A method for resolving and storing circularly polarized light using a chiral cluster semiconductor interface and its application.

Abstract

This invention discloses a method for resolving and storing circularly polarized light using a chiral cluster semiconductor interface, and its applications. The invention utilizes chiral clusters as units for circularly polarized light detection, photoelectric signal conversion, and storage, and semiconductors as units for transmitting and outputting electrical signals, thus constructing a chiral cluster semiconductor interface. This interface enables the transmission of circularly polarized light information, achieving integrated sensing and storage of circularly polarized light, effectively reducing device fabrication costs and structural complexity. The circularly polarized light phototransistor device provided by this invention has broad application prospects in fields such as encrypted transmission, encoding / decoding, and anti-counterfeiting.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor materials and optoelectronic devices, and relates to a method for realizing circularly polarized light resolution and storage using chiral cluster semiconductor interfaces and its application. Background Technology

[0002] Light is essentially an electromagnetic wave, possessing all the properties of electromagnetic waves. Light exhibits wave-particle duality, carrying not only information about electromagnetic waves (intensity, wavelength, and phase) but also energy carried by photons. Light can interact with matter, both physically and chemically, essentially involving the transfer and exchange of energy. Photothermal conversion involves the transfer of photon energy to phonons, converting it into heat energy; photoelectric conversion involves the transfer of photon energy to excitons, converting it into the kinetic energy of electrons (holes). Electricity is currently the easiest form of energy for humans to control, produce, store, and transmit. Therefore, converting light into electricity is a crucial way for humans to utilize light, as seen in solar cells and photodiodes. The core of photoelectric conversion lies in photoelectric materials. Photoelectric materials are materials that convert light into electricity, and the devices that utilize light energy to convert it into electrical energy are called photoelectric devices.

[0003] Modern optoelectronic devices can detect light intensity (radiometers, densitometers, etc.) and wavelength (near-infrared detectors, visible light detectors, X-ray detectors, etc.), but often neglect the phase information carried by light. The electric field of light consists of two mutually perpendicular linear components. Phase changes in these two perpendicular components alter the polarization of the light, resulting in linearly polarized, elliptically polarized, and circularly polarized light. Polarized light, due to its unique phase information, is widely used in fields such as optical filters and information encryption. Therefore, the detection of polarized light has high application value. Most optoelectronic materials have specific absorption wavelengths and absorption coefficients, but these cannot be combined with the phase information of light, thus preventing direct use for polarized light detection. Based on the principle of linear polarization, parallel light passing through a half-polarizer becomes polarized light. Therefore, if an optoelectronic material has a parallel and equidistant grating structure similar to that used for half-polarized light, it can detect polarized light. Thus, most linearly polarized light detectors are based on photoelectric-responsive semiconductor crystal materials. Semiconductor crystal materials are highly designable, diverse, and easy to fabricate, thus the development of linearly polarized light detectors has been 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 linearly polarized light, and then through a 1 / 4 polarizer. Therefore, semiconductor crystal materials are difficult to meet the requirements of circularly polarized light detectors.

[0004] Chiral materials have been shown to resolve circularly polarized light, although many theories and reasonable conjectures exist regarding their mechanistic explanations (such as plasmon hybridization theory and mode coupling theory). While chiral materials are quite common in nature, such as DNA and glucose, those with photoelectric properties are relatively limited. Representative chiral photoelectric materials include helicene, chiral two-dimensional perovskites, and chiral thermally activated delayed fluorescence (TADF) organic small molecules. These materials share the common feature of possessing chiral structural units and π systems (benzene rings, thiophene rings, etc.), with the former providing the chiral environment and the latter providing charge transport channels. Although the aforementioned chiral optoelectronic materials have achieved excellent detection and resolution capabilities for circularly polarized light ((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 numerous material synthesis steps, high costs, and complex design strategies have limited the development of circularly polarized light detection devices. Therefore, developing new design strategies or expanding the application scope of circularly polarized detection will drive the development of circularly polarized light optoelectronic devices. Summary of the Invention

[0005] The purpose of this invention is to provide a method and its application for resolving and storing circularly polarized light using a chiral cluster semiconductor interface. By constructing an interface between a chiral cluster and a semiconductor, the chiral cluster serves as both the receiving and storing unit for circularly polarized light information, while the semiconductor acts as the transmission unit for electrical signals. The chiral cluster semiconductor interface then functions as a channel for photoelectric information transmission, enabling the resolution and storage of circularly polarized light—that is, achieving integrated sensing and storage. This allows for the simultaneous processing and resolving of circularly polarized light information and in-situ storage of the information. This strategy is simple to implement, widely applicable, and low-cost, providing a new design approach for circularly polarized light optoelectronic devices.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A method for resolving and storing circularly polarized light includes the following steps: constructing a chiral cluster semiconductor interface on a substrate surface by forming a semiconductor thin film and a chiral cluster thin film;

[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 one 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 thin film below. The root mean square roughness of the semiconductor thin film should be <3 nm.

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

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

[0015] S1. Form the semiconductor thin film on the upper surface of the substrate;

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

[0017] In step S1, the substrate can be any physically supportive structure used in the fabrication of a semiconductor device. For example, the substrate can be a glass substrate, a metal electrode, a charge transport medium, a dielectric layer, a charge blocking layer, a nanowire, or a nanosphere.

[0018] In step S1, the semiconductor thin film is made of one or more of organic semiconductor materials, inorganic semiconductor materials, and two-dimensional materials whose energy level band gap is within the defined range of semiconductor materials; preferably, organic semiconductor materials are used.

[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), polypyrrolopyrroledionethiophene vinylthiophene (PDVT), and polyperylimide dithiophene (N2200). Organic polymer semiconductor materials often require orthogonal solvation considerations, or direct modification and alteration of the organic polymer semiconductor material, including the addition of thermal or photocrosslinking agents to achieve inter-chain crosslinking and curing, thus resisting solvent erosion.

[0021] The organic small molecule semiconductor material is one or more of pentadiene, fullerene, perylene tetracarboxylate diimide, and naphthalene tetracarboxylate diimide. Due to their small molecular weight, the stacking structure of organic small molecule semiconductor materials is easily disrupted by the upper layer solution, and they are also readily soluble in common solvents; therefore, only a few material systems meet the requirements. For organic small molecule semiconductor materials, they must be resistant to the corrosive effects of at least one or more commonly used solvents, meaning that the solvent covering their surface cannot penetrate the bulk or interior, nor can it dissolve or damage the surface microscopic physicochemical 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] Because 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: the organic polymer semiconductor material is added to a solvent, a crosslinking agent is added, and after blending, the semiconductor thin film is obtained by solution annealing on the substrate surface.

[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 crosslinking agent is (10-100):1, preferably 10:1.

[0030] The crosslinking agent is a thermal crosslinking agent, and the blended system is formed into a film using a solution-based processing method (spin coating, rod coating, doctor blade coating, etc.) followed by annealing. According to an embodiment of the present invention, the spin coating conditions are: a rotation speed of 1500-2500 rpm / s, preferably 1800 rpm / s; and an annealing temperature of 130-150℃, preferably 135℃, for a time of 10-30 min, preferably 20 min. The annealing temperature should be equal to or exceed the initiation and reaction temperature of the thermal crosslinking agent.

[0031] The crosslinking agent is a photocrosslinking agent. The blended system is formed into a film using a solution-based processing method (spin coating, rod coating, blade coating, etc.), followed by annealing and exposure. The spin coating conditions are: rotation speed of 1500-2500 rpm / s; the annealing conditions are: temperature of 90-200℃ and time of 5-15 min; the exposure conditions are: wavelength of 365 nm or 254 nm and time of 10-60 min.

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

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

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

[0035] When the semiconductor thin film is made of a two-dimensional material, the thickness of the semiconductor thin 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 possess the following characteristics:

[0037] Chiral signals: Chiral clusters are detected as having different signals for left-handed and right-handed light on circular dichroism, vibrational circular dichroism, or circular polarization fluorescence spectrometry.

[0038] Chiral source: The synthesis of chiral cluster materials requires the introduction of a chiral source or chiral environment, including chiral ligands, chiral inducers, or chiral solvents. The final chiral structure of the chiral cluster will derive from the chiral ligands, the chiral core, and the chiral core-shell connecting unit.

[0039] Chiral structure stability: The chirality of chiral clusters cannot spontaneously racemize during processing; they should always maintain the stability of their chiral structure.

[0040] Solubility: Chiral clusters should be soluble in one or more solvents and maintain their physicochemical structure in solution. The solubility of chiral clusters in solvents should not be less than 3 mg / mL.

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

[0042] S21. N,N-dimethylacetamide and acetonitrile are mixed to obtain a mixed solution; 2-amino-3-methyl-1-butanol chiral enantiomer and silver nitrate are dissolved in the mixed solution to obtain a ligand solution and a silver nitrate solution, respectively; under stirring, the ligand solution is added dropwise to the silver nitrate solution to obtain a clear yellow solution, which is then placed in the dark to obtain a bulk chiral cluster single crystal; the crystal is washed and dried.

[0043] S22. The chiral cluster single crystal is dissolved in a solvent, and the resulting chiral cluster solution is coated onto the surface of the semiconductor thin film by spin coating to obtain the chiral cluster thin film.

[0044] In step S21, the mass ratio of N,N-dimethylacetamide to 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 2-amino-3-methyl-1-butanol chiral enantiomer 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 detergent used for washing is methanol or tetrahydrofuran.

[0050] In step S21, the drying conditions are: temperature 40-70℃, preferably 50℃, 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 conditions are: a rotation speed of 2000-7000 rpm / s, preferably 5000 rpm / s.

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

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

[0056] SB, The semiconductor thin film is formed 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 sheet, Corning glass, a metal electrode, a charge transport medium, a dielectric layer, a charge blocking layer, a nanowire, or a nanosphere, etc.

[0058] In step SA, the material of the chiral cluster film is 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. Dissolve the chiral cluster single crystal in a solvent, and then coat the resulting chiral cluster solution onto the substrate surface using a spin-coating process to obtain the chiral cluster 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 conditions are: a rotation speed of 2000-8000 rpm / s, preferably 5000-6000 rpm / s.

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

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

[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 commonly dissolved in chlorine-containing solvents, which can easily damage the underlying chiral cluster film. Therefore, the transfer heat bonding method is chosen to prepare the semiconductor film.

[0069] The organic small molecule semiconductor materials are 6,13-bis(triisopropylsilylethynyl)pentabenzene (TIPS-Pen), bisnaphtho[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 thin 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 thin film by vacuum evaporation to form the semiconductor thin film.

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

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

[0073] Vacuum evaporation rate: <0.2 Preferably 0.1

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

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

[0076] The circularly polarized light phototransistor device is one of the following: 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.

[0077] Thirdly, the present invention further provides a method for fabricating the circularly polarized phototransistor device, comprising the following steps:

[0078] For the chiral cluster semiconductor interface of the first structure, a source / drain electrode is formed on the lower surface of the semiconductor thin film, a dielectric layer is formed on the upper surface of the chiral cluster thin film, and a gate electrode is formed on the upper surface of the dielectric layer to obtain the circularly polarized phototransistor device.

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

[0080] In the first method, 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 method, the gate electrode is made of one of aluminum, silver, and gold, preferably aluminum. The thickness of the gate electrode is 20-100 nm, preferably 50 nm.

[0082] In Method 1, the dielectric layer and the gate electrode are achieved by vapor deposition; the vapor deposition process conditions are as follows: 40-1000 mg of parylene is placed in the sample chamber, the vacuum is evacuated to below 1 Torr, and the vaporization temperature is set to 150°C, the pyrolysis temperature to 650°C, and the deposition chamber temperature to 25°C.

[0083] In the second method, the source and drain electrodes are made of Au. The thickness of the source and drain electrodes is 20-30 nm.

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

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

[0086] 1. This invention provides a design concept for a circularly polarized light detection and storage device structure. Chiral clusters serve as the receiving and storage units for circularly polarized light information, semiconductors serve as the transmission units for electrical signals, and the interface of the chiral cluster semiconductor acts as a channel for photoelectric information transmission, satisfying the efficient and rapid transmission of photogenerated charges at the interface of circularly polarized light, thereby realizing the resolution and storage of circularly polarized light, that is, realizing the integration of sensing and storage, so as to process and resolve circularly polarized light information while storing the information in situ.

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

[0088] 3. This interface structure is applicable to the integration of various devices and provides two solutions: one for chiral clusters and the other for stacked semiconductor physical spaces. Moreover, chiral clusters can be designed with external ligands and fabrication processes to obtain chiral cluster structures with different circularly polarized light absorptions, while the semiconductor can be extended to all known semiconductor material systems, ensuring that electrical signal transmission is not limited by chiral clusters. Attached Figure Description

[0089] Figure 1 The diagram shows the structure of the chiral cluster semiconductor interface prepared according to Examples 1 and 2 of the present invention; the left diagram shows the interface structure of Example 1, and the right diagram shows the interface structure of Example 2.

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

[0091] Figure 3 The transfer characteristic curve of the phototransistor device in Embodiment 2 of the present invention is shown.

[0092] Figure 4 The circular dichroism spectrum of the chiral cluster thin film in Example 2 of the present invention.

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

[0094] Figure 6 The phototransistor device in Embodiment 2 of the present invention stores a memory image of circularly polarized light.

[0095] In the figure: 1. Chiral cluster; 2. Semiconductor. Detailed Implementation

[0096] The present invention will be further described below with reference to 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 Example 1 below is a hard Corning glass substrate coated with 20-40nm patterned source and drain electrodes.

[0099] The poly(3-hexylthiophene) (P3HT) used in Example 1 below was purchased from Sigma Aldrich.

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

[0101] The parylene (Parylene C) used in Example 1 below was purchased from Sigma Aldrich.

[0102] The substrate used in Example 2 below is a silicon wafer that has undergone thermal oxidation of 300nm silicon dioxide and polishing.

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

[0104] The (S)-(+)-2-amino-3-methyl-1-butanol chiral enantiomers used in Examples 1 and 2 below were purchased from Sigma Aldrich.

[0105] Example 1

[0106] The steps are as follows:

[0107] S1. Preparation of semiconductor thin films:

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

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

[0110] S2. Preparation of chiral cluster thin films and chiral cluster semiconductor interfaces:

[0111] (2) Mix N,N-dimethylacetamide and acetonitrile in a weight ratio of 3.5:1 to prepare a mixed solution; dissolve (S)-(+)-2-amino-3-methyl-1-butanol chiral enantiomer as a ligand and silver nitrate in a molar ratio of 1.2:1 in the above mixed solution 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 to stir at room temperature. The stirring speed was controlled between 300-500 rpm / s. After all the ligand solution was added, stirring was continued for 1-5 minutes to obtain a clear yellow solution. The solution was then placed in the dark with the container open. After 1-3 days, blocky chiral cluster single crystals were obtained from the mother liquor.

[0113] The obtained chiral cluster single crystals were washed with methanol and then placed in a vacuum oven at 50°C to dry. The vacuum level was 0.1 atmospheres. The crystals were stored in the dark.

[0114] (3) A 5 mg / mL chiral cluster solution was prepared by dissolving a single chiral cluster in dichloromethane solvent. This chiral cluster solution was then spin-coated onto the surface of the resulting semiconductor film at a spin speed of 5000 rpm / s. The solvent evaporated naturally during the spin-coating process, eliminating the need for annealing. This yielded a chiral cluster film, which formed a chiral cluster semiconductor interface with the semiconductor film. The structure is as follows: Figure 1 As shown in the middle left figure.

[0115] S3. Fabrication of circularly polarized light phototransistor devices:

[0116] (4) Parylene C molecules were vapor-deposited as a dielectric layer with a thickness of 300 nm on the surface of the obtained chiral cluster film. The preparation was carried out in strict accordance with the operating instructions on the website of Specialty Coating Systems.

[0117] (5) A gate electrode is deposited on the surface of the obtained dielectric layer. The gate electrode thickness is 50 nm. The selected material 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] The steps are as follows:

[0120] S1. Preparation of chiral cluster thin films:

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

[0122] The ligand solution was slowly added dropwise to the silver nitrate solution. A magnetic stirrer was added and the mixture was stirred at room temperature. The stirring speed was controlled between 300-500 rpm / s. After all the ligand solution was added, the mixture was stirred for 1-5 minutes to obtain a clear yellow solution. The solution was then placed in the dark with the container open. After 1-2 days, blocky chiral cluster single crystals were obtained from the mother liquor.

[0123] After washing the crystals with methanol or tetrahydrofuran, place them in a vacuum oven at 50°C and dry them under a vacuum of 0.1 atm. Store the crystals away from light.

[0124] (2) Dissolve the above chiral cluster single crystal in dichloromethane solvent to prepare a 5 mg / mL chiral cluster solution; then cover the above chiral cluster solution onto the substrate surface by spin coating at a speed of 5000-6000 rpm / s. The solvent evaporates naturally during the spin coating process, and no annealing treatment is required afterward to obtain a chiral cluster film.

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

[0126] (3) After sublimation purification of the organic small molecule semiconductor material DNTT powder, 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 between the semiconductor film and the chiral cluster film. The structure is as follows: Figure 1 As shown in the middle right figure.

[0127] S3. Fabrication of circularly polarized light phototransistor devices:

[0128] (4) Source and drain electrodes are prepared on the surface of the obtained semiconductor thin film by vacuum evaporation. The process conditions for vacuum evaporation are: vacuum chamber vacuum degree: 2×10⁻⁶ -5 Pa; Vacuum evaporation rate: 0.1 Rotation speed: 120° / s, resulting in a circularly polarized light phototransistor device. Structure as follows: Figure 2 As shown.

[0129] Effect verification:

[0130] 1. For example Figure 3 As shown, it can be seen that the hysteresis of the device transfer characteristic curve increases and the maximum current decreases after light is applied, indicating that there are photogenerated charge generation, separation, charge transfer and charge recombination processes between the cluster and the semiconductor during the light application process, proving that the cluster and semiconductor interface can have a good response to light.

[0131] 2. For example Figure 4 As shown, the chiral clusters exhibit circular dichroism, with the maximum value located at 277 nm.

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

[0133] The test conditions were as follows: a 270nm LED parallel light source was used, and 270nm left-handed and right-handed circularly polarized light was obtained through a 1 / 2 linear polarizer and a 1 / 4 circular polarizer. The circularly polarized light was perpendicularly incident on the device surface, and the intensity of the circularly polarized light received by the device was 100μW / cm². 2 Furthermore, the light intensity of left-handed and right-handed circularly polarized light remains consistent.

[0134] A gate voltage of 0V and a source-drain voltage of -1V were applied to the device obtained in Example 2. The changes in source-drain current as circularly polarized light switched between left-handed and right-handed polarization were recorded. The left-handed and right-handed polarization light alternated at 30-second intervals. The results are as follows: Figure 5 As shown, the device demonstrates the ability to recognize and distinguish between left-handed and right-handed circularly polarized light.

[0135] A gate voltage of 0V and a source-drain voltage of -5V were applied to the device obtained in Example 2. Left-handed / right-handed circularly polarized light pulses were applied to the phototransistor device for 15 seconds, and the changes in source-drain current were recorded. The results are as follows: Figure 6 As shown, the solid line represents the change in current value under right-handed polarized light irradiation, and the dashed line represents the change in current value under left-handed polarized light irradiation.

[0136] The current results show that the device current rises slowly during the illumination process and then slowly decreases to a plateau after the light pulse ends. Furthermore, throughout the entire process, the device current value under right-handed circularly polarized light illumination is consistently higher than that under left-handed circularly polarized light illumination. Therefore, the device can not only identify circularly polarized light but also store circularly polarized light information in real time and in situ.

[0137] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A method for resolving and storing circularly polarized light, comprising the following steps: forming a semiconductor thin film and a chiral cluster thin film on a substrate surface, and constructing 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: The root mean square roughness should be <3 nm; Defect state density: The defect state density should be <10. -16 cm -3 ; In step S2, the material of the chiral cluster film is a chiral cluster material; The chiral cluster thin film is prepared according to the following steps: S21. N,N-dimethylacetamide and acetonitrile are mixed to obtain a mixed solution; 2-amino-3-methyl-1-butanol chiral enantiomer and silver nitrate are dissolved in the mixed solution to obtain a ligand solution and a silver nitrate solution, respectively; under stirring conditions, the ligand solution is added dropwise to the silver nitrate solution to obtain a clear yellow solution, which is then placed in the dark to obtain a bulky chiral cluster single crystal. Wash and dry; S22. The chiral cluster single crystal is dissolved in a solvent, and the resulting chiral cluster solution is coated onto the surface of the semiconductor thin film by spin coating to obtain the chiral cluster thin film.

2. The method for resolving and storing circularly polarized light according to claim 1, characterized in that: The chiral cluster semiconductor interface of structure one is prepared according to the following steps: S1. Form the semiconductor thin film on the upper surface of the substrate; S2. The chiral cluster film is formed on the surface of the semiconductor thin film to obtain the chiral cluster semiconductor interface.

3. The method for resolving and storing circularly polarized light according to claim 2, characterized in that: In step S1, the semiconductor thin film is made of one or more of organic semiconductor materials, inorganic semiconductor materials, and two-dimensional materials whose energy level band gap is within the defined range of semiconductor materials; 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, polypyrrolopyrroledionethiophene, and polyperylimide dithiophene; The organic small molecule semiconductor material is one or more of the following: pentacene, fullerene, perylene tetracarboxylate diimide, and naphthalene tetracarboxylate 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 semiconductor thin film is made of the organic semiconductor material, the thickness of the semiconductor thin film is 10-2000 nm. When the semiconductor thin film is made of the inorganic semiconductor material, the thickness of the semiconductor thin film obtained is 5-300 nm. When the semiconductor thin film is made of the two-dimensional material, the thickness of the semiconductor thin film is 1-30 nm.

4. The method for resolving and storing circularly polarized light according to claim 3, characterized in that: In step S1, the semiconductor thin film is prepared according to the following steps: The organic polymer semiconductor material is added to a solvent, a crosslinking agent is added, and after blending, the semiconductor thin film is formed on the substrate surface by solution method and annealed. 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 crosslinking agent is (10-100):1; The crosslinking agent is a thermal crosslinking agent, and the blended system is formed by spin coating followed by annealing; wherein, the spin coating conditions are: a rotation speed of 1500-2500 rpm / s, an annealing temperature of 130-150℃, and a time of 10-30 min; The crosslinking agent is a photocrosslinking agent. The blended system is formed by spin coating, followed by annealing and exposure. The spin coating conditions are: rotation speed of 1500-2500 rpm / s; the annealing conditions are: temperature of 90-200℃ and time of 5-15 min; the exposure conditions are: wavelength of 365 nm or 254 nm and time of 10-60 min.

5. The method for resolving and storing circularly polarized light according to any one of claims 2-4, characterized in that: In step S21, the mass ratio of N,N-dimethylacetamide to acetonitrile is (3.5-4):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 2-amino-3-methyl-1-butanol chiral enantiomer 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 detergent used for washing is methanol or tetrahydrofuran; In step S21, the drying conditions are: temperature 40-70℃, 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 conditions are: rotation speed 2000-7000 rpm / s.

6. The method for resolving and storing circularly polarized light according to claim 5, characterized in that: In step S21, the mass ratio of N,N-dimethylacetamide to acetonitrile is 4:1 or 3.5:

1.

7. The method for resolving and storing circularly polarized light according to claim 1, characterized in that: The chiral cluster semiconductor interface of structure two is prepared according to the following steps: SA, forming the chiral cluster film on the substrate surface; SB, The semiconductor thin film is formed on the surface of the chiral cluster thin film to obtain the chiral cluster semiconductor interface.

8. The method for resolving and storing circularly polarized light according to claim 7, characterized in that: In step SA, the substrate is one or more of the following: silicon wafer, quartz sheet, Corning glass, metal electrode, charge transport medium, dielectric layer, charge blocking layer, nanowire and nanosphere; The chiral cluster film is made of chiral cluster material; The chiral cluster thin film is prepared according to the following steps: SA1, preparation of bulk chiral cluster single crystals; SA2. Dissolve the chiral cluster single crystal in a solvent, and cover the resulting chiral cluster solution onto the substrate surface by spin coating 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 conditions are: rotation speed 2000-8000 rpm / s.

9. The method for resolving and storing circularly polarized light according to claim 7 or 8, characterized in that: In step SB, the semiconductor thin film is made of two-dimensional materials and organic semiconductor materials; 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 the following: 6,13-bis(triisopropylsilylethynyl)pentabenzene, bisnaphtho[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-perylenedicarboximide.

10. A circularly polarized phototransistor device comprising the chiral cluster semiconductor interface described in any one of claims 1-9; The circularly polarized light phototransistor device is one of the following: 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.

11. The method for fabricating the circularly polarized phototransistor device according to claim 10, comprising the following steps: For the chiral cluster semiconductor interface of the first structure, a source / drain electrode is formed on the lower surface of the semiconductor thin film, a dielectric layer is formed on the upper surface of the chiral cluster thin film, and a gate electrode is formed on the upper surface of the dielectric layer to obtain the circularly polarized phototransistor device. For the chiral cluster semiconductor interface of the second structure, source and drain electrodes are formed on the upper surface of the semiconductor thin film to obtain the circularly polarized phototransistor device.

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