A circularly polarized light detector and a preparation method and application thereof

Abstract

The application discloses a circularly polarized light detector and a preparation method and application thereof, and belongs to the technical field of organic semiconductor materials. The circularly polarized light detector provided by the application is a top-gate bottom-contact or top-gate top-contact double-heterojunction structure organic field effect transistor; the double-heterojunction includes a chiral active layer and a semiconductor active layer; the material of the chiral active layer is a split chiral material with circular dichroism, without field effect mobility or with field effect mobility; and the material of the semiconductor active layer is a semiconductor material with field effect mobility. The circularly polarized light detector can detect circularly polarized light without relying on the field effect mobility of chiral molecules, and by using the specific response of chiral molecules to circularly polarized light and the charge transmission characteristics in the heterojunction.

Description

Technical Field

[0001] This invention relates to the field of organic semiconductor materials technology, specifically to a circularly polarized light detector, its fabrication method, and its applications. Background Technology

[0002] Chiral photonics based on circularly polarized light has wide-ranging applications, such as circularly and elliptically polarized imaging, optical communication using spin information, quantum-based optical computing, information processing, biology, and medicine. The interaction between the optical rotation of circularly polarized light and the chirality of molecules demonstrates the potential for these applications. The helicality of molecules or structures can now be detected by the absorption or reflection of circularly polarized light. Applying chiral molecules with transmission properties to organic field-effect transistors can also detect circularly polarized light via photocurrent. However, synthesizing and preparing chiral molecules with transmission properties suitable for detecting polarized light is extremely difficult. Therefore, designing a transistor-based circularly polarized light detector that is independent of the field-effect mobility of chiral molecules is urgently needed. Summary of the Invention

[0003] This invention provides a circularly polarized light detector, its fabrication method, and its application. This detector does not rely on the field-effect mobility of chiral molecules. Instead, it utilizes the specific response of chiral molecules to circularly polarized light and the charge transport characteristics in a heterojunction to achieve the detection of circularly polarized light.

[0004] This invention first provides a circularly polarized light detector, which is an organic field-effect transistor with a double-layer heterojunction structure of top-gate bottom contact or top-gate top contact.

[0005] The bilayer heterojunction includes a chiral active layer and a semiconductor active layer;

[0006] The material of the chiral active layer is a split chiral material that has circular dichroism and either does not have field-effect mobility or has field-effect mobility properties.

[0007] The semiconductor active layer is made of a semiconductor material with field-effect mobility properties.

[0008] Specifically, the circularly polarized light detector includes a substrate, and source / drain electrodes, a chiral active layer, a semiconductor active layer, an insulating layer, and a gate electrode sequentially disposed on the substrate.

[0009] In the aforementioned circularly polarized light detector, the material used to prepare the chiral active layer is any one of the following: chiral small molecule material, chiral polymer material, self-assembled chiral supramolecular material, and chiral liquid crystal material;

[0010] Specifically, the chiral small molecule material is based on chiral helicenes and multiple helicene derivatives, chiral tartaric acid derivatives, or chiral cyclohexanediamine derivatives.

[0011] More specifically, the material used to prepare the chiral active layer is any one of the following: azidoperylimide trimer (NTPH-P), 1-aza[6]helicene (1-aza[6]helicene), and spirocyclic fused trinaphthalene-diphenyl dimer (SDT).

[0012] The material used to prepare the semiconductor active layer is any one of the following: fused-ring aromatic hydrocarbons and their derivatives, chalcogen heterocyclic oligomers, thiophene-aromatic copolymer oligomers, chalcogen fused rings and their derivatives, tetrathiofulvalene derivatives, nitrogen-containing conjugated macrocyclic rings, fluorinated compounds, compounds containing acid anhydride groups, compounds containing imide groups, cyano compounds, fullerenes and their derivatives, conjugated polymer materials, donor-acceptor copolymers, amorphous polymer semiconductor materials, ladder polymers, non-ladder polymers, and perylene-based polymers.

[0013] Specifically, the polycyclic aromatic hydrocarbons and their derivatives include, but are not limited to, pentanebenzene, red fluorene, 2,6-diphenylanthracene (DPA), or 2,6-diphenylvinyl-substituted anthracene (DPVAnt);

[0014] The thiophene-aromatic ring copolymer oligomers include, but are not limited to, α-tetrathiophene (α-4T);

[0015] The chalcogenide fused rings and their derivatives include, but are not limited to, 2,7-dioctyl[1]benzothiophene[3,2-b][1]benzothiophene (C8-BTBT);

[0016] The tetrathiofulvalene derivatives include, but are not limited to, tetrathiofulvalene (TTF);

[0017] The nitrogen-conjugated macromolecular rings contained therein include, but are not limited to, copper phthalocyanine (CuPc);

[0018] The fluorinated compounds include, but are not limited to, perfluoropentabenzene or perfluorocopper phthalocyanine;

[0019] The compounds containing anhydride groups include, but are not limited to, naphthalene dihydroxy anhydride;

[0020] The compounds containing imide groups include, but are not limited to, naphthalenetetramethylimide derivatives (NDIs) or perylenetetramethylimide derivatives (PDIs);

[0021] The cyano-containing compounds include, but are not limited to, 7,7,8,8-tetracyano-p-benzoquinone dimethane (TCNQ);

[0022] The fullerenes and their derivatives include, but are not limited to, isomethyl [6,6]-phenyl-C61-butyrate (

[60] PCBM) or isomethyl [6,6]-phenyl-C71-butyrate (

[70] PCBM);

[0023] The conjugated polymeric materials include, but are not limited to, polythiophene or polyfluorene; the polythiophene may specifically be poly-3-alkylthiophene (P3Ats) or poly-3-hexylthiophene (P3HT); the polyfluorene may specifically be 9,9-dioctylfluorene (PFO) or copolymers based on PFO or dithiophene (F8T2).

[0024] More specifically, the material used to prepare the semiconductor active layer can be any of the following: 2,6-diphenylanthracene (DPA), tetracyanotrithiophenone (TTT-CN), pentanebenzene, 2,7-dioctyl[1]benzothiophene[3,2-b][1]benzothiophene (C8-BTBT) and copper phthalocyanine (CuPc).

[0025] In the aforementioned circularly polarized light detector, the substrate is a light-transmitting substrate; the light-transmitting substrate is a rigid substrate and / or a flexible substrate;

[0026] Specifically, the rigid substrate is quartz and / or Corning glass, etc.

[0027] The flexible substrate is at least one of polyethylene terephthalate (PET), polyimide (PI), polydimethylsiloxane (PDMS), polyvinyl alcohol (PVA), polyethylene dinaphthalate (PEN), or textile materials.

[0028] The material used to prepare the source and drain electrodes is any one of the following: metal, carbon material, and conductive polymer;

[0029] The material used to prepare the insulating layer is any one of the following: inorganic insulating materials and polymer insulating materials;

[0030] The material used to prepare the gate is any one of the following: metal, carbon material, and conductive polymer.

[0031] Specifically, the metal is gold, silver, aluminum, or platinum;

[0032] The carbon material is graphene;

[0033] The inorganic insulating material is silicon dioxide (SiO2) or aluminum oxide (Al2O3);

[0034] The polymer insulating material is polymethyl methacrylate (PMMA), polystyrene (PS), sodium polystyrene sulfonate (PSS), perfluoropolymer (CYTOP), polyimide (PI), organosiloxane polymer (BCB), parylene, polytetrafluoroethylene (PTFE), acrylonitrile-butadiene-styrene copolymer (ABS), or polyvinyl alcohol (PVA).

[0035] In the aforementioned circularly polarized light detector, the thickness of the substrate is not limited, and any commercially available substrate can be used.

[0036] The thickness of the source and drain electrodes is 1–40 nm;

[0037] The thickness of the chiral active layer is 5–25 nm;

[0038] The thickness of the semiconductor active layer is 20–50 nm;

[0039] The thickness of the insulating layer is 200–700 nm;

[0040] The thickness of the gate is 1–70 nm.

[0041] The present invention also provides a method for fabricating the above-mentioned circularly polarized optical detector, comprising the following steps:

[0042] (1) The source and drain electrodes are fabricated on the surface of the substrate;

[0043] (2) The chiral active layer is prepared on the source and drain electrodes;

[0044] (3) The semiconductor active layer is prepared on the chiral active layer;

[0045] (3) The insulating layer is prepared on the semiconductor active layer;

[0046] (4) The gate is fabricated on the insulating layer to obtain the circularly polarized light detector.

[0047] The source and drain electrodes can be prepared by, but not limited to, evaporation, printing, atomic vapor deposition, or physical transfer.

[0048] When using vapor-deposited metal electrodes, it is necessary to introduce an adhesive layer of chromium or nickel.

[0049] The chiral active layer and the semiconductor active layer can be prepared directly by phase separation, or the chiral active layer and the semiconductor active layer can be prepared separately.

[0050] Specifically, the chiral active layer can be prepared by, but is not limited to, spin coating, drop casting, vapor deposition, blade coating, printing, Langmuir-Blodgett film, or physical transfer; the semiconductor active layer can be prepared by spin coating, drop casting, vapor deposition, or physical transfer of orthogonal solvents.

[0051] The insulating layer can be prepared using conventional methods in the art, such as spin coating, vapor deposition, physical transfer, or printing.

[0052] The gate can be fabricated using methods conventional in the art, such as mask evaporation, physical transfer, printing, or silver mirror reaction.

[0053] The application of the aforementioned circularly polarized light detector in polarized light detection also falls within the scope of protection of this invention.

[0054] In the above applications, the polarized light is either left-handed or right-handed circularly polarized light.

[0055] The circularly polarized light detector of the present invention can detect light with different wavelengths and different polarization behaviors by adjusting the active layer, including but not limited to left-handed and right-handed circularly polarized light.

[0056] The circularly polarized light detector of the present invention is a type of organic field-effect transistor that has a specific response to light, mainly a specific response to circularly polarized light of a specific wavelength.

[0057] The specific response described in this invention refers to the significant changes in the electrical properties of a field-effect transistor under different optical conditions, including leakage current and threshold voltage, while ensuring that the electrical testing conditions are constant.

[0058] This invention, by selecting spectrally matched chiral and semiconductor materials, can ensure that the circularly polarized light detector has good transmission performance in both light and dark states, while avoiding the influence of semiconductor material absorption on the response of chiral molecules to circularly polarized light.

[0059] This invention can be fabricated using a flexible substrate to obtain device properties similar to those on a rigid substrate, as well as a specific response to circularly polarized light.

[0060] The circularly polarized light detector of this invention requires low testing conditions, has high stability and repeatability, and can be tested rapidly and multiple times in an atmospheric environment.

[0061] The circularly polarized light detector of this invention can quickly and directly detect left-handed and right-handed circularly polarized light through the electrical properties of transistors, laying a solid foundation for the subsequent large-scale fabrication of air-stable flexible light detectors.

[0062] The present invention has the following advantages:

[0063] 1) The preparation method is simple and easy to implement, requires no complex and expensive equipment, has good reproducibility, and has very good universality;

[0064] 2) The requirements for the transport properties of the desired chiral molecules are reduced, and transistor-like properties are no longer required;

[0065] 3) There are multiple options for the required organic semiconductors, which can be selected based on the fabrication process and energy level;

[0066] 4) The circularly polarized light detector can directly respond to light through the electrical properties of the transistor, including leakage current, gate voltage, etc.

[0067] 5) The circularly polarized light detector has stable electrical properties, fast response speed, and high sensitivity;

[0068] 6) Devices can be fabricated on flexible substrates using similar methods, and the resulting flexible devices still have good circularly polarized light detection performance;

[0069] 7) The circularly polarized light detector device is mainly prepared by evaporation deposition of electrodes. Therefore, large-area integrated devices can be prepared by designing the electrodes. Attached Figure Description

[0070] Figure 1 This is a schematic diagram of the device structure of the circularly polarized optical detector of the present invention;

[0071] The markings in the figure are as follows: 1 Substrate; 2 Source electrode; 3 Drain electrode; 4 Chiral active layer; 5 Semiconductor active layer; 6 Insulating layer; 7 Gate.

[0072] Figure 2 The UV-Vis absorption spectra of the chiral molecule (NTPH-P) and semiconductor material (DPA) thin film used in Example 1 of this invention are shown.

[0073] Figure 3 The circular dichroism spectrum of the chiral molecule (NTPH-P) enantiomer thin film used in Example 1 of this invention is shown.

[0074] Figure 4 The transfer characteristic curve and output characteristic curve of the circularly polarized optical detector prepared in Example 1 of the present invention are shown; wherein, Figure 4 In the figure, 'a' represents the transfer characteristic curve of the circularly polarized light detector. Figure 4 In the figure, b represents the output characteristic curve of circularly polarized light.

[0075] Figure 5 The specific response curve of the circularly polarized light detector to circularly polarized light was prepared for Example 1 of the present invention; Figure 5 In the diagram, 'a' represents the response of a circularly polarized light detector based on the split NTP-P(P, P, P) to changes in circularly polarized light. Figure 5 In the figure, b is the response of the circularly polarized light detector based on the split NTP-P(M, M, M) to changes in circularly polarized light. Detailed Implementation

[0076] The present invention will be further described in detail below with reference to specific embodiments. The embodiments given are only for illustrating the present invention and are not intended to limit the scope of the present invention.

[0077] Unless otherwise specified, the experimental methods described in the following examples are conventional methods.

[0078] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0079] The structure of the circularly polarized optical detector of the present invention is as follows: Figure 1 As shown, this is an organic field-effect transistor with top-gate bottom contact, including a substrate 1, a source electrode 2, a drain electrode 3, a chiral active layer 4, a semiconductor active layer 5, an insulating layer 6, and a gate 7 disposed on the substrate 1.

[0080] The substrate is a light-transmitting substrate; the light-transmitting substrate needs to have no obvious absorption in the detected wavelength band; specifically, the light-transmitting substrate is a rigid substrate (such as quartz or Corning glass) and / or a flexible substrate (such as at least one of polyethylene terephthalate (PET), polyimide (PI), polydimethylsiloxane (PDMS), polyvinyl alcohol (PVA), polyethylene dinaphthalate (PEN) and textile materials).

[0081] The circularly polarized light detector prepared by this invention emits light from the substrate (back side) during the testing process. The use of a specific material as the substrate of the device is to reduce light absorption and ensure that the light can directly act on the chiral active layer.

[0082] The materials used to prepare the source electrode and the drain electrode are any of the following: metals (such as gold, silver or platinum), carbon materials (such as graphene), and conductive polymers.

[0083] The material used to prepare the chiral active layer is any one of the following: chiral small molecule materials (such as chiral helicene and multiple helicene derivatives, chiral tartaric acid derivatives or chiral cyclohexanediamine derivatives), chiral polymer materials, self-assembled chiral supramolecular materials, and chiral liquid crystal materials.

[0084] The semiconductor active layer can be selected according to the requirements of the energy level spectrum; specifically, the material used to prepare the semiconductor active layer is any one of the following: small molecule materials (such as fused ring aromatics and their derivatives; specifically, it can be pentane, rubrene, 2,6-diphenylanthracene (DPA), 2,6-diphenylvinyl-substituted anthracene (DPVAnt)), sulfide heterocyclic oligomers, thiophene-aromatic copolymer oligomers (such as α-tetrathiophene (α-4T)), sulfide fused rings and their derivatives (such as 2,7-dioctyl[1]benzothiophene[3,2-b][1]benzothiophene (C8-BTBT)), tetrathiofulvalene derivatives (such as tetrathiofulvalene (TTF)), nitrogen-containing conjugated macrocyclic rings (such as copper phthalocyanine (CuPc)), fluorine-containing compounds (such as perfluoropentane, perfluorocopper phthalocyanine), compounds containing anhydride groups (such as naphthalene dihydroxy anhydride), acyl-containing compounds Imine group compounds (such as naphthalenetetramethylimide derivatives (NDIs), perylenetetramethylimide derivatives (PDIs)), cyano-containing compounds (such as 7,7,8,8-tetracyano-p-benzoquinone dimethyl ester (TCNQ)), fullerenes and their derivatives (such as isomethyl [6,6]-phenyl-C61-butyrate (

[60] PCBM), isomethyl [6,6]-phenyl-C71-butyrate (

[70] PCBM)), conjugated polymers (such as polythiophenes; specifically poly-3-alkylthiophene (P3Ats), poly-3-hexylthiophene (P3HT); polyfluorenes; specifically 9,9-dioctylfluorene (PFO), copolymers based on PFO and dithiophene (F8T2)), donor-acceptor copolymers, amorphous polymer semiconductor materials, ladder polymers, non-ladder polymers and perylene-imide-based polymers).

[0085] The material used to prepare the insulating layer is any one of the following: inorganic insulating materials (such as silicon dioxide (SiO2), aluminum oxide (Al2O3)) and polymer insulating materials (such as polymethyl methacrylate (PMMA), polystyrene (PS), sodium polystyrene sulfonate (PSS), perfluoropolymer (CYTOP), polyimide (PI), organosiloxane polymer (BCB), parylene, polytetrafluoroethylene (PTFE), acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl alcohol (PVA)).

[0086] The material used to prepare the gate can be any of the following: metals (such as gold, silver, platinum, aluminum), carbon materials, and conductive polymers; good conductivity is required.

[0087] The method for fabricating the circularly polarized optical detector of the present invention includes the following steps:

[0088] (1) Prepare source and drain electrodes on a clean, transparent substrate surface;

[0089] Source and drain electrodes can be fabricated by vapor deposition, printing, atomic vapor deposition, or physical transfer.

[0090] When using vapor-deposited metal electrodes, it is necessary to introduce an adhesive layer of chromium or nickel.

[0091] (2) A chiral active layer and a semiconductor active layer are prepared on a transparent substrate on which a source electrode and a drain electrode have been prepared;

[0092] The chiral active layer and the semiconductor active layer can be prepared directly by phase separation, or the chiral active layer and the semiconductor active layer can be prepared separately.

[0093] Specifically, the chiral active layer can be prepared by spin coating, drop casting, evaporation, blade coating, printing, Langmuir-Blodgett film, or physical transfer; the semiconductor active layer can be prepared by spin coating, drop casting, evaporation, or physical transfer of orthogonal solvents.

[0094] (3) An insulating layer is prepared on the semiconductor active layer;

[0095] The insulating layer can be prepared using conventional methods in the art, such as spin coating, vapor deposition, physical transfer, or printing.

[0096] (4) A gate is fabricated on the insulating layer to obtain the circularly polarized light detector.

[0097] The gate can be fabricated using methods conventional in the art, such as mask evaporation, physical transfer, printing, or silver mirror reaction.

[0098] Example 1: Circularly Polarized Optical Detector Based on DPA Crystal and Chiral NTPH-P Molecules

[0099] 1. The DPA (2,6-diphenylanthracene) used in this example was synthesized according to the method in the literature (Liu J. et al. Thin filmfield-effect transistors of 2,6-diphenylanthracene (DPA). Chem. Comm. 2015, 51(59), 11777-11779.);

[0100] NTPH-P (azaperylene hexaimide trimer) was synthesized and enantiomers were obtained according to the method in the literature (Ma Z. et al. A C2-symmetric triple[5]helicene based on N-annulated triperylene hexaimide for chiroptical electronics. Sci. China Chem. 2019, 63(2), 208-214.).

[0101] 2. In this example, the DPA crystals were prepared by physical vapor transport, specifically by heating and sublimating DPA at 175°C and 25 Pa for 2 hours to obtain DPA crystals.

[0102] 3. Fabrication of Circularly Polarized Optical Detectors

[0103] according to Figure 1 The device structure shown is used to fabricate a circularly polarized light detector. The substrate is made of quartz, the chiral active layer is a pair of enantiomers of NTPH-P, the semiconductor active layer is made of DPA crystal, and the insulating layer is made of polymer insulating layer perfluoropolymer (CYTOP) (purchased from Asahi Glass Co., Ltd., Japan).

[0104] Step 1: Vapor deposition is performed on a cleaned quartz substrate using a photomask at a depth of 6×10. -6 Under the condition of mbar First, a 4nm layer of metallic chromium is deposited as an adhesion layer, and then... A 25nm thick gold layer is deposited at a high speed as the source and drain electrodes; the gold thickness is required to be above 15nm to ensure conductivity; the substrate after deposition is cleaned a second time with acetone and isopropanol.

[0105] Step 2: Spin-coating was performed using a 4 mg / mL solution of the separated NTPH-P chiral molecules (a 2:1 volume ratio of chloroform to n-hexane) at a spin speed of 2000 r / s, with a chiral active layer film thickness of 10 nm.

[0106] Step 3: Transfer the DPA crystal onto the chiral active layer using a physical transfer method; the thickness of the DPA crystal is 34 nm.

[0107] Step 4: Spin-coat a 600nm thick CYTOP layer as an insulating layer on the surface of the semiconductor active layer; the specific rotation speed is 500r / s for 3s, then 2000r / s for 20s. Immediately after spin-coating, anneal at 90℃ for 20min under nitrogen protection in a glove box.

[0108] Step 5: Using a mask on the insulating layer, expose the area directly above the channel, then apply a 6×10... -6 Under the condition of mbar A 30nm layer of metallic aluminum is deposited at a high speed to serve as the gate electrode, thus obtaining a circularly polarized light detector.

[0109] Figure 2 The UV-Vis absorption spectra of chiral NTPH-P thin films and semiconductor DPA thin films are presented. The testing method involved spin-coating NTPH-P (P,P,P) thin films (concentration, solvent, rotation speed, and thickness as described above) and vapor-depositing DPA thin films (at 6 × 10⁻⁶) onto clean quartz substrates. -6 Under the condition of mbar The UV-Vis absorption spectrum of a 30nm DPA thin film was measured at a high speed, and the obtained data were normalized. Figure 2 The spectra show that the DPA film has strong absorption at 435 nm, but the absorption is relatively weak after 470 nm. In contrast, the chiral NTPH-P film has strong absorption after 500 nm, with a peak around 534 nm. Figure 3 The circular dichroism (CD) spectrum of the chiral NTPH-P thin film is shown. The testing method involved spin-coating split NTPH-P solutions (concentration 8 mg / mL, solvent, spin speed, and thickness as described above) onto a clean quartz substrate. NTPH-P(P,P,P) and NTPH-P(M,M,M) are a pair of enantiomers of NTPH-P after splitting. The CD spectrum shows distinct peaks at 414 nm, 489 nm, and 551 nm. The detection wavelength in this example was determined based on the spectra of the chiral molecule and semiconductor material, as well as the CD spectrum of the chiral molecular thin film. The detection wavelength required significant absorption in both the CD spectrum and the UV-Vis absorption spectrum of the chiral molecular thin film at that wavelength, while the semiconductor material showed no significant absorption at that wavelength.

[0110] The fabricated circularly polarized light detector was tested using a Keysight B1500 instrument, and the output characteristic curve and transfer characteristic curve of the circularly polarized light detector were obtained. Figure 4 ) and curves showing the variation of source and drain current over time under different illumination conditions ( Figure 5 ).

[0111] Figure 4 During the testing process, it is necessary to ensure that the source-drain voltage is -60V and the gate voltage test range is -20V to -60V under conditions of no light. Figure 4 It is evident that circularly polarized light detectors exhibit excellent organic field-effect transistor performance and superior field-effect mobility.

[0112] Figure 5 During the testing process, the circularly polarized light detector needs to be placed vertically in the optical path and the light needs to be shone vertically onto the circularly polarized light detector from one side of the substrate. The electrodes are then connected to the probe stage. Figure 5 This is the specific response curve of a circularly polarized light detector to circularly polarized light. (From...) Figure 5 As can be seen in the figure, the device is initially exposed to right-handed circularly polarized light, and the position indicated by the arrow is transformed to left-handed circularly polarized light, with the transformation occurring every 30 seconds. It can be seen from the figure that the enantiomers have opposite responses to circularly polarized light.

[0113] Example 2: Circularly Polarized Optical Detector Based on DPA Thin Film and Chiral NTPH-P Molecules

[0114] according to Figure 1 The device structure shown is used to fabricate a circularly polarized light detector. The substrate is made of quartz, the chiral active layer is a pair of enantiomers of NTPH-P, the semiconductor active layer is a vapor-deposited DPA film, and the insulating layer is a polymer insulating layer CYTOP.

[0115] The preparation process is the same as in Example 1, except that the method for preparing the semiconductor active layer is changed from physical transfer of DPA crystal to vacuum deposition of DPA film. The deposition of the DPA film requires a 6×10⁻⁶ kJ / m²·cm²· ... -6 Under the condition of mbar The deposition rate is 30nm.

[0116] The testing methods and procedures are the same as in Example 1, and the properties of the obtained circularly polarized light detector (including the transfer characteristic curve and the output characteristic curve) and its specific response to circularly polarized light are similar to those in Example 1.

[0117] Example 3: Circularly polarized light detector based on DPA crystals or DPA thin films and chiral NTPH-P molecules

[0118] according to Figure 1 The device structure shown is used to fabricate a circularly polarized light detector. The substrate is made of flexible PET, the chiral active layer is a pair of enantiomers of NTPH-P, the semiconductor active layer is a physically transferred DPA crystal or a vapor-deposited DPA film, and the insulating layer is a polymer insulating layer CYTOP.

[0119] The preparation process is the same as in Examples 1 and 2, except that before depositing the source and drain electrodes, a clean PET film needs to be bonded to a rigid substrate (such as a suitably sized glass slide) using high-temperature resistant tape. Then, the source and drain electrodes are deposited to prepare the chiral active layer and the semiconductor active layer. It is worth noting that the flexible substrate will undergo some deformation at excessively high temperatures. Therefore, during the preparation of the CYTOP insulating layer, the spin-coated film needs to be annealed for 20 minutes on a hot plate at 75°C under nitrogen protection in a glove box.

[0120] Before testing, the flexible device was physically peeled off from the rigid substrate. The testing method and process were the same as in Example 1, and the properties of the resulting circularly polarized light detector and its specific response to circularly polarized light were similar to those in Example 1.

[0121] Example 4: Circularly polarized light detector prepared based on TTT-CN and chiral helixene derivative molecules

[0122] The TTT-CN (tetracyanotrithiophenequinone) used in this example was synthesized according to the method described in the literature (Xiong, Y. et al. A Furan–Thiophene-Based Quinoidal Compound: A New Class of Solution-Processable High-Performance n-Type Organic Semiconductor. Adv. Mater. 2016, 28(28), 5949-5953.).

[0123] 1-aza[6]helicene was synthesized and enantiomers were obtained according to the method described in the literature (Takenaka, N. et al. Helical Chiral Pyridine N-Oxides: A New Family of Asymmetric Catalysts. Angew. Chem. Int. Ed. 2008, 47(50), 9708-9710.).

[0124] according to Figure 1 The device structure shown is used to fabricate a circularly polarized light detector. The substrate is made of quartz, the chiral active layer is a pair of enantiomers of 1-aza[6]helicene, the semiconductor active layer is a vapor-deposited TTT-CN thin film, and the insulating layer is a polymer insulating layer CYTOP.

[0125] The preparation process is the same as in Example 1, except that the chiral active layer (1-aza[6]spiroene) and the TTT-CN semiconductor active layer are prepared by vapor deposition, which requires a vapor deposition process at 6×10⁻⁶ ℃.-6 Under the condition of mbar The vapor deposition was carried out at a speed of 25 nm for 1-aza[6]helicene and 30 nm for TTT-CN.

[0126] The testing methods and procedures are the same as in the embodiments, and the properties of the obtained circularly polarized light detector and its specific response to circularly polarized light are similar to those in Embodiment 1.

[0127] Example 5: Circularly polarized light detector fabricated based on pentacene thin film and chiral NTPH-P molecules

[0128] according to Figure 1 The device structure shown is used to fabricate a circularly polarized light detector. The substrate is made of quartz, the chiral active layer is a pair of enantiomers of NTPH-P, the semiconductor material is a pentacene thin film deposited by vapor deposition, and the insulating layer is a polymer insulating layer CYTOP.

[0129] The preparation process is the same as in Example 1, except that the semiconductor active layer is a vapor-deposited pentacene thin film, and the film needs to be deposited at 6×10⁻⁶ mm. -6 Under the condition of mbar The deposition rate is 30nm.

[0130] The testing method and process are the same as in Example 1, and the properties of the obtained circularly polarized light detector (and its specific response to circularly polarized light) are similar to those in Example 1.

[0131] Example 6: Circularly Polarized Optical Detector Based on Copper Phthalocyanine Thin Film and Chiral NTPH-P Molecules

[0132] according to Figure 1 The device structure shown is used to fabricate a circularly polarized light detector. The substrate is made of quartz, the chiral active layer is a pair of enantiomers of NTPH-P, the semiconductor material is a copper phthalocyanine thin film deposited by vapor deposition, and the insulating layer is a polymer insulating layer CYTOP.

[0133] The preparation process is the same as in Example 1, except that the semiconductor active layer is a vapor-deposited copper phthalocyanine thin film, and the film needs to be deposited at a density of 6 × 10⁻⁶. -6 Under the condition of mbar The deposition rate is 30nm.

[0134] The testing method and process are the same as in Example 1, and the properties of the obtained circularly polarized light detector (and its specific response to circularly polarized light) are similar to those in Example 1.

[0135] Example 7: Circularly polarized light detector fabricated based on C8-BTBT thin film and chiral NTPH-P molecules

[0136] according to Figure 1The device structure shown is used to fabricate a circularly polarized light detector. The substrate is made of quartz, the chiral active layer is a pair of enantiomers of NTPH-P, the semiconductor material is a C8-BTBT (2,7-dioctyl[1]benzothiophene[3,2-b][1]benzothiophene) thin film, and the insulating layer is a polymer insulating layer CYTOP.

[0137] The preparation process is the same as in Example 1, except that the semiconductor active layer is a vapor-deposited C8-BTBT thin film, and the film needs to be deposited at 6×10⁻⁶ mm². -6 Under the condition of mbar The deposition rate is 30nm.

[0138] The testing method and process are the same as in Example 1, and the properties of the obtained circularly polarized light detector (and its specific response to circularly polarized light) are similar to those in Example 1.

[0139] Example 8: Circularly polarized light detector fabricated based on DPA thin film and chiral SDT molecules

[0140] according to Figure 1 The device structure shown is used to fabricate a circularly polarized light detector. The substrate is quartz, the chiral active layer is an enantiomer of SDT (spirocyclic fused trinaphthalene-diphenyl dimer) according to the literature (Feng J, et al. A near-infrared circularly polarized luminescent dye by dissymmetric spiro-fusion[J]. Chemical Communications, 2019, 56(6).), the semiconductor material is a DPA thin film deposited by vapor deposition, and the insulating layer is a polymer insulating layer CYTOP.

[0141] The preparation process is the same as in Example 1, except that the semiconductor active layer is a vapor-deposited DPA film, and the film needs to be deposited at 6×10⁻⁶ mm. -6 Under the condition of mbar The deposition rate is 30nm.

[0142] The testing method and process are the same as in Example 1, and the properties of the obtained circularly polarized light detector and its specific response to circularly polarized light are similar to those in Example 1.

[0143] As can be seen from the above embodiments, the method of the present invention is a method for preparing a circularly polarized light detector with good universality, simple operation, high stability and repeatability. The detector can achieve rapid in-situ detection and effectively convert circularly polarized light signals into electrical signals.

Claims

1. A circularly polarized light detector, which is an organic field-effect transistor with a double-layer heterojunction structure of top-gate bottom contact or top-gate top contact; The bilayer heterojunction includes a chiral active layer and a semiconductor active layer; The material of the chiral active layer is a chiral material with circular dichroism that does not have field-effect mobility. The material used to prepare the chiral active layer is any one of the following: azaperylimide trimer, 1-aza[6]spiroene, and spirocyclic fused trinaphthalene-diphenyl dimer; The semiconductor active layer is made of a semiconductor material with field-effect mobility properties; The material used to prepare the semiconductor active layer is any one of the following: 2,6-diphenylanthracene, tetracyanotrithiophenone, pentanebenzene, 2,7-dioctyl[1]benzothiophene[3,2-b][1]benzothiophene and copper phthalocyanine.

2. The circularly polarized light detector according to claim 1, characterized in that: The circularly polarized light detector includes a substrate, and source / drain electrodes, a chiral active layer, a semiconductor active layer, an insulating layer, and a gate electrode sequentially disposed on the substrate.

3. The circularly polarized light detector according to claim 2, characterized in that: The substrate is a light-transmitting substrate; the light-transmitting substrate is a rigid substrate and / or a flexible substrate; The material used to prepare the source and drain electrodes is any one of the following: metal, carbon material, and conductive polymer; The material used to prepare the insulating layer is any one of the following: inorganic insulating materials and polymer insulating materials; The material used to prepare the gate is any one of the following: metal, carbon material, and conductive polymer.

4. The circularly polarized light detector according to claim 2 or 3, characterized in that: The thickness of the source and drain electrodes is 1~40 nm; The thickness of the chiral active layer is 5~25 nm; The thickness of the semiconductor active layer is 20~50 nm; The thickness of the insulating layer is 200~700 nm; The thickness of the gate is 1~70 nm.

5. A method for fabricating a circularly polarized light detector according to any one of claims 2-4, comprising the following steps: (1) The source and drain electrodes are fabricated on the surface of the substrate; (2) The chiral active layer is prepared on the source and drain electrodes; (3) The semiconductor active layer is prepared on the chiral active layer; (3) The insulating layer is prepared on the semiconductor active layer; (4) The gate is fabricated on the insulating layer to obtain the circularly polarized light detector.

6. The application of the circularly polarized light detector according to any one of claims 1-4 in polarized light detection.

7. The application according to claim 6, characterized in that: The polarized light is either left-handed or right-handed circularly polarized.

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