors 100a, 100b, and 100c may be connected to charge storage devices 155a, 155b, and 155c. For example, the first electrodes 10a, 10b, and 10c of the first, second, and third sensors 100a, 100b, and 100c may be light-receiving electrodes, and the second electrodes 20a, 20b, and 20c of the first, second, and third sensors 100a, 100b, and 100c may be connected to charge storage device 155. For example, the second electrodes 20a, 20b, and 20c of the first, second, and third sensors 100a, 100b, and 100c can be light-receiving electrodes, and the first electrodes 10a, 10b, and 10c of the first, second, and third sensors 100a, 100b, and 100c can be connected to the charge memory 155.

[0210] The photoactive layer 30a of the first sensor 100a selectively absorbs light in one of the red, blue, or green wavelengths, thereby causing band bending at the Schottky junction interface. Charge carriers can be transferred from the first electrode 10a to the second electrode 20a by applying an external bias (e.g., a voltage bias applied between the first electrode 10a and the second electrode 20a). For example, the first sensor 100a may be a red device configured to absorb light in the red wavelength spectrum. An intermediate insulating layer 65 is formed on the first sensor 100a.

[0211] The second sensor 100b is formed on the intermediate insulating layer 65.

[0212] The photoactive layer 30b of the second sensor 100b can be configured to selectively absorb light in one of the red, blue, or green wavelengths, thereby causing band bending at the Schottky junction interface, and carriers can be transferred from the first electrode 10b to the second electrode 20b by applying an external bias (e.g., a voltage bias applied between the first electrode 10b and the second electrode 20b). For example, the second sensor 100b can be configured as a blue device that absorbs light in the blue wavelength spectrum.

[0213] An upper insulating layer 80 is formed on the second sensor 100b. The lower insulating layer 60, the middle insulating layer 65, and the upper insulating layer 80 have multiple trenches 85a, 85b, and 85c that expose charge storage devices 155a, 155b, and 155c.

[0214] The third sensor 100c is formed on the upper insulating layer 80.

[0215] The photoactive layer 30c of the third sensor 100c can be configured to selectively absorb light in one of the red, blue, or green wavelengths, thereby causing band bending at the interface of the Schottky junction, and carriers can be transferred from the first electrode 10c to the second electrode 20c by applying an external bias (e.g., a voltage bias applied between the first electrode 10c and the second electrode 20c). For example, the third sensor 100c can be configured as a green device that absorbs light in the green wavelength spectrum.

[0216] A focusing lens (not shown) may be further formed on the third sensor 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.

[0217] The figure shows a structure in which the first sensor 100a, the second sensor 100b, and the third sensor 100c are stacked in sequence, but is not limited thereto, and the stacking order can be changed in different ways.

[0218] As described above, the first sensor 100a, the second sensor 100b, and the third sensor 100c, which are configured to absorb light in different wavelength spectra, have a stacked structure, thereby further reducing the size of the image sensor and implementing a size-reduced image sensor.

[0219] Figure 10 This is a top view illustrating another example of an image sensor implemented according to some exemplary methods, and Figure 11 It is shown Figure 10 A cross-sectional view of an example of an image sensor.

[0220] Reference Figure 10 and 11 The image sensor 1100 includes a device 90 on a semiconductor substrate 110, and the device 90 includes a plurality of devices 90-1, 90-2, and 90-3. The plurality of devices 90-1, 90-2, and 90-3 can be configured to absorb light of different wavelength spectra (e.g., blue light, green light, or red light). Reference Figure 11 Multiple devices 90-1, 90-2, and 90-3 are arranged in parallel on the semiconductor substrate 110 in a horizontal direction, and may partially or completely overlap each other in a direction parallel to the upper surface 110a of the semiconductor substrate 110. Each device 90-1, 90-2, and 90-3 is connected to a charge memory 155 integrated in the semiconductor substrate 110 via a trench 85.

[0221] Each of the devices 90-1, 90-2, and 90-3 may be the sensor 100 described above. For example, two or more devices 90-1, 90-2, and 90-3 may include different portions of a common continuous layer extending continuously between devices 90-1, 90-2, and 90-3. For example, multiple 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 devices 90-1, 90-2, and 90-3 may have different photoactive layers 30 configured to absorb light in different wavelength spectra of incident light. Other structures of the image sensor 1100 may be referenced. Figures 4 to 9 The image sensor described is one or more of the same.

[0222] Figure 12 This is a cross-sectional view illustrating one example of an image sensor according to some exemplary implementations.

[0223] refer to Figure 12 The image sensor 1200 includes a semiconductor substrate 110 and devices 90-1 and 91 stacked on the semiconductor substrate 110. Device 91 includes a plurality of devices 90-2 and 90-3, and the plurality of devices 90-2 and 90-3 may be arranged to overlap each other in a direction extending parallel to the upper surface 110a of the semiconductor substrate 110. The plurality of devices 90-1, 90-2 and 90-3 may be configured to absorb light of different wavelength spectra (e.g., blue light, green light or red light).

[0224] As an example, device 91 may include multiple horizontally arranged devices configured to absorb light in different wavelength spectra. As an example, device 90-1 may be configured to absorb light selected from a wavelength spectrum of blue, green, and red light. As an example, device 91 may completely or partially overlap with device 90-1. Other structures of the image sensor 1200 may be referenced. Figures 4 to 9 The image sensor described is one or more of the same.

[0225] Figure 13 This is a cross-sectional view illustrating another example of an image sensor implemented according to some exemplary embodiments.

[0226] refer to Figure 13 The image sensor 1300 includes: a semiconductor substrate 110 in which photosensitive devices 150a and 150b, a transfer transistor (not shown), and a charge memory 155 are integrated; an upper insulating layer 80 and a color filter layer 70 are on the semiconductor substrate 110; a lower insulating layer 60 and a device 90 are under the semiconductor substrate 110. The device 90 may be the aforementioned sensor 100. Figure 13In this configuration, device 90 is disposed beneath semiconductor substrate 110, thereby separating device 90 and color filter layer 70 from photosensing devices 150a and 150b. Other structures of the image sensor 1300 are comparable to those in the reference numeral. Figures 4 to 9 The image sensor described is one or more of the same.

[0227] The sensors described herein include any one of sensors 100, 300, 400, 500, 600, 1100, 1200, 1300, and / or any combination thereof, including any exemplary embodiment of sensor 100 comprising a first electrode 10 and a second electrode 20 and a photoactive layer 30 according to any exemplary embodiment.

[0228] The aforementioned devices and sensors can be applied to a variety of electronic devices, such as, but not limited to, mobile phones, camera modules (also referred to herein as cameras), surveillance cameras, biometric devices, medical devices, and / or automotive electronic components.

[0229] Figure 14 These are schematic diagrams of electronic devices implemented according to some examples.

[0230] refer to Figure 14 The electronic device 1700 may include a processor 1720, a memory 1730, and an image sensor 1740 electrically connected to each other via a bus 1710. The image sensor 1740 may include any sensor and / or device according to any example implementation (e.g., any one and / or any combination of sensors 100, 300, 400, 500, 600, 1100, 1200, 1300 according to any example implementation). In some example implementations, the image sensor 1740 may be a camera including any of the sensors and / or devices according to any example implementation. The memory 1730, as a non-transitory computer-readable medium, may store instruction programs. The processor 1720 may execute the stored instruction programs to implement one or more functions. As an example, the processor 1720 may process electrical signals generated by the image sensor. The processor 1720 may generate output (e.g., an image to be displayed on a display interface) based on such processing.

[0231] Memory 1730 may be a non-transitory computer-readable medium and may store instruction programs. 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). Processor 1720 may execute the stored instruction programs to implement one or more functions. For example, processor 1720 may be configured to process electrical signals generated by image sensor 1740. Processor 1720 may include: processing circuitry, such as hardware including logic circuitry; hardware / software combinations, such as a processor executing software; or combinations thereof. For example, processing circuitry may more specifically include, but is not limited to, a central processing unit (CPU), an arithmetic logic unit (ALU), a digital signal processor, a microcomputer, a field-programmable gate array (FPGA), a system-on-a-chip (SoC), a programmable logic unit, a microprocessor, an application-specific integrated circuit (ASIC), etc. The processor 1720 may be configured to generate an output (e.g., an electrical signal) based on such processing and / or process the output from the image sensor 1740 (e.g., an electrical signal based on carrier transport transferred to the second electrode of the image sensor 1740).

[0232] Figure 18 This is a flowchart illustrating a method of operating a sensor according to some exemplary embodiments. The method can be performed with respect to a sensor according to any exemplary embodiment, including a sensor comprising a first electrode 10, a second electrode 20, and a photoactive layer 30 between the first and second electrodes 10 and 20, the photoactive layer 30 comprising a light-absorbing semiconductor according to any exemplary embodiment.

[0233] In S1802, incident light (e.g., incident light 900) may enter a sensor (e.g., a sensor including sensor 100 according to any example embodiment) and may enter the photoactive layer 30 of the sensor such that the photoactive layer 30 may absorb at least a portion of the incident light to generate photogenerated carriers, as described herein according to any example embodiment.

[0234] In S1804, the photoactive layer 30 may capture at least some or all of the photogenerated carriers (which are generated in S1802) at carrier trapping sites 30a in the photoactive layer 30, wherein the carrier trapping site 30a may be any carrier trapping site according to any example implementation.

[0235] In S1806, the sensor can induce band bending at the interface of the Schottky junction between the first electrode 10 and the photoactive layer 30, wherein the band bending is based on or caused by trapped photogenerated carriers (which are trapped in S1804). To reiterate, in S1806, the sensor can cause the trapped photogenerated carriers to induce band bending at the interface of the Schottky junction between the first electrode 10 and the photoactive layer 30. This band bending can be induced as described herein according to any exemplary embodiment. In some exemplary embodiments, the photogenerated carriers generated in S1802 act as a switch to induce band bending at the interface of the Schottky junction.

[0236] In S1808, according to any exemplary embodiment, a bias voltage (also referred to herein as a voltage bias, voltage difference, etc.) may be applied between the first electrode 10 and the second electrode 20 to cause the sensor to transfer charge carriers from the first electrode 10 to the second electrode 20 via the photoactive layer 30. For example, a first voltage (e.g., 0 MV / cm, 0.1 MV / cm, 0.2 MV / cm, 0.5 MV / cm, etc.) may be applied to the first electrode 10, and a second voltage (which may be different from the first voltage) (e.g., 0.1 MV / cm, 0.2 MV / cm, 0.5 MV / cm, etc.) may be applied to the second electrode 20, wherein a voltage difference (e.g., a bias voltage) is applied between the first electrode 10 and the second electrode 20, and wherein, according to any exemplary embodiment, the bias voltage causes charge carriers to transfer from the first electrode 10 to the second electrode 20 via the photoactive layer 30. The applied bias voltage may be greater than about 0 MV / cm and less than or equal to about 0.5 MV / cm. The amount of charge carriers transferred to the second electrode can be greater than the amount of photogenerated charge carriers generated in S1802 by the photoactive layer based on the absorption of incident light. In some exemplary embodiments, the external quantum efficiency (EQE) of the sensor can exceed approximately 100%.

[0237] In S1810, the electrical signal transmitted to the second electrode 20 is read according to any exemplary embodiment. For example, the transferred charge carriers transferred to and reaching the second electrode 20 may define the electrical signal transmitted to the second electrode 20 and may be output as an electrical signal from the second electrode (e.g., output to the processing circuitry according to any exemplary embodiment), said electrical signal being transmitted to the second electrode and read from the sensor. The electrical signal transmitted to the second electrode may not include (e.g., may exclude) the electrical signal generated by photogenerated charge carriers. For example, the electrical signal may completely include the charge carriers transferred to the second electrode 20.

[0238] In the following description, some exemplary embodiments are illustrated in more detail with reference to examples. However, the scope of the inventive concept is not limited to the following embodiments.

[0239] Device manufacturing

[0240] Example 1

[0241] ITO (WF: 4.7 eV) was sputtered onto a glass substrate to form a lower electrode approximately 150 nm thick. Subsequently, a compound represented by Formula 1 was deposited on the lower electrode to form a buffer layer 5 nm thick. Then, a p-type semiconductor (λ) represented by Formula 2 was deposited on the buffer layer. 最大 =555nm) to form a 400nm thick photoactive layer. ITO is sputtered onto the photoactive layer to form a 28nm thick top electrode, thereby fabricating a Schottky device.

[0242] [Chemical Formula 1]

[0243]

[0244] [Chemical Formula 2]

[0245]

[0246] Example 2

[0247] The Schottky-type device was fabricated in the same manner as in Example 1, except that Al was deposited on the photoactive layer instead of ITO to form an 80 nm thick top electrode.

[0248] Reference ratio 1

[0249] ITO (WF: 4.7 eV) was sputtered onto a glass substrate to form a lower electrode approximately 150 nm thick. Subsequently, a compound represented by Chemical Formula 1 was deposited on the lower electrode to form a 5 nm thick buffer layer. Then, a p-type semiconductor (λ) represented by Chemical Formula 2 was... 最大 A 400 nm thick photoactive layer is formed by co-depositing a 555 nm thick pn junction device with an n-type semiconductor fullerene (C60) on a buffer layer. ITO is then sputtered onto the photoactive layer to form a 28 nm thick top electrode.

[0250] Reference ratio 2

[0251] The pn junction device was fabricated in the same manner as in Reference 1, except that Al was deposited on the photoactive layer instead of ITO to form an 80 nm thick top electrode.

[0252] Evaluation I

[0253] The external quantum efficiency (EQE) of the devices according to the embodiments and reference models is evaluated based on the external electric field.

[0254] External quantum efficiency (EQE) is evaluated by reading the current generated by light passing through the device while simultaneously modulating the wavelength of light by applying a voltage between the upper and lower electrodes.

[0255] The results are shown in Tables 1 and 2, and Figure 15 and 16 middle.

[0256] Figure 15 This is a graph showing the variation of the external quantum efficiency (EQE) of the device according to Embodiment 1 and Reference 1 according to some exemplary embodiments, and Figure 16 This is a graph showing the variation of the external quantum efficiency (EQE) of the device according to embodiment 2 and reference 2 based on some exemplary implementations.

[0257] Table 1

[0258] Example 1 125 Reference ratio 1 70

[0259] Table 2

[0260] Example 2 2468 Reference ratio 2 70

[0261] Refer to Tables 1 and 2 and Figure 15 and 16 The external quantum efficiency (EQE) of the device according to the embodiments increases with increasing electric field, and is also significantly higher than that of the device according to the reference model at a specific (or alternatively predetermined) electric field or higher (about 0.3 MV / cm or higher). In particular, the device according to the embodiments can achieve an external quantum efficiency (EQE) greater than 100% at a specific (or alternatively predetermined) electric field or higher.

[0262] Evaluation II

[0263] The wavelength-dependent external quantum efficiency (EQE) of the device according to Example 1 was evaluated.

[0264] Figure 17 This is a graph showing the wavelength-dependent external quantum efficiency (EQE) of the device according to Embodiment 1 according to some exemplary embodiments.

[0265] refer to Figure 17 The device according to Example 1 shows that the external quantum efficiency (EQE) varies with the applied voltage, and when about 20V is applied, an external quantum efficiency (EQE) greater than 100% can be achieved in the green wavelength spectrum of about 500nm to 600nm.

[0266] Evaluation III

[0267] Evaluate the leakage current characteristics of the devices according to the embodiments and reference models.

[0268] Leakage current is evaluated by applying a reverse bias to the device in dark conditions, reading the current value at -3V or -20V, and converting the current value to electrons per square.

[0269] Table 3 shows the results.

[0270] Table 3

[0271] Example 2 0.8 <![CDATA[1.7x10 3 ]]> Reference ratio 2 1.5 <![CDATA[5.4x10 3 ]]>

[0272] Referring to Table 3, the device according to the embodiment has a lower leakage current compared to the device according to the reference scale.

[0273] Evaluation IV

[0274] The detectability of the device was evaluated according to the embodiments and references.

[0275] The detectability is obtained by dividing the amount of incident light by the photocurrent, and then dividing the result by the dark current (which is noise).

[0276] The results are shown in Tables 4 and 5.

[0277] Table 4

[0278]

[0279] Table 5

[0280]

[0281] Referring to Tables 4 and 5, the device according to the embodiments shows improved detectability compared to the device according to the reference scale.

[0282] Evaluation V

[0283] The design application is based on the device according to Example 1 and Reference Example 1. Figure 5 and 6 The image sensor (structure I, pixel size = 1.12 μm) and the device applied according to Example 2 and Reference 2. Figure 4 An image sensor (Structure II, pixel size = 1.4 μm) was developed, and the YSNR10 of the image sensor was evaluated.

[0284] The YSNR10 of an image sensor is the minimum light intensity (in lux) where the signal-to-noise ratio (signal / noise) is 10. The signal is the signal sensitivity obtained by performing a color correction step using a color correction matrix (CCM) on the raw RGB signal calculated by FDTD (Finite-Difference Time-Domain Method), and the noise is the noise generated when measuring the signal in the image sensor. The color correction step is a process of reducing the difference from true colors by performing image processing on the raw RGB signal obtained from the image sensor. With a lower YSNR10 value, image characteristics improve under low light intensity.

[0285] The results are shown in Tables 6 and 7.

[0286] Table 6

[0287] Example 1 59 Reference ratio 1 75

[0288] Table 7

[0289] Example 2 47.2 Reference ratio 2 75

[0290] Referring to Tables 6 and 7, compared with the image sensor used in the device according to the reference scale, the image sensor used in the device according to the embodiment has a lower YSNR10, which can improve the sensitivity of the image sensor according to the embodiment.

[0291] Although this disclosure has been described in conjunction with exemplary embodiments currently considered to be practice, it will be understood that the concept of the invention is not limited to the disclosed exemplary embodiments. Rather, the concept of the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. Sensors, including: First electrode and second electrode, and A photoactive layer is provided between the first electrode and the second electrode. The photoactive layer includes a light-absorbing semiconductor configured to form a Schottky junction with the first electrode. The light-absorbing semiconductor is either a p-type semiconductor or an n-type semiconductor, but does not include both p-type and n-type semiconductors together. The photoactive layer has carrier trapping sites configured to trap photogenerated carriers generated by a light-absorbing semiconductor that absorbs incident light entering the photoactive layer at least near the first electrode. The sensor is configured to have an external quantum efficiency (EQE) that is adjustable based on the voltage bias energy applied between the first and second electrodes. The photoactive layer has a first surface near the first electrode and a second surface near the second electrode, the second surface being opposite to the first surface, such that the first surface and the second surface are opposite surfaces of the photoactive layer, and the carrier trapping sites in the photoactive layer extend in a direction perpendicular to the first surface of the photoactive layer within 50% of the total thickness of the photoactive layer from the first surface of the photoactive layer.

2. The sensor of claim 1, wherein as the voltage bias between the first electrode and the second electrode increases, the external quantum efficiency (EQE) of the sensor increases, such that the magnitude of the external quantum efficiency (EQE) of the sensor is proportional to the magnitude of the voltage bias between the first electrode and the second electrode.

3. The sensor of claim 2, wherein the voltage bias applied between the first electrode and the second electrode is greater than 0 MV / cm and less than or equal to 0.5 MV / cm.

4. The sensor of claim 1, wherein the external quantum efficiency (EQE) of the sensor exceeds 100%.

5. The sensor as claimed in claim 1, wherein the p-type semiconductor is a p-type nonpolymer semiconductor and the n-type semiconductor is an n-type nonpolymer semiconductor.

6. The sensor of claim 5, wherein the photoactive layer at least partially defines a single continuous phase, the single continuous phase comprising one of the p-type nonpolymer semiconductor or the n-type nonpolymer semiconductor.

7. The sensor as claimed in claim 5, wherein The p-type nonpolymer semiconductor is a p-type monomer with a molecular weight of less than or equal to 5000 Daltons and greater than 0 Daltons. The n-type nonpolymer semiconductor is an n-type monomer with a molecular weight of less than or equal to 5000 Daltons and greater than 0 Daltons.

8. The sensor of claim 7, wherein the p-type monomer is an organic semiconductor comprising an electron-donating portion, a π-conjugated portion, and an electron-receiving portion.

9. The sensor of claim 5, wherein the light-absorbing semiconductor is configured to absorb light in at least one of the blue wavelength spectrum, green wavelength spectrum, red wavelength spectrum, or infrared wavelength spectrum.

10. The sensor of claim 1, wherein the light-absorbing semiconductor comprises 90% to 100% of the total volume of the photoactive layer, such that 90% to 100% of the total volume of the photoactive layer is the light-absorbing semiconductor.

11. The sensor of claim 1, wherein the thickness of the photoactive layer is equal to or greater than 100 nm and less than or equal to 3 μm.

12. The sensor as claimed in claim 1, wherein The surface roughness of the first surface of the photoactive layer is between 0 nm and 10 nm.

13. The sensor of claim 1, wherein the photogenerated carriers are configured to act as switches that cause interfacial band bending in the Schottky junction. Charge carriers are transferred from the first electrode to the second electrode by a voltage bias, and The amount of charge carriers transferred from the first electrode to the second electrode is greater than the amount of photogenerated charge carriers generated by the light-absorbing semiconductor based on the absorption of incident light entering the photoactive layer at least near the first electrode.

14. The sensor of claim 1, further comprising a buffer layer between the photoactive layer and the second electrode.

15. The sensor of claim 1, further comprising a semiconductor substrate, The semiconductor substrate includes a charge storage device electrically connected to the second electrode.

16. The sensor of claim 15, further comprising a color filter layer on the semiconductor substrate, the color filter layer at least partially overlapping the photoactive layer in a direction extending perpendicular to the upper surface of the semiconductor substrate.

17. The sensor of claim 15, wherein the semiconductor substrate further comprises a photodiode.

18. The sensor of claim 17, wherein The light-absorbing semiconductor is configured to absorb light in a first wavelength spectrum, which is one of a blue wavelength spectrum, a green wavelength spectrum, or a red wavelength spectrum. The photodiode includes a first photodiode configured to sense light in a second wavelength spectrum, the second wavelength spectrum being another of a blue wavelength spectrum, a green wavelength spectrum, or a red wavelength spectrum. The first wavelength spectrum and the second wavelength spectrum are different from each other.

19. The sensor of claim 18, wherein The photodiode further includes a second photodiode, which is stacked with the first photodiode in the semiconductor substrate in a direction extending perpendicularly or parallel to the upper surface of the semiconductor substrate. The second photodiode is configured to sense light in a third wavelength spectrum, which is another of the blue, green, or red wavelength spectra. The third wavelength spectrum is different from both the first wavelength spectrum and the second wavelength spectrum.

20. A method of operating a sensor as claimed in any one of claims 1-19, the method comprising: Based on the absorption of incident light, the photoactive layer generates photogenerated carriers at the photoactive layer. The photogenerated carriers are captured at carrier trapping sites in the photoactive layer. The captured photogenerated carriers cause the interfacial band bending of the Schottky junction between the first electrode and the photoactive layer. Applying a voltage bias between the first and second electrodes causes the sensor to transfer charge carriers from the first electrode to the second electrode via the photoactive layer. An electrical signal is generated from the sensor based on the charge carriers transferred to the second electrode.

21. The method of claim 20, wherein the electrical signal transmitted to the second electrode does not include a separate electrical signal generated by the photogenerated carriers.

22. A camera comprising a sensor as described in any one of claims 1-19.

23. An electronic device including a sensor as described in any one of claims 1-19 or a camera as described in claim 22.

Images