Novel photoelectric detector based on room temperature triplet effect and preparation method thereof
By introducing an NDI-COF film into a tungsten disulfide photodetector device and using interface charge transfer to form room temperature trions, the problem of low photocurrent in existing devices is solved, and the photocurrent is significantly increased and the device stability is improved.
Patent Information
- Application Number
- CN202411437188.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-15
- Publication Date
- 2025-01-21
AI Technical Summary
The photocurrent magnitude of existing tungsten disulfide-based photodetection devices at room temperature is much lower than the theoretical value, mainly due to the influence of structural defects and impurities, resulting in device instability.
By preparing tungsten sulfide/NDI-COF new photoelectric detection devices, the charging phenomenon at the interface is used to form a triple temperature of the room temperature, increasing the light current. This device is composed of tungsten sulfide, graphene and NDI-COF film from the bottom to top. The synthetic components of the NDI-COF film include 5,10,15,20-4 (4-amino benzene) , 1,4,5,8-, 甲 酸 酸 酸 、 and SOS surfactants.
By forming a triple temperature of the room temperature, the optical current of tungsten sulfide optical components is significantly increased, and the stability of the device is improved.
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Figure CN119342973A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of novel photoelectric detection devices, and in particular relates to a novel photoelectric detection device based on room temperature triplet effect and a preparation method thereof. Background Art
[0002] Two-dimensional transition metal dichalcogenides (2D TMDCs) are emerging as a typical two-dimensional semiconductor prototype for high-performance optoelectronic devices. Among them, tungsten disulfide is currently the most studied one because of its strong spin-orbit coupling and good electronic and optical properties. This unique property makes tungsten disulfide a promising candidate in basic research and chemical research and physical sensing. For example, tungsten disulfide can be an ideal channel material in photodetection devices, and its functional complexity can be further improved by chemical functionalization, which is the epitome of the More Than Moore strategy in the post-silicon era. However, the recent development of high-end electronic products based on tungsten disulfide is still subject to obvious limitations, such as the photocurrent size in photodetection devices is far below the theoretical value at room temperature, mainly because of the collective effect of structural defects and the presence of impurities (impurities introduced by the environment or processing), which ultimately jeopardizes its application. Therefore, improving the charge transport of monolayer tungsten disulfide by non-invasive methods is of great concern.
[0003] Passivation using layered hexagonal boron nitride (hBN), inorganic materials (such as hafnium oxide, aluminum oxide, and CaF2), organic molecule modification, and even doping strategies are effective methods to improve the performance of TMDCs devices. Compared with the commonly used atomic layer deposition (ALD) dry transfer technique in inorganic materials, small organic molecule passivation is a simpler, more versatile, and cheaper method. For example, the interface of TMDCs with organic molecules with electron-donating / electron-withdrawing groups can lead to the doping of semiconductors through controllable local modification of their surface potential. More importantly, when the molecules self-assemble onto 2DMs nanosheets into ordered supramolecular structures, the doping intensity can be amplified through synergistic effects. However, the 2D supramolecular structures held together by non-covalent interactions undergo dynamic rearrangements upon humidity or high temperature exposure, leading to instability in the operating 2D TMDCs (opto) photodetection devices.
[0004] Therefore, it is very necessary to use stronger interactions to tie molecular units into crystalline films with long-range order. Two-dimensional covalent organic frameworks (2D-COFs) are a new type of crystalline organic materials composed of two-dimensional polymer sheets with ordered structure, clear porosity, high surface area and easy chemical tunability. Two-dimensional COFs films along the in-plane direction are particularly attractive. Due to the tunability of the energy bands of two-dimensional COFs films, we can select the energy bands of two-dimensional COFs and construct them with 2D TMDCs to form a type II energy band arrangement, thereby utilizing the charge transfer process at the interface to improve the stability of 2D TMDCs (opto) photodetection devices. Summary of the invention
[0005] The purpose of the present invention is to provide a new photoelectric detection device based on the room-temperature trion effect and a preparation method thereof. The method prepares a new tungsten disulfide / NDI-COF photoelectric detection device, utilizes the charge transfer phenomenon at the interface to form room-temperature trions, and increases the photocurrent size in the tungsten disulfide photoelectric device.
[0006] To achieve the above-mentioned purpose, the technical solution of the present invention is: a new type of photoelectric detection device based on the room temperature triplet effect, comprising tungsten disulfide, graphene, and NDI-COF film stacked in sequence from bottom to top, wherein the synthetic components of the NDI-COF film are 5,10,15,20-tetrakis(4-aminophenyl)porphyrin, 1,4,5,8-naphthalenetetracarboxylic anhydride and SOS surfactant.
[0007] In one embodiment of the present invention, the concentrations of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin, 1,4,5,8-naphthalenetetracarboxylic anhydride and SOS surfactant in the synthesized NDI-COF film are all 1 mg / mL. -1 .
[0008] In one embodiment of the present invention, the NDI-COF film has a flake-like morphology and a lateral dimension greater than 20 μm.
[0009] In one embodiment of the present invention, the tungsten disulfide has a flake-like morphology, and a lateral dimension greater than 10 μm.
[0010] In one embodiment of the present invention, the graphene is in the form of a thin sheet, and a lateral dimension is greater than 10 μm.
[0011] In one embodiment of the present invention, tungsten disulfide is located on a silicon wafer substrate engraved with gold electrodes, and the tungsten disulfide is located between two gold electrodes of the silicon wafer substrate.
[0012] In one embodiment of the present invention, graphene is located above a gold electrode opposite to tungsten disulfide.
[0013] The present invention also provides a method for preparing a novel photoelectric detection device based on the room temperature triplet effect, comprising the following steps: Step 1: peel off a single layer of tungsten disulfide from the PDMS substrate by mechanical peeling, and then transfer the single layer of tungsten disulfide to a silicon wafer substrate engraved with gold electrodes, ensuring that the single layer of tungsten disulfide is transferred to a precise position between two gold electrodes on the silicon wafer substrate; Step 2: peel off two pieces of few-layer graphene by mechanical peeling, and then transfer the few-layer graphene to the top of the gold electrode and the single-layer tungsten disulfide to construct a tungsten disulfide photodetector; Step 3: Prepare the NDI-COF film by the air-interface method, rinse off various organic matter during the growth process of the NDI-COF film with ethanol, transfer the NDI-COF film to the top of the least layer of graphene after natural air drying, and then anneal the entire device in a tube furnace for 15 min at a temperature set to 100°C to remove water molecules and various organic solvents on the surface of the entire device, enhance the coupling between the interfaces of various materials, and obtain a new photoelectric detection device based on the room temperature triplen effect.
[0014] In one embodiment of the present invention, in step 1, the channel size of the gold electrode is about 10 μm, and the thickness is about 300 nm.
[0015] Compared with the prior art, the present invention has the following beneficial effects: the present invention prepares a new tungsten disulfide / NDI-COF photoelectric detection device, utilizes the charge transfer phenomenon at the interface to form room temperature trions, and increases the photocurrent size in the tungsten disulfide photoelectric device. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 This is an optical microscope image of the NDI-COF film prepared in Example 1 of the present invention; Figure 2 This is an atomic force microscope image of the NDI-COF film prepared in Example 1 of the present invention; Figure 3 This is a transmission electron microscope image of the NDI-COF film prepared in Example 1 of the present invention; Figure 4 is a comparison spectrum of triplet specific gravity at room temperature obtained by photoluminescence spectrum test of Example 1 of the present invention and Comparative Example 1 at room temperature; Figure 5 This is a schematic diagram of the process of forming room temperature trions at the interface of Example 1 of the present invention; Figure 6 This is a schematic diagram of the structure of the novel photoelectric detection device prepared in Example 1 of the present invention: Figure 7This is an optical microscope image of the novel photoelectric detection device prepared in Example 1 of the present invention: Figure 8 This is an optical microscope image of the tungsten disulfide photoelectric detection device prepared in Comparative Example 1 of the present invention: Fig. 9 The current curves obtained by applying voltage to the embodiment 1 and the comparative example 1 of the present invention under the condition of laser irradiation and without laser irradiation; Fig.10 1 is a light response curve obtained by testing Example 1 of the present invention and Comparative Example 1 under applied voltage. DETAILED DESCRIPTION
[0017] The technical solution of the present invention is described in detail below in conjunction with the accompanying drawings.
[0018] The invention provides a novel photoelectric detection device based on the room temperature triplet effect, comprising tungsten disulfide, graphene, and an NDI-COF film stacked in sequence from bottom to top, wherein the synthesis components of the NDI-COF film are 5,10,15,20-tetrakis(4-aminophenyl)porphyrin, 1,4,5,8-naphthalenetetracarboxylic anhydride, and an SOS surfactant.
[0019] The present invention also provides a method for preparing a novel photoelectric detection device based on the room temperature triplet effect, comprising the following steps: Step 1: peel off a single layer of tungsten disulfide from the PDMS substrate by mechanical peeling, and then transfer the single layer of tungsten disulfide to a silicon wafer substrate engraved with gold electrodes, ensuring that the single layer of tungsten disulfide is transferred to a precise position between two gold electrodes on the silicon wafer substrate; Step 2: peel off two pieces of few-layer graphene by mechanical peeling, and then transfer the few-layer graphene to the top of the gold electrode and the single-layer tungsten disulfide to construct a tungsten disulfide photodetector; Step 3: Prepare the NDI-COF film by the air-interface method, rinse off various organic matter during the growth process of the NDI-COF film with ethanol, transfer the NDI-COF film to the top of the least layer of graphene after natural air drying, and then anneal the entire device in a tube furnace for 15 min at a temperature set to 100°C to remove water molecules and various organic solvents on the surface of the entire device, enhance the coupling between the interfaces of various materials, and obtain a new photoelectric detection device based on the room temperature triplen effect.
[0020] The following are specific implementation examples of the present invention.
[0021] Example 1 1.1. Synthesis of organic film (i.e. NDI-COF film) by the following method: 1) First, add 50 mL of ultrapure water into a 90 mm diameter culture dish, and use a microinjector to add 20 uL of SOS surfactant dissolved in chloroform at the gas-liquid interface, and wait for the solvent to evaporate for 30 min; 2) Add 0.5 mL of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin solution (dissolved in 0.12 M HCl solution, 1 mg / mL) to the aqueous phase and allow 5,10,15,20-tetrakis(4-aminophenyl)porphyrin to disperse in water for 30 min; 3) Add 0.1 mL of 1,4,5,8-naphthalenetetracarboxylic anhydride solution (dissolved in 0.08 M LiOH solution, 1 mg / mL) to the aqueous phase and polymerize at room temperature to obtain an organic film.
[0022] 1.2. Use the organic film obtained by polymerization in 1.1 to prepare a new photoelectric detection device based on the room temperature triplet effect. The preparation method is as follows: (1) A silicon wafer with a gold electrode of about 300 nm thickness and a channel size of about 10 μm was used as the substrate for the new photodetector device; (2) By mechanical peeling, a 100 μm thick film was peeled off from the PDMS substrate. 2 A monolayer of tungsten disulfide is then transferred to a silicon wafer substrate; (3) Two pieces with an area of about 1000 μm were peeled off from the PDMS substrate by mechanical peeling. 2 The few-layer graphene is then transferred to a gold electrode and a single layer of tungsten disulfide to form a tungsten disulfide photodetector. (4) The organic film obtained in 1.1 is rinsed with ethanol, and after natural air drying, the organic film is transferred to the top of the least graphene layer. The device is then annealed in a tube furnace for 15 min at a temperature of 100 °C to remove water molecules and various organic solvents on the device surface and enhance the coupling between the interfaces of various materials, thereby obtaining a new photoelectric detection device based on the room temperature triplet effect.
[0023] Comparative Example 1 The tungsten disulfide photodetector constructed in this comparative example 1.2 (3) is different from that in Example 1 in that the organic film is not transferred to above the at least one layer of graphene.
[0024] The morphology, thickness and structure of NDI-COF films were characterized by optical microscopy, atomic force microscopy and transmission electron microscopy, respectively. Figure 1 , Figure 2 , Figure 3 .
[0025] The photoluminescence spectrum of Example 1 and Comparative Example 1 was tested and compared using a photoluminescence spectrum with a wavelength of 405 nm. The luminescence peak of room temperature triplet was observed at 627 nm. The result of the increase in the proportion of room temperature triplet in Example 1 was obtained by fitting the Lorentz function. Figure 4 .
[0026] The formation process of room temperature trions can be seen in Figure 5 .
[0027] An optical microscope was used to test the microstructures of the photodetector devices obtained in Example 1 and Comparative Example 1. The test structures are shown in FIG. Figure 7 , Figure 8 .
[0028] The electrical characteristics of the photoelectric detection devices obtained in Example 1 and Comparative Example 1 were tested using a probe station, a source meter and a 405 nm laser: 1) A voltage of 0.5 V was applied to the electrodes at both ends of the photodetector device, and the current response characteristics of the photodetector devices of Example 1 and Comparative Example 1 were tested under the conditions of not turning on the laser and turning on the laser. The test results are shown in FIG. Fig. 9 As shown, the dark current of the new photodetector device is higher than that of the single-layer tungsten disulfide photodetector device, which indicates that room-temperature trions are formed in the new photodetector device, and the separation of room-temperature trions leads to the increase of dark current.
[0029] 2) A voltage of 0.5 V was applied to the electrodes at both ends of the photodetector device, and a laser with a wavelength of 405 nm and a power of 1.8 mw was used to irradiate the photodetector devices in Example 1 and Comparative Example 1, respectively. The time-dependent dynamic curve test results of the devices are shown in FIG. Fig.10 As shown, for the monolayer tungsten disulfide photodetector, the photocurrent rises rapidly after laser irradiation, and the recovery time after irradiation is slow, showing a trend of continuous increase. For the new photodetector, no obvious increase in photocurrent and maintenance of dark current were observed during the entire cycle. This stable photocurrent can be attributed to the electron transfer from the NDI-COF film to the monolayer tungsten disulfide to form room temperature trions, which fill the defect states of the monolayer tungsten disulfide, thereby suppressing the above phenomenon.
[0030] Therefore, by comparing the test results of Example 1 and Comparative Example 1, it can be seen that the prepared new photoelectric detection device has a stronger photoelectric response. In summary, the present invention prepares NDI-COF film, combines NDI-COF film with tungsten disulfide photoelectric device, obtains a new photoelectric detection device combining tungsten disulfide and NDI-COF film, and uses a probe station and a source meter to characterize its performance. Through comparative experiments, it is found that due to the charge transfer phenomenon at the interface of the new photoelectric detection device, room temperature triplens are formed at the interface, which increases the photocurrent size of the tungsten disulfide photoelectric detection device. The present invention uses the room temperature triplen to increase the photocurrent size of the photoelectric detection device to construct a new photoelectric detection device, which has certain significance for the future development of the field of photoelectric detection devices.
[0031] The embodiments of the present invention are described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in the relevant technical field without departing from the purpose of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.
[0032] The above are preferred embodiments of the present invention. Any changes made according to the technical solution of the present invention, as long as the resulting functions do not exceed the scope of the technical solution of the present invention, belong to the protection scope of the present invention.
Claims
1. A new photoelectric detection device based on room temperature triplet effect, characterized in that: The invention comprises tungsten disulfide, graphene and NDI-COF film which are stacked in sequence from bottom to top. The synthesis components of the NDI-COF film are 5,10,15,20-tetrakis(4-aminophenyl)porphyrin, 1,4,5,8-naphthalenetetracarboxylic anhydride and SOS surfactant.
2. A novel photoelectric detection device based on room temperature triplet effect according to claim 1, characterized in that: The concentrations of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin, 1,4,5,8-naphthalenetetracarboxylic anhydride and SOS surfactant in the synthesized NDI-COF film were all 1 mg / mL -1 .
3. A novel photoelectric detection device based on room temperature triplet effect according to claim 1, characterized in that: The NDI-COF film has a flake-like morphology and a lateral size greater than 20 μm.
4. The novel photoelectric detection device based on the room temperature triplet effect according to claim 1, characterized in that: The tungsten disulfide has a flake shape and a lateral size greater than 10 μm.
5. The novel photoelectric detection device based on the room temperature triplet effect according to claim 1, characterized in that: The graphene is in the form of flakes, and its lateral size is greater than 10 μm.
6. The novel photoelectric detection device based on the room temperature triplet effect according to claim 1, characterized in that: The tungsten disulfide is located on a silicon wafer substrate engraved with gold electrodes, and the tungsten disulfide is located between two gold electrodes on the silicon wafer substrate.
7. The novel photoelectric detection device based on the room temperature triplet effect according to claim 6, characterized in that: The graphene sits on top of a gold electrode that sits on top of tungsten disulfide.
8. A method for preparing a novel photoelectric detection device based on room temperature triplet effect as claimed in any one of claims 1 to 7, characterized in that: The steps include: Step 1: peel off a single layer of tungsten disulfide from the PDMS substrate, and then transfer the single layer of tungsten disulfide to a silicon wafer substrate engraved with gold electrodes, ensuring that the single layer of tungsten disulfide is transferred to a precise position between two gold electrodes on the silicon wafer substrate; Step 2: peeling off two pieces of few-layer graphene, and then transferring the few-layer graphene to the top of the gold electrode and the single-layer tungsten disulfide to construct a tungsten disulfide photodetector; Step 3: Prepare the NDI-COF film by the air-interface method, rinse off various organic matter during the growth process of the NDI-COF film with ethanol, transfer the NDI-COF film to the top of the least layer of graphene after natural air drying, and then anneal the entire device in a tube furnace for 15 min at a temperature set to 100°C to remove water molecules and various organic solvents on the surface of the entire device, enhance the coupling between the interfaces of various materials, and obtain a new photoelectric detection device based on the room temperature triplen effect.
9. The method for preparing a novel photoelectric detection device based on room temperature triplet effect according to claim 8, characterized in that: In step 1, the channel size of the gold electrode is 10 μm and the thickness is 300 nm.
10. The method for preparing a novel photoelectric detection device based on room temperature triplet effect according to claim 8, characterized in that: Step 1 and step 2 are both peeled off by mechanical peeling method.