A polarized photoelectric detection device based on an organic semiconductor material and a preparation method and application thereof

Abstract

This invention discloses a polarization photodetector based on organic semiconductor materials, its fabrication method, and its applications. This polarization photodetector uses anisotropic organic semiconductors as the active layer, utilizing the intrinsic anisotropy of the organic semiconductors to achieve response and detection of light polarization. This invention effectively solves the problems of traditional polarization photodetector systems being complex, large in size, and difficult to miniaturize and integrate. The designed novel polarization photodetector has a relatively simple structure, strong adaptability, high integration, and is easy to miniaturize. It helps reduce the fabrication difficulty of polarization photodetectors, enabling mass production, and is particularly compatible with flexible wearable devices, playing a significant role in promoting the development of polarization photodetection and polarization photodetector devices.

Description

Technical Field

[0001] This invention belongs to the field of polarization photodetector, specifically relating to a polarization photodetector based on organic semiconductor materials, its preparation method, and its application. Background Technology

[0002] In recent years, polarization photodetector technology has received widespread attention in the scientific research field. Its main purpose is to detect and study the properties of light waves in the polarization dimension, beyond intensity and wavelength, using traditional optoelectronic devices. This includes aspects such as photon absorption, photon-electron interactions, the relationship between material structure and photoelectric response, and the design and control of device structures. Furthermore, it aims to combine these technologies with traditional optical and electrical characteristics to achieve the development of novel, highly integrated polarization photodetector devices.

[0003] Traditional polarization photodetectors containing inorganic semiconductor materials require the integration of optical elements such as gratings or polarizers onto the photodetector to achieve a response to light polarization. These polarization photodetectors suffer from system complexity and large size, making it difficult to meet the future trends of miniaturization and wearable devices. How to simplify the device structure design to achieve miniaturization and integration of polarization detection photodetectors, and thus realize large-area controllable fabrication of polarization photodetectors, has become a pressing technical problem to be solved in this field. Summary of the Invention

[0004] This invention provides a polarization photodetector containing an organic semiconductor material. The polarization photodetector utilizes the intrinsic anisotropy of the organic semiconductor material to achieve a response to the polarization direction of light.

[0005] According to an embodiment of the present invention, the organic semiconductor material possesses excellent photoelectric properties, which refer to strong light absorption and good carrier transport characteristics. For example, the organic semiconductor material can be an organic small molecule material or a polymeric semiconductor material. For example, the organic small molecule material can be selected from 2,6-diphenylanthracene (DPA), 2,6-dinathynethracene (dNaAnt), 2,6-bis(p-hexylbenzene)anthracene (C6-DPA), 2,6-bis(p-octylhexylbenzene)anthracene (C8-DPA), 2,6-bis(p-decylbenzene)anthracene (C8-DPA), and C8-decylbenzene (C8-DPA). 10 -DPA), perfluorophthalocyanine copper (F 16At least one of CuPc and copper phthalocyanine (CuPc), preferably 2,6-diphenylanthracene or 2,6-dinaphthylanthracene. For example, the polymeric semiconductor polymer may be selected from at least one of poly(3-hexylthiophene) (P3HT), poly{[N,N′-bis(2-octyldodecyl)benzo[LMN][3,8]o-diazaphenanthroline-1,3,6,8(2H,7H)-tetraone-4,9-diyl)([2,2′]dithienyl-5,5′-diyl)} (trade name N2200), and polypyrrolopyrrolodionethiophene copolymer (PDPP3T), preferably poly(3-hexylthiophene) or polypyrrolopyrrolodionethiophene copolymer.

[0006] According to an embodiment of the present invention, the polarization photodetector includes a structural unit comprising an organic semiconductor active layer, an electrode layer, a dielectric layer, and a supporting substrate; the organic semiconductor active layer is formed of the aforementioned organic semiconductor material.

[0007] According to embodiments of the present invention, the organic semiconductor active layer can be fabricated using any processing method that facilitates the formation of planar anisotropy of the organic semiconductor material, including but not limited to at least one of solution shearing, solution epitaxy, physical vapor transport (PVT), spin coating, and inkjet printing. Those skilled in the art will understand that the specific method employed can be selected based on the physical properties (e.g., solubility, melting and boiling points) of the organic semiconductor material used.

[0008] For example, the method for preparing the organic semiconductor active layer can be selected from any of the following methods:

[0009] Method 1: The organic small molecule material is grown in a tube furnace by physical vapor transport method, and the single crystal is transferred to the dielectric layer. The single crystal is bonded to the surface of the dielectric layer under the action of van der Waals force to obtain an organic semiconductor active layer.

[0010] Method 2: Preparation and growth of single-crystal thin films of the organic small molecule material by solution epitaxy: The organic small molecule material is dissolved in an organic solvent that is immiscible with water. The resulting homogeneous solution is slowly added dropwise to the surface of water. The mixed solution spreads on the surface of water. After the organic solvent evaporates, the single-crystal thin film is obtained.

[0011] A support substrate with a dielectric layer is inserted into water, causing the single-crystal thin film to transfer to the surface of the dielectric layer, thus obtaining an organic semiconductor active layer.

[0012] Method 3: Preparation of single-crystal thin films of the organic small molecule material by solution shearing: The organic small molecule material is dissolved in an organic solvent, and the resulting uniformly mixed solution is dropped onto a support substrate with a dielectric layer. The dropped solution is then slowly sheared and stretched to form an organic semiconductor active layer.

[0013] The organic semiconductor material is formed into an organic semiconductor active layer by any one or more of the above methods. The organic semiconductor material can spontaneously form planar anisotropy under the interaction force of organic molecules. The planar anisotropy means that the physical properties of the material are significantly different in different directions of the plane, especially the optical absorption characteristics.

[0014] According to an embodiment of the present invention, the thickness of the organic semiconductor active layer is in the nanometer to submicrometer range, for example, 10-900 nm, or 50-500 nm. Those skilled in the art can adjust the thickness of the organic semiconductor active layer according to actual needs.

[0015] According to an embodiment of the present invention, the electrode layer is a metal layer; for example, the metal may be selected from at least one of gold, platinum, copper, etc. Those skilled in the art will understand that the specific type of metal selected may need to be adjusted according to the energy band of the organic semiconductor material.

[0016] According to an embodiment of the present invention, the electrode layer can be prepared by a method known in the art. For example, at least one of vacuum thermal evaporation, inkjet printing, and electron beam deposition methods can be selected.

[0017] According to embodiments of the present invention, there is no particular limitation on the type of dielectric layer, which can be an inorganic material dielectric layer and / or an organic material dielectric layer. Exemplarily, the dielectric layer is an inorganic material dielectric layer, such as a dielectric layer formed of inorganic oxide (SiO2).

[0018] According to an embodiment of the present invention, the dielectric layer can be prepared by a method known in the art. For example, at least one of thermal growth method, physical vapor deposition method, spin coating method, etc., can be selected.

[0019] According to an embodiment of the present invention, the thickness of the dielectric layer can be in the nanometer to submicrometer range, for example, 10-900 nm, or 50-500 nm. Those skilled in the art can adjust the thickness of the dielectric layer according to actual needs.

[0020] According to an embodiment of the present invention, the supporting substrate is a rigid substrate (e.g., silicon dioxide, glass, or quartz) or a flexible substrate (e.g., PC, PMMA, PDMS).

[0021] According to an embodiment of the present invention, the polarization photodetector does not contain a grating and / or a polarizer.

[0022] According to an embodiment of the present invention, the arrangement order of the organic semiconductor active layer, electrode layer, dielectric layer, and supporting substrate can be adjusted according to the structure of the polarization photodetector. For example, the polarization photodetector can be a two-terminal device or a three-terminal gate control device; for example, the structure of the three-terminal gate control device can be bottom-gate bottom contact, bottom-gate top contact, top-gate bottom contact, top-gate top contact, etc.

[0023] According to an embodiment of the present invention, van der Waals forces exist between the organic semiconductor active layer and the dielectric layer.

[0024] According to an exemplary embodiment of the present invention, the polarization photodetector includes a structural unit, which is composed of an organic semiconductor active layer, an electrode layer, a dielectric layer, and a supporting substrate;

[0025] The dielectric layer is located on the surface of the supporting substrate, and the organic semiconductor active layer and electrode layer are located on the dielectric layer. The electrode layer is located at both ends of the organic semiconductor active layer (e.g., Figure 1 (Structure shown);

[0026] The organic semiconductor active layer is a single crystal layer of 2,6-diphenylanthracene (DPA) or 2,6-dinaphthylanthracene (dNaAnt). The single crystal layer of 2,6-diphenylanthracene (DPA) or 2,6-dinaphthylanthracene (dNaAnt) can spontaneously form planar anisotropy under the influence of molecular interaction forces.

[0027] According to an embodiment of the present invention, the polarization photodetector exhibits a photocurrent directly related to the direction of the polarization light when illuminated by polarized light.

[0028] The present invention also provides a method for fabricating the above-mentioned polarization photodetector, including using an organic semiconductor material as the organic semiconductor active layer of the polarization photodetector.

[0029] Preferably, the selection of the organic semiconductor material and the preparation of the organic semiconductor active layer have the meanings described above.

[0030] According to an embodiment of the present invention, the method for fabricating the polarization photodetector includes the following steps: assembling structural units containing an organic semiconductor active layer, an electrode layer, a dielectric layer and a supporting substrate to obtain the polarization photodetector.

[0031] According to an embodiment of the present invention, the electrode layer, dielectric layer and supporting substrate have the selections shown above.

[0032] According to embodiments of the present invention, the preparation of the electrode layer and the dielectric layer has the options shown above.

[0033] The present invention also provides the application of the polarization photodetector in image enhancement for geological remote sensing or machine vision.

[0034] The present invention also provides the application of the above-described polarization photodetector as a wearable device.

[0035] Organic semiconductors are mostly composed of molecules made up of atoms such as carbon and hydrogen. The inventors of this application have discovered that the relatively complex structure of organic semiconductor molecules gives them strong asymmetry. Under suitable fabrication methods, they exhibit anisotropy in their aggregated structure, resulting in dichroism in optical properties and a response to the polarization direction of light. Therefore, to overcome the shortcomings of traditional polarization photodetectors, this invention proposes using organic semiconductor materials as photoactive layers in the fabrication of polarization photodetectors. This greatly simplifies the design of the device structure, thereby helping to achieve the miniaturization and integration of polarization detection photodetectors. This method is simple and efficient, enabling large-area controllable fabrication of polarization photodetectors. Compared to inorganic semiconductor materials, organic semiconductor materials are an excellent platform for researching and developing polarization photodetectors. Furthermore, due to the flexibility of organic semiconductors, they can be integrated with wearable devices, which is more advantageous for expanding the functionality and application scenarios of wearable devices.

[0036] The beneficial effects of this invention are:

[0037] 1. The organic polarization photodetector of the present invention utilizes the intrinsic anisotropy of organic semiconductor materials to detect and respond to the polarization direction of light; the organic polarization photodetector of the present invention can greatly simplify the design of polarization photodetector devices and contribute to the integration and miniaturization of devices.

[0038] 2. The organic semiconductor-based polarization photodetector used in this invention has the following advantages: 1) It effectively solves the challenges to integration and miniaturization brought about by the complexity and large size of traditional polarization photodetectors; 2) The device structure is relatively simple, highly adaptable, and highly integrated, providing a new method and approach for constructing polarization photodetectors; 3) It helps reduce the fabrication difficulty of polarization photodetectors, enabling mass production. In particular, it has good compatibility with organic semiconductor devices based on solution processing and can achieve good compatibility with flexible wearable devices, playing an important role in promoting the development of polarization photodetectors.

[0039] 3. This invention, by developing polarization photodetectors based on organic semiconductors, maximizes the advantages of abundant, lightweight, inexpensive, and easily fabricated organic semiconductor materials, providing an effective solution for the large-area, controllable, and array-based fabrication of organic polarization photodetectors. Furthermore, the design is simple, efficient, and highly compatible in fabrication, which opens up possibilities for further fabrication of organic polarization photoelectric composite devices and their applications in organic electronics and polarization photodetection. Attached Figure Description

[0040] Figure 1 This is an optical microscope image of the organic polarization photodetector device prepared by the transfer electrode method in Example 1.

[0041] Figure 2 The polarization response data and curves of the organic polarization photodetector device prepared in Example 1 are shown. Detailed Implementation

[0042] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Furthermore, it should be understood that after reading the disclosure of this invention, those skilled in the art can make various modifications or alterations to the present invention, and these equivalent forms also fall within the scope of protection defined by this invention.

[0043] Unless otherwise specified, the experimental methods used in the following examples are conventional methods; unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0044] Example 1: Polarization photodetector based on 2,6-diphenylanthracene (DPA) organic single crystal

[0045] 1) Growth of 2,6-diphenylanthracene (DPA) organic single crystals:

[0046] The "physical vapor transport method" is used to grow organic single crystals of 2,6-diphenylanthracene (DPA) in a tube furnace. During growth, solid powder of 2,6-diphenylanthracene (DPA) organic molecules is placed in a high-temperature heating zone at temperatures ranging from 100°C to 400°C. By passing an inert gas through the tube furnace, the heated and sublimated organic molecules of 2,6-diphenylanthracene (DPA) are transported by the gas to a low-temperature zone at temperatures ranging from 50°C to 300°C, where they grow as single crystals.

[0047] 2) Silicon wafer cleaning and water-soluble layer modification:

[0048] Before use, silicon wafers with a SiO2 oxide layer are first cleaned with a hydrogen peroxide and concentrated sulfuric acid solution (heated in an electric furnace and boiled) in a volume ratio of approximately 1:2. Then, they are ultrasonically cleaned with deionized water, anhydrous ethanol, and acetone for about 10 minutes each, and finally dried quickly with nitrogen gas.

[0049] 3) Fabrication of gold electrodes:

[0050] A patterned metal mask is fixed to a substrate, and gold of 150nm is thermally evaporated onto it using a vacuum coating machine.

[0051] 4) Assembly of 2,6-diphenylanthracene (DPA) organic single crystal devices:

[0052] 2,6-Diphenylanthracene (DPA) organic single-crystal devices are realized using van der Waals integration technology. Specifically, the organic single crystal grown in step 1) is first transferred to a silicon wafer that has been cleaned and modified with a water-soluble layer in step 2). The organic single crystal adheres to the surface of the silicon wafer under the action of van der Waals forces, forming an organic single-crystal active layer (20nm to 400nm). Then, the gold electrodes deposited in step 3) are separated from their native substrate using a PDMS stamp, and subsequently bonded to both ends of the ideal organic single crystal (e.g., ...). Figure 1 The entire device is fabricated as shown in the diagram. In this device, the silicon wafer is the gate, the oxide layer on the silicon wafer is the dielectric layer, the 2,6-diphenylanthracene (DPA) organic single crystal is the active layer that realizes the polarization response, and the gold electrode is the source and drain electrode of the device.

[0053] 5) Characterization of the polarization response characteristics of organic single-crystal devices:

[0054] In polarization testing, a laser is used as the light source to illuminate the sample. A polarizer with a high extinction ratio is used to achieve linear polarization of the laser, while a half-wave plate is used to change the polarization direction of the laser.

[0055] The polarization response characteristics of the organic single-crystal device prepared in step 4) were tested in a polarization testing system, and the obtained polarization response data are as follows: Figure 2 As shown, the prepared organic single-crystal device does indeed have good polarization response characteristics and can be used in fields such as geological remote sensing or machine vision image enhancement.

[0056] Example 2: Polarization photodetector based on 2,6-bis(p-hexylphenyl)anthracene (C6-DPA) organic single-crystal thin film

[0057] 1) Growth of 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) organic single-crystal thin films:

[0058] Solution epitaxy is used to prepare and grow 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) organic single-crystal films. In the growth process, the organic molecular solid powder of 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) is first dissolved in an organic solvent (toluene, chlorobenzene, or o-dichlorobenzene) to prepare a solution with a mass fraction of 0.1 mg / mL to 10 mg / mL. Then, the well-mixed solution is slowly dropped onto the surface of water. Because it is immiscible with water, the solution gradually and uniformly spreads on the water surface. After the organic solvent in the mixed solution has completely evaporated, a 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) organic single-crystal film with molecular-level thickness is grown on the water surface.

[0059] 2) Silicon wafer cleaning and water-soluble layer modification:

[0060] Before use, silicon wafers with a SiO2 oxide layer are first cleaned with a hydrogen peroxide and concentrated sulfuric acid solution (heated in an electric furnace and boiled) in a volume ratio of approximately 1:2. Then, they are ultrasonically cleaned with deionized water, anhydrous ethanol, and acetone for about 10 minutes each, and finally dried quickly with nitrogen gas.

[0061] 3) Transfer of 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) organic single-crystal thin films

[0062] Slowly insert the clean silicon wafer obtained in step 2) into the water in step 1), and slowly lift the silicon wafer upward to complete the transfer of the 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) organic single crystal film obtained in step 1) onto the silicon wafer.

[0063] 4) Fabrication of 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) organic single-crystal thin-film devices:

[0064] The patterned metal mask is fixed to the 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) organic single crystal thin film prepared in step 3), and the device is fabricated by thermally evaporating 150 nm of gold on it using a vacuum coating machine.

[0065] In this device, the silicon wafer is the gate, the oxide layer on the silicon wafer is the dielectric layer, the 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) organic single crystal thin film is the active layer that realizes polarization response, and the gold electrode is the source and drain electrode of the device.

[0066] 5) Characterization of polarization response characteristics of organic single-crystal thin-film devices:

[0067] In polarization testing, a laser is used as the light source to illuminate the sample. A polarizer with a high extinction ratio is used to achieve linear polarization of the laser, while a half-wave plate is used to change the polarization direction of the laser.

[0068] The polarization response characteristics of the organic single-crystal thin film device prepared in step 4) are tested and characterized in a polarization testing system. The polarization response characteristics of the device in this embodiment are at least comparable to those of the device in Example 1.

[0069] Example 3: Polarization photodetector based on highly oriented organic thin film of 2,6-bis(p-hexylphenyl)anthracene (C6-DPA)

[0070] 1) Silicon wafer cleaning and water-soluble layer modification:

[0071] Before use, silicon wafers with a SiO2 oxide layer are first cleaned with a hydrogen peroxide and concentrated sulfuric acid solution (heated in an electric furnace and boiled) in a volume ratio of approximately 1:2. Then, they are ultrasonically cleaned with deionized water, anhydrous ethanol, and acetone for about 10 minutes each, and finally dried quickly with nitrogen gas.

[0072] 2) Growth of highly oriented organic thin films of 2,6-bis(p-hexylbenzene)anthracene (C6-DPA):

[0073] The "solution shearing method" was used to prepare 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) organic single-crystal thin films. First, the organic molecular solid powder of 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) was dissolved in an organic solvent (toluene, chlorobenzene, or o-dichlorobenzene) to prepare a solution with a mass fraction of 0.1 mg / mL to 10 mg / mL. The solution was then dropped onto the silicon wafer substrate obtained in step 1), and the droplets were processed using the "solution shearing method" to form a highly oriented organic thin film of 2,6-bis(p-hexylbenzene)anthracene (C6-DPA).

[0074] 3) Fabrication of highly oriented organic thin-film devices made of 2,6-bis(p-hexylphenyl)anthracene (C6-DPA):

[0075] The patterned metal mask is fixed to the 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) highly oriented organic thin film prepared in step 2), and the device is fabricated by thermally evaporating 150 nm of gold on it using a vacuum deposition machine.

[0076] In this device, the silicon wafer is the gate, the oxide layer on the silicon wafer is the dielectric layer, the highly oriented 2,6-bis(p-hexylbenzene)anthracene (C6-DPA) thin film is the active layer that realizes polarization response, and the gold electrode is the source and drain electrode of the device.

[0077] 4) Characterization of polarization response characteristics of organic single-crystal thin-film devices:

[0078] In polarization testing, a laser is used as the light source to illuminate the sample. A polarizer with a high extinction ratio is used to achieve linear polarization of the laser, while a half-wave plate is used to change the polarization direction of the laser.

[0079] The polarization response characteristics of the highly oriented organic thin film device prepared in step 3) are tested and characterized in a polarization testing system. The polarization response characteristics of the device in this embodiment are at least comparable to those of the device in Example 1.

[0080] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A polarization photodetector, characterized in that, The polarization photodetector contains a structural unit, which includes an organic semiconductor active layer, an electrode layer, a dielectric layer, and a supporting substrate; the organic semiconductor active layer is formed of an organic semiconductor material. The organic semiconductor material is an organic small molecule material, which is selected from at least one of 2,6-diphenylanthracene, 2,6-dinathyne anthracene, 2,6-di(p-hexylbenzene)anthracene, 2,6-di(p-octylhexylbenzene)anthracene, and 2,6-di(p-decylbenzene)anthracene. The organic semiconductor active layer is prepared using a method that facilitates the formation of planar anisotropy of organic semiconductor materials, and is selected from at least one of solution shearing, solution epitaxial growth and physical vapor deposition. The polarization photodetector does not contain gratings or polarizers.

2. The polarization photodetector according to claim 1, characterized in that, The organic small molecule material is 2,6-diphenylanthracene or 2,6-dinaphthylanthracene.

3. The polarization photodetector according to claim 1, characterized in that, The thickness of the organic semiconductor active layer is in the nanometer to submicrometer range.

4. The polarization photodetector according to claim 1, characterized in that, The thickness of the organic semiconductor active layer is 10-900 nm.

5. The polarization photodetector according to claim 1, characterized in that, The electrode layer is a metal layer; the metal is selected from at least one of gold, platinum, and copper. And / or, the electrode layer is prepared by at least one of vacuum thermal evaporation, inkjet printing, and electron beam deposition.

6. The polarization photodetector according to claim 1, characterized in that, The dielectric layer is an inorganic material dielectric layer and / or an organic material dielectric layer; And / or, the dielectric layer is prepared by at least one of thermal growth method, physical vapor deposition method, and spin coating method; And / or, the thickness of the dielectric layer is in the nanometer to submicrometer range.

7. The polarization photodetector according to claim 1, characterized in that, The supporting substrate can be a rigid substrate or a flexible substrate.

8. The polarization photodetector according to claim 1, characterized in that, The arrangement order of the organic semiconductor active layer, electrode layer, dielectric layer, and supporting substrate is adjusted according to the structure of the polarization photodetector.

9. The polarization photodetector according to claim 1, characterized in that, The polarization photodetector is a two-terminal device or a three-terminal gate modulation device.

10. The polarization photodetector according to claim 1, characterized in that, The polarization photodetector contains a structural unit, which is composed of an organic semiconductor active layer, an electrode layer, a dielectric layer, and a supporting substrate. The dielectric layer is located on the surface of the supporting substrate, the organic semiconductor active layer and the electrode layer are located on the dielectric layer, and the electrode layer is located at both ends of the organic semiconductor active layer; The organic semiconductor active layer is a 2,6-diphenylanthracene single crystal layer or a 2,6-dinaphthylanthracene single crystal layer. The 2,6-diphenylanthracene single crystal layer or the 2,6-dinaphthylanthracene single crystal layer can spontaneously form planar anisotropy under the influence of molecular interaction forces.

11. A method for fabricating a polarization photodetector according to any one of claims 1-10, characterized in that, The polarization photodetector is obtained by assembling structural units containing an organic semiconductor active layer, an electrode layer, a dielectric layer, and a supporting substrate.

12. The application of the polarization photodetector according to any one of claims 1-10 in image enhancement for geological remote sensing or machine vision.

13. The application of the polarization photodetector according to any one of claims 1-10 as a wearable device.

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