Method for realizing circularly polarized light resolution and storage by using chiral cluster semiconductor interface and application thereof

Abstract

The invention discloses a method for distinguishing and storing circularly polarized light by using a chiral cluster semiconductor interface and application of the method. A chiral cluster is used as a circularly polarized light detection, photoelectric signal conversion and storage unit, a semiconductor is used as an electric signal transmission and output unit, and a chiral cluster semiconductor interface is constructed. The interface realizes the transmission of circularly polarized light information, realizes sensing and storage integration of distinguishing and storage of circularly polarized light, and effectively reduces the manufacturing and processing cost of the device and the structural complexity of the device. The circularly polarized light photoelectric transistor device provided by the invention has a wide application prospect in the fields of encryption transmission, coding and decoding, anti-counterfeiting and the like.

Description

Technical Field

[0001] The invention belongs to the field of semiconductor materials and optoelectronic devices, and relates to a method for realizing circularly polarized light resolution and storage by utilizing a chiral cluster semiconductor interface and an application thereof. Background Art

[0002] The essence of light is electromagnetic waves, and light has all the properties of electromagnetic waves. Light has the dual nature of wave and particle, and not only carries the information of electromagnetic waves (light intensity, wavelength and phase), but can also be regarded as photons carrying energy. Light can interact with matter, both physically and chemically, which is essentially the transfer and exchange of energy. Photothermal conversion is the transfer of photon energy to phonons and conversion into thermal energy; photoelectric conversion is the transfer of photon energy to excitons and conversion into the kinetic energy of electrons (holes). Electricity is currently the most easily controlled, prepared, stored and transported form of energy by humans, so converting light into electricity is an important way for humans to use light, such as solar cells, photodiodes, etc., and the core of photoelectric conversion lies in photoelectric materials. Photoelectric materials are materials that convert light into electricity, and the above-mentioned devices that convert light energy into electrical energy are photoelectric devices.

[0003] Today's common optoelectronic devices can sense light intensity (radiometers, densitometers, etc.) and wavelength (near-infrared detectors, visible light detectors, X-ray detectors, etc.), but often ignore the phase information carried by light. The electric field of light consists of two mutually perpendicular linear components. The phase change of the two perpendicular component waves causes the polarization of light to change, including linear polarization, elliptically polarized light, circularly polarized light, etc. Polarized light is widely used in filter lenses, information encryption and other fields because of its unique phase information. Therefore, the detection of polarized light has a high application value. Most optoelectronic materials have specific absorption wavelengths and absorption coefficients, but they cannot be combined with the phase information of light, so they cannot be directly used for the detection of polarized light. Based on the principle of linear polarization, parallel light can obtain polarized light by passing through a 1 / 2 polarizer. Therefore, if the optoelectronic material has a parallel and equidistant grating structure similar to 1 / 2 polarized light in structure, the ability to detect polarized light can be obtained. Therefore, most linear polarization light detectors are based on semiconductor crystal materials with photoelectric response. The semiconductor crystal material is highly designable, has many types and is easy to prepare, so the development of linear polarization light detectors is relatively smooth ((a) Yang, Y.; da Costa, R.; Fuchter, M.; et al. Nature Photon 7, 634–638 (2013). (b) Seo, S.; Jo, SH.; Kim, S.; et al. Nat Commun 9, 5106 (2018)). However, circularly polarized light requires parallel light to pass through a 1 / 2 polarizer to obtain linear polarization light, and then pass through a 1 / 4 polarizer to obtain linear polarization light. Therefore, semiconductor crystal materials are difficult to meet the requirements of circularly polarized light detectors.

[0004] Chiral materials have been shown to be able to distinguish circularly polarized light, although there are many theories and reasonable conjectures on the mechanism explanation (plasmon hybridization theory and mode coupling theory, etc.). Although chiral materials are quite common in nature, such as DNA and glucose, chiral materials with optoelectronic properties are relatively limited. The more representative chiral optoelectronic materials include helicene, chiral two-dimensional perovskite, chiral thermally activated delayed fluorescence (TADF) organic small molecules, etc. The common point of these materials is that they have chiral structural units and π systems (benzene rings, thiophene rings, etc.). The former provides a chiral environment, and the latter provides a charge transfer channel. Although the above-mentioned chiral optoelectronic materials have excellent circularly polarized light detection and resolution capabilities ((a) Yang, Y.; daCosta, R.; Fuchter, M.; et al. Nature Photon 7, 634–638 (2013). (b) Seo, S.; Jo, SH.; Kim, S.; et al. Nat Commun 9, 5106 (2018)), the development of circularly polarized light detection devices is limited by the many steps of material synthesis, high cost, and complex design strategies. Therefore, developing new design strategies or realizing more application space for circular polarization detection will promote the development of circularly polarized light optoelectronic devices. Summary of the invention

[0005] The purpose of the present invention is to provide a method and application thereof for realizing circularly polarized light resolution and storage by using a chiral cluster semiconductor interface. By constructing an interface between a chiral cluster and a semiconductor, the chiral cluster is used as a receiving unit and a storage unit for circularly polarized light information, the semiconductor is used as a transmission unit for electrical signals, and the chiral cluster semiconductor interface serves as a channel for photoelectric information transmission, which can realize circularly polarized light resolution and storage, that is, realize sensing and storage integration, and store information in situ while processing and resolving circularly polarized light information. This strategy has simple process, good universality, and low cost, and provides a new design idea for circularly polarized light photoelectric devices.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A method for realizing circularly polarized light resolution and storage comprises the following steps: constructing a chiral cluster semiconductor interface by forming a semiconductor film and a chiral cluster film on a substrate surface;

[0008] The structure of the chiral cluster semiconductor interface is one of the following two structures:

[0009] Structure 1: The chiral cluster film is physically located above the semiconductor film;

[0010] Structure 2: The chiral cluster film is physically located below the semiconductor film.

[0011] The chiral cluster semiconductor interface of structure 1 has the following characteristics:

[0012] Roughness: The roughness of the chiral cluster semiconductor interface depends on the roughness of the upper surface of the semiconductor film below. The root mean square roughness of the semiconductor film should be <3nm.

[0013] Low defect state density: defect state density should be <10 -16 cm -3 .

[0014] Furthermore, the chiral cluster semiconductor interface of the structure 1 is prepared according to the following steps:

[0015] S1, forming the semiconductor thin film on the upper surface of the substrate;

[0016] S2. Forming the chiral cluster thin film on the surface of the semiconductor thin film to obtain the chiral cluster semiconductor interface.

[0017] In step S1, the substrate is any structure with physical support in the construction of semiconductor devices, for example, the substrate is a glass substrate, a metal electrode, a charge transfer medium, a dielectric layer, a charge blocking layer, a nanowire or a nanosphere.

[0018] In step S1, the material of the semiconductor film is one or more of an organic semiconductor material, an inorganic semiconductor material and a two-dimensional material whose energy level band gap is within the definition range of a semiconductor material; preferably, an organic semiconductor material.

[0019] The organic semiconductor material is an organic polymer semiconductor material or an organic small molecule semiconductor material.

[0020] The organic polymer semiconductor material is one or more of poly(3-hexylthiophene) (P3HT), 9,9-dioctylfluorene (PFO), polypyrrolopyrrole diketothiophene vinylthiophene (PDVT) and polyperylene imide dithiophene (N2200). Organic polymer semiconductor materials often require orthogonal solvation considerations, or directly modify and modify the organic polymer semiconductor material, including adding a thermal crosslinker or a photocrosslinker to crosslink and solidify the polymer chains and resist solvent erosion.

[0021] The organic small molecule semiconductor material is one or more of pentacene, fullerene, perylenetetracarboxylic acid diimide, and naphthalenetetracarboxylic acid diimide; due to the small molecular weight, the stacking mode of organic small molecule semiconductor materials is easily destroyed by the upper solution and they are also easily soluble in common solvents, so only a few material systems meet the requirements. For organic small molecule semiconductor materials, it is required to withstand the erosion of at least one or several commonly used solvents, that is, the solvent covers its surface and cannot penetrate into the body and the interior, and cannot dissolve or destroy the surface microscopic physical and chemical structure.

[0022] The inorganic semiconductor material is one or both of boron-doped single crystal silicon and phosphorus-doped single crystal silicon.

[0023] The two-dimensional material is one or more of graphene, graphyne, molybdenum disulfide and black phosphorus.

[0024] Since inorganic semiconductor materials and two-dimensional materials have good solvent resistance and high temperature resistance, no additional treatment is required.

[0025] According to an embodiment of the present invention, in step S1, the semiconductor thin film is prepared according to the following steps: adding the organic polymer semiconductor material into a solvent, then adding a cross-linking agent, blending, and then annealing the mixture on the surface of the substrate by a solution method to obtain the semiconductor thin film;

[0026] The solvent is chlorobenzene;

[0027] The thermal crosslinking agent is 6-Silanetetrayl-1,2,3,4,5-hexapentaenylidene (C6Si);

[0028] In the blended system, the concentration of the organic polymer semiconductor material is 4-10 mg / mL, preferably 6 mg / mL;

[0029] The mass ratio of the organic polymer semiconductor material to the cross-linking agent is (10-100):1, preferably 10:1.

[0030] The crosslinking agent is a thermal crosslinking agent, and the blended system is annealed after film formation by a solution method process (spin coating, rod coating, blade coating, etc.); according to an embodiment of the present invention, the spin coating conditions are: a rotation speed of 1500-2500rpm / s, preferably 1800rpm / s; the annealing temperature is 130-150°C, preferably 135°C, and the time is 10-30min, preferably 20min. The annealing temperature should be equal to or higher than the initiation and reaction temperature of the thermal crosslinking agent.

[0031] The crosslinking agent is a photocrosslinking agent, and the blended system adopts a solution method processing technology (spin coating, rod coating, blade coating, etc.) to form a film, anneal, and expose; the spin coating conditions are: a rotation speed of 1500-2500rpm / s; the annealing conditions are: a temperature of 90-200°C and a time of 5-15min; the exposure conditions are: a wavelength of 365nm or 254nm and a time of 10-60min.

[0032] The cross-linked organic polymer semiconductor material can withstand conventional solvents, including alcohols (methanol, ethanol, 2-methoxyethanol, etc.), ketones (acetone, pentanone), chlorine-containing reagents (dichloromethane, chloroform, tetrachloroethane, chlorobenzene, o-dichlorobenzene, etc.) and tetrahydrofuran, anisole, ethyl butyrate, etc.

[0033] In step S1, when the material of the semiconductor film is an organic semiconductor material, the thickness of the corresponding semiconductor film is 10-2000 nm, preferably 20-50 nm.

[0034] When the material of the semiconductor film is an inorganic semiconductor material, the thickness of the corresponding semiconductor film is 5-300 nm, preferably 40-100 nm.

[0035] When the material of the semiconductor film is a two-dimensional material, the corresponding thickness of the semiconductor film is 1-30 nm, preferably 5-15 nm.

[0036] In step S2, the chiral cluster film is made of a chiral cluster material. The chiral cluster material needs to have the following characteristics:

[0037] Chiral signal: Chiral clusters are detected as different signals for left-handed and right-handed light on a circular dichroism spectrometer, a vibrational circular dichroism spectrometer, or a circularly polarized fluorescence spectrometer.

[0038] Chirality source: Chiral cluster materials need to introduce chiral sources or chiral environments during preparation and synthesis, including chiral ligands, chiral inducers or chiral solvents. The final chirality of the chiral cluster structure will come from the chiral ligands, chiral cores and chiral core-shell connecting units.

[0039] Stable chiral structure: The chirality of the chiral cluster cannot spontaneously racemize during the processing and should always maintain its own chiral structure stability.

[0040] Solubility: The chiral clusters should be able to dissolve in one or more solvents and keep their physical and chemical structures unchanged in the solution. The solubility of the chiral clusters in the solvent is not easy to be lower than 3 mg / mL.

[0041] In step S2, the chiral cluster film is prepared according to the following steps:

[0042] S21, mixing N,N-dimethylacetamide with acetonitrile to obtain a mixed solution; dissolving the chiral enantiomer of 2-amino-3-methyl-1-butanol and silver nitrate in the mixed solution respectively to obtain a ligand solution and a silver nitrate solution; under stirring, adding the ligand solution dropwise to the silver nitrate solution to obtain a clear yellow solution, and placing it in a dark place without a lid to obtain a block-shaped chiral cluster single crystal; washing and drying;

[0043] S22, dissolving the chiral cluster single crystal into a solvent, and covering the obtained chiral cluster solution on the surface of the semiconductor film by a spin coating process to obtain the chiral cluster film.

[0044] In step S21, the mass ratio of the N,N-dimethylacetamide to the acetonitrile is (3.5-4):1, preferably 4:1 or 3.5:1.

[0045] In step S21, the chiral enantiomer of 2-amino-3-methyl-1-butanol is (S)-(+)-2-amino-3-methyl-1-butanol or (R)-(-)-2-amino-3-methyl-1-butanol.

[0046] In step S21, the molar ratio of the chiral enantiomer of 2-amino-3-methyl-1-butanol or prime silver nitrate to the mixed solution is (1-1.5):1, preferably 1.2:1.

[0047] In step S21, the stirring speed is controlled between 200-500 rpm / s, preferably 300 rpm / s.

[0048] In step S21, the placement time is 1-3 days.

[0049] In step S21, the washing agent used in the washing is methanol or tetrahydrofuran.

[0050] In step S21, the drying conditions are: temperature 40-70°C, preferably 50°C, and vacuum degree 0.05-0.2 atmospheres, preferably 0.1 atmospheres.

[0051] In step S22, the solvent is dichloromethane or tetrahydrofuran.

[0052] In step S22, the concentration of the chiral cluster solution is 2-8 mg / mL, preferably 5 mg / mL.

[0053] In step S22, the spin coating condition is: a rotation speed of 2000-7000 rpm / s, preferably 5000 rpm / s.

[0054] The chiral cluster semiconductor interface of the structure 2 is prepared according to the following steps:

[0055] SA, forming the chiral cluster film on the surface of the substrate;

[0056] SB, forming the semiconductor thin film on the surface of the chiral cluster thin film to obtain the chiral cluster semiconductor interface.

[0057] In step SA, the substrate is a silicon wafer, a quartz wafer, Corning glass, a metal electrode, a charge transfer medium, a dielectric layer, a charge blocking layer, a nanowire or a nanosphere, etc.

[0058] In step SA, the chiral cluster film is made of a chiral cluster material.

[0059] According to an embodiment of the present invention, in step SA, the chiral cluster film is prepared according to the following steps:

[0060] SA1. Same as step S21.

[0061] SA2. Dissolving the chiral cluster single crystal into a solvent, and coating the obtained chiral cluster solution on the surface of the substrate by a spin coating process to obtain the chiral cluster thin film.

[0062] In step SA2, the solvent is dichloromethane or tetrahydrofuran.

[0063] In step SA2, the concentration of the chiral cluster solution is 5-8 mg / mL, preferably 5-6 mg / mL.

[0064] In step S22, the spin coating condition is: a rotation speed of 2000-8000 rpm / s, preferably 5000-6000 rpm / s.

[0065] In step SB, the semiconductor film is made of a semiconductor material that will not damage the chiral cluster film, such as a two-dimensional material and an organic semiconductor material. Inorganic semiconductor materials often require high temperature preparation, so inorganic semiconductor materials are difficult to use in this structure.

[0066] The two-dimensional material needs to be bonded onto the upper surface of the chiral cluster layer using a transfer heat bonding method, and the heat bonding temperature should be lower than the thermal decomposition temperature of the chiral clusters.

[0067] The organic semiconductor material is an organic polymer semiconductor material or an organic small molecule semiconductor material.

[0068] The organic polymer semiconductor material is usually dissolved in a chlorine-containing solvent, which easily destroys the underlying chiral cluster film. Therefore, the transfer heat bonding method is selected to prepare the semiconductor film.

[0069] The organic small molecule semiconductor materials are 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pen), dinaphtho[2,3-B:2′,3′-F]thieno[3,2-B]thiophene (DNTT), copper phthalocyanine (CuPc), 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT), benzo[B]benzo[4,5]thieno[2,3-D]thiophene (BTBT), N,N′-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8), etc.

[0070] According to an embodiment of the present invention, in step SB, the semiconductor film is prepared according to the following steps: the organic small molecule semiconductor material powder is sublimated and purified, and then deposited on the surface of the chiral cluster film by vacuum evaporation to form the semiconductor film.

[0071] The process parameters of the vacuum evaporation method are as follows:

[0072] Vacuum degree of vacuum chamber: (3-5)×10 -6 mBar, preferably 4×10 -6 mBar;

[0073] Vacuum evaporation rate: <0.2 Preferably 0.1

[0074] Rotation rate: 115-125° / s, preferably 120° / s.

[0075] In a second aspect, the present invention further provides a circularly polarized light phototransistor device, comprising the chiral cluster semiconductor interface.

[0076] The circularly polarized light phototransistor device is one of a circularly polarized light detector, a circularly polarized light memory, a circularly polarized light photodiode, a circularly polarized light light emitting diode and a circularly polarized light memristor.

[0077] In a third aspect, the present invention further provides a method for preparing the circularly polarized light phototransistor device, comprising the following steps:

[0078] For the chiral cluster semiconductor interface of the structure 1, source and drain electrodes are formed on the lower surface of the semiconductor film, a dielectric layer is formed on the upper surface of the chiral cluster film, and a gate electrode is formed on the upper surface of the dielectric layer to obtain the circularly polarized light phototransistor device;

[0079] For the chiral cluster semiconductor interface of the structure 2, source and drain electrodes are formed on the upper surface of the semiconductor film to obtain the circularly polarized light phototransistor device.

[0080] In the first embodiment, the dielectric layer is made of Parylene C, and the thickness of the dielectric layer is 200-400 nm, preferably 300 nm.

[0081] In the first embodiment, the gate electrode is made of one of aluminum, silver and gold, preferably aluminum. The gate electrode has a thickness of 20-100 nm, preferably 50 nm.

[0082] In the first method, the dielectric layer and the gate electrode are realized by evaporation; the process conditions of the evaporation are: 40-1000 mg of polyparaxylene is placed in the sample chamber, and after evacuating to less than 1 Torr, the vaporization temperature is set to 150°C, the cracking temperature is set to 650°C, and the deposition chamber temperature is set to 25°C.

[0083] In the second embodiment, the source-drain electrode is made of Au and has a thickness of 20-30 nm.

[0084] In the second method, the source-drain electrode is realized by vacuum evaporation method; the process conditions of the vacuum evaporation method are: the vacuum degree is (1-5)×10 -5 Pa, preferably 2×10 -5 Pa; vacuum evaporation rate <0.2 Preferably 0.1 The rotation rate is 115-125° / s, preferably 120° / s.

[0085] The present invention has the following technical effects:

[0086] 1. The present invention provides a design idea for the structure of a circularly polarized light detection and storage device, in which the chiral clusters serve as receiving units and storage units for circularly polarized light information, the semiconductors serve as transmission units for electrical signals, and the chiral cluster semiconductor interface serves as a channel for photoelectric information transmission, thereby meeting the requirements for the effective and rapid transmission of photogenerated charges of circularly polarized light at the interface, and realizing the resolution and storage of circularly polarized light, that is, realizing the integration of sensing and storage, thereby storing the information in situ while processing and resolving the circularly polarized light information.

[0087] 2. Compared with other design strategies, this strategy has simple process, good universality and low cost.

[0088] 3. This interface structure can be applied to the integration of various devices, and provides two solutions caused by the stacking of chiral clusters and semiconductor physical space. Moreover, chiral clusters can obtain chiral cluster structures with different circularly polarized light absorption through external ligand design and preparation process, while semiconductors can be applied to the semiconductor material system known today, ensuring that the transmission of electrical signals is not restricted by chiral clusters. BRIEF DESCRIPTION OF THE DRAWINGS

[0089] Figure 1 Schematic diagram of the structure of the chiral cluster semiconductor interface prepared by Example 1 and Example 2 provided in the present invention; the left figure is the interface structure of Example 1, and the right figure is the interface structure of Example 2.

[0090] Figure 2 This is a schematic diagram of the structure of the phototransistor device in Example 2 provided by the present invention.

[0091] Figure 3 This is a transfer characteristic curve diagram of the phototransistor device in Example 2 provided by the present invention.

[0092] Figure 4 This is the circular dichroism spectrum of the chiral cluster film in Example 2 provided by the present invention.

[0093] Figure 5 This is a diagram showing circularly polarized light recognition by the phototransistor device in Example 2 provided by the present invention.

[0094] Figure 6 This is a memory diagram of circularly polarized light storage by the phototransistor device in Example 2 provided by the present invention.

[0095] In the figure: 1. Chiral cluster; 2. Semiconductor. DETAILED DESCRIPTION

[0096] The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments.

[0097] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0098] The substrate used in the following Example 1 is a hard Corning glass substrate coated with a 20-40 nm patterned source and drain electrode.

[0099] Poly(3-hexylthiophene) (P3HT) used in the following Example 1 was purchased from Sigma Aldrich.

[0100] The thermal crosslinking agent 6-silanetetrayl-1,2,3,4,5-hexapentaenylidene (C6Si) used in the following Example 1 was purchased from Sigma Aldrich.

[0101] Parylene C used in the following Example 1 was purchased from Sigma Aldrich.

[0102] The substrate used in the following Example 2 is a silicon wafer that has been thermally oxidized to form 300 nm of silicon dioxide and polished.

[0103] The organic small molecule semiconductor material C8-BTBT used in the following Example 2 was purchased from Sigma Aldrich.

[0104] The chiral enantiomer of (S)-(+)-2-amino-3-methyl-1-butanol used in the following Examples 1 and 2 was purchased from Sigma Aldrich.

[0105] Example 1

[0106] Here are the steps:

[0107] S1. Preparation of semiconductor thin films:

[0108] (1) dissolving a semiconductor material poly(3-hexylthiophene) (P3HT) in chlorobenzene to obtain a semiconductor material solution with a concentration of 6 mg / mL; adding a thermal crosslinking agent 6-Silanetetrayl-1,2,3,4,5-hexapentaenylidene (C6Si) to the above solution at a mass ratio of semiconductor:crosslinking agent = 10:1 to obtain a semiconductor solution containing a thermal crosslinking agent;

[0109] The semiconductor solution containing the thermal crosslinking agent was spin-coated on a glass substrate at a rotation speed of 1600 rpm / s, followed by annealing at 135° C. for 10 min to obtain a semiconductor film with a thickness of 30-40 nm.

[0110] S2. Preparation of Chiral Cluster Thin Films and Chiral Cluster Semiconductor Interfaces:

[0111] (2) N,N-dimethylacetamide and acetonitrile are mixed in a weight ratio of 3.5:1 to prepare a mixed solution; (S)-(+)-2-amino-3-methyl-1-butanol chiral enantiomer is used as a ligand and is dissolved in the mixed solution with silver nitrate in a molar ratio of 1.2:1 to obtain a ligand solution and a silver nitrate solution;

[0112] The ligand solution was slowly added dropwise to the silver nitrate solution, and a magnetic stirrer was added and the stirring speed was controlled between 300-500 rpm / s until all the ligand solution was added dropwise. After stirring for 1-5 minutes, a clear yellow solution was obtained. The solution was left uncovered in a dark place. After 1-3 days, blocky chiral cluster single crystals were obtained in the mother liquor.

[0113] The obtained chiral cluster single crystal was washed with methanol and then placed in a vacuum oven for heating and drying at 50°C with a vacuum degree of 0.1 atmospheres. The crystal was stored away from light.

[0114] (3) Dissolve the chiral cluster single crystal in dichloromethane solvent to prepare a 5 mg / mL chiral cluster solution; the chiral cluster solution is coated on the surface of the obtained semiconductor film by spin coating at a speed of 5000 rpm / s. The solvent evaporates naturally during the spin coating process and no annealing treatment is required to obtain a chiral cluster film, which forms a chiral cluster semiconductor interface with the semiconductor film. The structure is as follows Figure 1 Shown in the middle left picture.

[0115] S3. Preparation of circularly polarized light phototransistor device:

[0116] (4) Parylene C molecules were evaporated on the surface of the obtained chiral cluster film as a dielectric layer with a thickness of 300 nm. The preparation strictly followed the operating instructions on the official website of Specialty Coating Systems.

[0117] (5) A gate electrode is evaporated on the surface of the obtained dielectric layer. The thickness of the gate electrode is 50 nm and the material selected for the gate electrode is aluminum. Finally, a circularly polarized light phototransistor device based on the chiral cluster semiconductor interface is obtained.

[0118] Example 2

[0119] Here are the steps:

[0120] S1. Preparation of chiral cluster films:

[0121] (1) N,N-dimethylacetamide and acetonitrile are mixed in a weight ratio of 4:1 to prepare a mixed solution; (S)-(+)-2-amino-3-methyl-1-butanol chiral enantiomer is used as a ligand and is dissolved in the mixed solution with silver nitrate in a molar ratio of 1.2:1 to obtain a ligand solution and a silver nitrate solution;

[0122] The ligand solution was slowly added dropwise to the silver nitrate solution, and a magnetic stirrer was added at room temperature. The stirring speed was controlled between 300-500 rpm / s until all the ligand solution was added dropwise. The solution was stirred for 1-5 minutes to obtain a clear yellow solution. The solution was placed in a dark place without a lid. After 1-2 days, a block-shaped chiral cluster single crystal was obtained in the mother solution.

[0123] The crystals were washed with methanol or tetrahydrofuran and then placed in a vacuum oven at 50°C for drying with a vacuum degree of 0.1 atmosphere. The crystals were stored away from light.

[0124] (2) dissolving the chiral cluster single crystal in dichloromethane solvent to prepare a 5 mg / mL chiral cluster solution; then coating the chiral cluster solution on the substrate surface by spin coating at a rotation speed of 5000-6000 rpm / s, wherein the solvent evaporates naturally during the spin coating process, and no annealing treatment is performed afterwards to obtain a chiral cluster film.

[0125] S2. Preparation of semiconductor thin films and chiral cluster semiconductor interfaces

[0126] (3) After the organic small molecule semiconductor material DNTT powder is sublimated and purified, it is placed in a quartz crucible and deposited on the surface of the obtained chiral cluster film by vacuum evaporation to form a semiconductor film, and a chiral cluster semiconductor interface is formed with the chiral cluster film. The structure is as follows Figure 1 As shown in the middle right picture.

[0127] S3. Preparation of circularly polarized light phototransistor device:

[0128] (4) preparing source and drain electrodes on the surface of the obtained semiconductor film by vacuum evaporation method, wherein the process conditions of the vacuum evaporation method are as follows: vacuum degree of the vacuum chamber: 2×10 -5 Pa; vacuum evaporation rate: 0.1 Rotation rate: 120° / s, a circularly polarized phototransistor device is obtained. Figure 2 shown.

[0129] Effect verification:

[0130] 1. If Figure 3 As shown, it can be seen that the hysteresis of the device transfer characteristic curve becomes larger and the maximum current decreases after adding light, indicating that there are photogenerated charge generation, separation, charge transfer and charge recombination processes between the clusters and the semiconductor during the light addition process, proving that the cluster and semiconductor interface can have good responsiveness to light.

[0131] 2. If Figure 4 As shown, it can be seen that the chiral clusters have circular dichroism, and the maximum value is located at 277nm.

[0132] 3. Testing of circularly polarized light recognition and circularly polarized light storage functions

[0133] The test conditions are as follows: the light source is a 270nm LED parallel light source, and 270nm left-handed and right-handed circularly polarized light is obtained through a 1 / 2 linear polarizer and a 1 / 4 circular polarizer. The circularly polarized light is irradiated vertically on the device surface, and the circularly polarized light intensity received by the device is 100μW / cm 2 , and the intensity of left-handed circularly polarized light and right-handed circularly polarized light is always consistent.

[0134] The device obtained in Example 2 was subjected to a gate voltage of 0 V and a source-drain voltage of -1 V. The source-drain current was read as the circularly polarized light switched back and forth between left-handed and right-handed. The left-handed light and the right-handed light alternated every 30 seconds. The results are shown in FIG. Figure 5 As shown, the device exhibits recognition and discrimination of left-handed circularly polarized light and right-handed circularly polarized light.

[0135] The device obtained in Example 2 was subjected to a gate voltage of 0 V and a source-drain voltage of -5 V. A left-handed / right-handed circularly polarized light pulse was applied to the phototransistor device for 15 seconds, and the source-drain current change value was read. The results are shown in FIG. Figure 6 As shown, the solid line represents the change in current value under right-hand polarized light irradiation, and the dotted line represents the change in current value under left-hand polarized light irradiation.

[0136] The current results show that the device current rises slowly during the light addition process, and slowly drops to a platform after the light pulse ends. In the whole process, the device current value under right-handed circularly polarized light is always higher than the device current value under left-handed circularly polarized light. Therefore, the device can not only identify circularly polarized light, but also store circularly polarized light information in real time.

[0137] Although the present invention has been described in detail above with general descriptions and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements may be made thereto based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A method for realizing circularly polarized light resolution and storage, comprising the following steps: forming a semiconductor film and a chiral cluster film on a substrate surface to construct a chiral cluster semiconductor interface; The structure of the chiral cluster semiconductor interface is one of the following two structures: Structure 1: The chiral cluster film is physically located above the semiconductor film; Structure 2: The chiral cluster film is physically located below the semiconductor film; The chiral cluster semiconductor interface has the following characteristics: Roughness: RMS roughness should be <3nm; Defect state density: Defect state density should be <10 -16 cm -3 .

2. The method for realizing circularly polarized light resolution and storage according to claim 1, characterized in that: The chiral cluster semiconductor interface of the structure 1 is prepared according to the following steps: S1, forming the semiconductor thin film on the upper surface of the substrate; S2. Forming the chiral cluster thin film on the surface of the semiconductor thin film to obtain the chiral cluster semiconductor interface.

3. The method for realizing circularly polarized light resolution and storage according to claim 2, characterized in that: In step S1, the material of the semiconductor film is one or more of an organic semiconductor material, an inorganic semiconductor material, and a two-dimensional material whose energy level band gap is within the definition range of a semiconductor material; The organic semiconductor material is an organic polymer semiconductor material or an organic small molecule semiconductor material; The organic polymer semiconductor material is one or more of poly(3-hexylthiophene), 9,9-dioctylfluorene, poly(diketopyrrolopyrrole diketothiophene vinylthiophene) and polyperylene imide dithiophene; The organic small molecule semiconductor material is one or more of pentacene, fullerene, perylenetetracarboxylic acid diimide, and naphthalenetetracarboxylic acid diimide; The inorganic semiconductor material is one or both of boron-doped single crystal silicon and phosphorus-doped single crystal silicon; The two-dimensional material is one or more of graphene, graphyne, molybdenum disulfide and black phosphorus; When the material of the semiconductor film is the organic semiconductor material, the thickness of the semiconductor film obtained is 10-2000nm; When the material of the semiconductor thin film is the inorganic semiconductor material, the thickness of the corresponding semiconductor thin film is 5-300 nm; When the material of the semiconductor film is the two-dimensional material, the corresponding thickness of the semiconductor film is 1-30 nm.

4. The method for realizing circularly polarized light resolution and storage according to claim 3, characterized in that: In step S1, the semiconductor film is prepared according to the following steps: The organic polymer semiconductor material is added into a solvent, and then a cross-linking agent is added, and after blending, a film is formed and annealed on the surface of the substrate by a solution method to obtain the semiconductor thin film; The solvent is one or more of chlorobenzene, o-dichlorobenzene and chloroform; The crosslinking agent is a thermal crosslinking agent and / or a photocrosslinking agent; In the blended system, the concentration of the organic polymer semiconductor material is 4-10 mg / mL; The mass ratio of the organic polymer semiconductor material to the cross-linking agent is (10-100): 1; The cross-linking agent is a thermal cross-linking agent, and the blended system is subjected to spin coating and then annealing; wherein the spin coating conditions are: a rotation speed of 1500-2500 rpm / s, an annealing temperature of 130-150° C., and a time of 10-30 min; The crosslinking agent is a photocrosslinking agent, and the blended system is formed by spin coating, followed by annealing and exposure; wherein the spin coating conditions are: a rotation speed of 1500-2500rpm / s; the annealing conditions are: a temperature of 90-200°C and a time of 5-15min; the exposure conditions are: a wavelength of 365nm or 254nm and a time of 10-60min.

5. The method for realizing circularly polarized light resolution and storage according to any one of claims 2 to 4, characterized in that: In step S2, the chiral cluster film is made of a chiral cluster material; The chiral cluster film is prepared according to the following steps: S21, mixing N,N-dimethylacetamide with acetonitrile to obtain a mixed solution; dissolving the chiral enantiomer of 2-amino-3-methyl-1-butanol and silver nitrate in the mixed solution respectively to obtain a ligand solution and a silver nitrate solution; under stirring, adding the ligand solution dropwise to the silver nitrate solution to obtain a clear yellow solution, and placing the solution in a dark place without being exposed to obtain a block-shaped chiral cluster single crystal; Washing and drying; S22, dissolving the chiral cluster single crystal into a solvent, and covering the obtained chiral cluster solution on the surface of the semiconductor film by a spin coating process to obtain the chiral cluster film; In step S21, the mass ratio of the N,N-dimethylacetamide to the acetonitrile is (3.5-4):1, preferably 4:1 or 3.5:1; In step S21, the chiral enantiomer of 2-amino-3-methyl-1-butanol is (S)-(+)-2-amino-3-methyl-1-butanol or (R)-(-)-2-amino-3-methyl-1-butanol; In step S21, the molar ratio of the chiral enantiomer of 2-amino-3-methyl-1-butanol to silver nitrate is (1-1.5):1; In step S21, the stirring speed is controlled between 200-500 rpm / s; In step S21, the placement time is 1-3 days; In step S21, the washing agent used in the washing is methanol or tetrahydrofuran; In step S21, the drying conditions are: temperature 40-70°C, vacuum degree 0.05-0.2 atmospheres; In step S22, the solvent is dichloromethane or tetrahydrofuran; In step S22, the concentration of the chiral cluster solution is 2-8 mg / mL; In step S22, the spin coating condition is: a rotation speed of 2000-7000 rpm / s.

6. The method for realizing circularly polarized light resolution and storage according to claim 1, characterized in that: The chiral cluster semiconductor interface of the structure 2 is prepared according to the following steps: SA, forming the chiral cluster film on the surface of the substrate; SB, forming the semiconductor thin film on the surface of the chiral cluster thin film to obtain the chiral cluster semiconductor interface.

7. The method for realizing circularly polarized light resolution and storage according to claim 6, characterized in that: In step SA, the substrate is one or more of a silicon wafer, a quartz wafer, Corning glass, a metal electrode, a charge transfer medium, a dielectric layer, a charge blocking layer, a nanowire, and a nanosphere; The chiral cluster film is made of chiral cluster material; The chiral cluster film is prepared according to the following steps: SA1, preparation of bulk chiral cluster single crystals; SA2, dissolving the chiral cluster single crystal into a solvent, and covering the obtained chiral cluster solution on the surface of the substrate by a spin coating process to obtain the chiral cluster film; In step SA2, the solvent is dichloromethane or tetrahydrofuran; In step SA2, the concentration of the chiral cluster solution is 5-8 mg / mL; In step S22, the spin coating condition is: a rotation speed of 2000-8000 rpm / s.

8. The method for realizing circularly polarized light resolution and storage according to claim 6 or 7, characterized in that: In step SB, the semiconductor film is made of two-dimensional material and organic semiconductor material; The organic semiconductor material is an organic polymer semiconductor material or an organic small molecule semiconductor material; The organic small molecule semiconductor material is one or more of 6,13-bis(triisopropylsilylethynyl)pentacene, dinaphtho[2,3-B:2′,3′-F]thieno[3,2-B]thiophene, copper phthalocyanine, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene, benzo[B]benzo[4,5]thieno[2,3-D]thiophene and N,N′-dioctyl-3,4,9,10-perylene dicarboximide.

9. A circularly polarized light phototransistor device, comprising the chiral cluster semiconductor interface described in any one of claims 1 to 8; The circularly polarized light phototransistor device is one of a circularly polarized light detector, a circularly polarized light memory, a circularly polarized light photodiode, a circularly polarized light emitting diode and a circularly polarized light memristor.

10. The method for preparing the circularly polarized light phototransistor device according to claim 9, comprising the following steps: For the chiral cluster semiconductor interface of the structure 1, source and drain electrodes are formed on the lower surface of the semiconductor film, a dielectric layer is formed on the upper surface of the chiral cluster film, and a gate electrode is formed on the upper surface of the dielectric layer to obtain the circularly polarized light phototransistor device; For the chiral cluster semiconductor interface of the structure 2, source and drain electrodes are formed on the upper surface of the semiconductor film to obtain the circularly polarized light phototransistor device.

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