Photoelectric dual-response anthryl two-dimensional covalent organic framework device and preparation and application thereof

Abstract

The invention belongs to the technical field of organic information storage, and particularly provides a photoelectric dual-response anthryl two-dimensional covalent organic framework device and preparation and application thereof. The structure of the device is a classic sandwich structure, a bottom electrode is a glass substrate coated with ITO, an active layer is a COF-DaTp thin film, and a top electrode is Al. By applying light pulses with different wavelengths to the device, the device shows dual-photoelectric modulation and shows remarkable photoelectric resistance switching to the light pulses, and 32 photoconductive states are achieved. Besides, the memristor shows history-related memristive behaviors in voltage scanning and electric pulse, has 32 conductive states, and has excellent prospects in the aspects of preparation of miniaturized devices and reduction of energy loss of storage devices.

Description

Technical Field

[0001] The present invention belongs to the field of organic neuromorphic information storage technology, and relates to the preparation and application of a photoelectric dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) with non-volatile storage and rewritable properties. Specifically, it relates to a neuromorphic device with a photoelectric dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) material as an active layer, and its preparation method and application. Background Art

[0002] The rapid development of artificial intelligence and neuromorphic computing requires the exploration of synaptic devices that mimic the behavior of neural synapses in artificial neural networks. Optoelectronic synaptic devices, which convert optical signals into electrical responses, are increasingly recognized for their potential in this field. The operation of these devices is similar to that of human visual neurons: they detect optical stimuli and convert them into neural pulse signals, thereby supporting perception functions in applications such as image sensing, encrypted optical communications, and wearable health monitoring. In addition, these devices can dynamically adjust synaptic weights by light stimulation, mimicking biological synaptic activities and potentially emulating cognitive processes in the human brain. The development of semiconductor technology has enabled the integration of various functional materials into the construction of optoelectronic synaptic devices, including oxide semiconductors, conjugated organic polymers, transition metal sulfides, perovskite materials, and metal nanoparticles and their composites. However, despite these developments, covalent organic frameworks (COFs) and their intrinsic 2D network structures have rarely been reported in the fabrication of optoelectronic synaptic devices. As a class of porous crystalline polymers with high crystallinity and an ordered backbone, COFs ensure the stability and reliability of nanodevices at the microscopic scale. The modular nature of COFs allows independent customization of their pore structures and functional groups. This adaptability facilitates the integration of specific active sites into their vast, permanently accessible surfaces, enhancing their functionality. Anthracene is a photosensitive compound that exhibits reversible structural isomerization when exposed to light of different wavelengths, enhancing its utility in molecular switches and optoelectronics. In addition, anthracene and its derivatives have a π-conjugated system that helps improve charge mobility, making them very suitable for use in organic semiconductor devices. Based on these properties, anthracene-based COFs are expected to be ideal candidates for building high-performance optoelectronic synaptic devices. Summary of the invention

[0003] The purpose of the present invention is to propose a memristor with a photoelectric dual-response anthracene-based two-dimensional covalent organic framework (COF-DaTp) material as an active layer, that is, a memory device with non-volatile storage and rewritable properties.

[0004] The second object of the present invention is to provide a method for preparing a non-volatile erasable memory using a photoelectric dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) material as an active layer.

[0005] The third object of the present invention is to provide a storage device with non-volatile storage and rewritable properties for use in low-power and high-density storage devices.

[0006] The technical solution of the present invention:

[0007] A photoelectric dual-response anthracene-based two-dimensional covalent organic framework (COF-DaTp) device, characterized in that: its structure is composed from bottom to top:

[0008] (1) Glass substrate;

[0009] (2) Indium tin oxide electrode (ITO);

[0010] (3) Photoelectric dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) material thin film active layer;

[0011] (4) Aluminum electrode.

[0012] Furthermore, the thickness of the anthracene-based two-dimensional covalent organic framework (COF-DaTp) material thin film active layer is 30nm-200nm.

[0013] Furthermore, the aluminum electrode has a thickness of 100-200 nm.

[0014] Furthermore, the photoelectric dual-response anthracene-based two-dimensional covalent organic framework (COF-DaTp) device has a photoelectric dual-response function: the device exhibits significantly different resistance states under different light pulses, exhibits significant photoelectric resistance switching to light pulses, and realizes 32 photoconductivity states. In addition, the device exhibits multiple resistance states within a small scanning voltage range, which shows that the photoelectric dual-response anthracene-based two-dimensional covalent organic framework device is also applicable to memristive devices.

[0015] The present invention also provides a method for preparing the polymer memory device having non-volatile storage and rewritable properties, comprising the following steps:

[0016] 1) Clean the glass substrate coated with ITO and dry it;

[0017] 2) Prepare COF-DaT film by interfacial polymerization, separate the reddish-brown COF-DaTp film, and transfer it to the ITO substrate. Wash the COF DaTp on the ITO substrate with 30 mL DMF, water, and ethanol to remove excess unpolymerized monomers;

[0018] 3) vacuum drying the obtained device overnight to remove excess solution;

[0019] 4) Finally, an Al top electrode is plated on the active layer to obtain the device Al / COF-DaTp / ITO.

[0020] Further preferably, the preparation method specifically comprises the following steps:

[0021] 1) Wash the ITO-coated glass substrate (preferably 1.5 cm×1.5 cm) with detergent and deionized water, then wash in ethanol, acetone and isopropanol respectively (preferably for 15 minutes) and dry.

[0022] 2) A polymer layer with a thickness of 100 nm to 200 nm is coated on the ITO glass by spin coating, and the excess solution is removed by vacuum drying overnight.

[0023] 3) Use a vacuum coating apparatus to coat an Al top electrode (preferably with a thickness of 100-200 nm and an area of ​​approximately 0.4×0.4 mm 2 ) is plated on the active layer through a mask, and finally the device Al / COF-DaTp / ITO is obtained.

[0024] The Al / COF-DaTp / ITO structure in the active layer film provided by the present invention is shown in the following formula:

[0025]

[0026] COF-DaTp

[0027] The preparation method of the active layer of the photoelectric dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) material of the present invention is as follows:

[0028] Preparation of COF-DaT film by interfacial polymerization: 0.05-0.09 mmol of 2,6-diaminoanthracene (Da) was dissolved in a mixture of 40-140 mL of 1,4-dioxane and water in the bottom layer, and 0.2-0.5 mmol of toluenesulfonic acid was added to complete the mixing; 0.02-0.08 mmol of 1,3,5-trihydroxy-2,4,6-triformylbenzene (Tp) was then dissolved in 90 mL of mesitylene in the upper layer; the upper layer liquid was gradually added dropwise to the surface of the lower layer liquid using a dropper while keeping the lower liquid phase stable; the density difference between the two solutions produced an obvious liquid-liquid interface; the mixture was kept at room temperature for 3 days; and a reddish-brown COF-DaTp film was obtained by separation.

[0029] Further, after the obtained COF-DaTp film was transferred to an ITO substrate, the COF DaTp on the ITO substrate was washed with 30 mL of DMF, water, and ethanol, respectively, to remove excess unpolymerized monomers, and then dried under vacuum at 50 ° C. The cleaned film will be used for subsequent characterization and device preparation.

[0030] Furthermore, the mixture of 1,4-dioxane and water is a mixture of 30-90 mL of 1,4-dioxane and 10-50 mL of water.

[0031] The above preparation method is more specific as follows: Preparation of COF-DaT film by interfacial polymerization: 1,3,5-trihydroxy-2,4,6-triformylbenzene (Tp) (0.05mmol) is dissolved in 90mL of mesitylene in the upper layer, while 2,6-diaminoanthracene (Da) (0.075mmol) is dissolved in a mixture of 90mL of 1,4-dioxane (60mL) and water (30mL) in the bottom layer. In addition, p-toluenesulfonic acid (0.25mmol) is added to the bottom solution. The upper liquid is gradually added while keeping the bottle liquid phase stable. The density difference between the two solutions produces a clear liquid-liquid interface. At this interface, the two functional monomers undergo imide polycondensation and dehydration. After being kept at room temperature for 3 days, the reaction continues. After a reaction period of 3 days, a reddish-brown COF-DaTp film is isolated and transferred to an ITO substrate. The COF DaTp on the ITO substrate is washed with 30mL of DMF, water and ethanol, respectively, to remove excess unpolymerized monomers. The film was dried in vacuum at 50 °C. The cleaned film will be used for subsequent characterization and device preparation.

[0032] The present invention also provides an application of the anthracene-based two-dimensional covalent organic framework (COF-DaTp) device with photoelectric dual response in a photoelectric synapse device.

[0033] Furthermore, by applying light pulses of different wavelengths to the device, the device exhibited dual photoelectric modulation, showing significant photoresistance switching in response to the light pulses, and realizing 32 photoconductivity states.

[0034] Furthermore, it exhibits history-dependent memristive behavior in voltage sweeps and electrical pulses, with 32 conductive states, and has excellent prospects in preparing miniaturized devices and reducing energy loss in memory devices.

[0035] Beneficial technical effects of the present invention:

[0036] 1. The simple adjustability of the optoelectronic synaptic device described in the present invention, which uses the optoelectronic dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) material film as the active layer. (e.g. Figure 2 , Figure 3 (shown)

[0037] 2.COF-DaTp as an active layer has good thermal stability and electrical properties. The storage device with (COF-DaTp) as the active layer has stable performance and high yield. Figure 6 Resistance state stability)

[0038] 3. The device has photoelectric dual response characteristics and is widely used in the field of new generation low-power information storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 Schematic diagram of the preparation of anthracene-based two-dimensional covalent organic framework (COF-DaTp) materials with dual photoelectric response

[0040] Figure 2 The photocurrent changes of the photoelectric dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) photoelectric synapse device under 365 and 254 nm light respectively.

[0041] Figure 3 The memristor curves of the optoelectronic dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) optoelectronic synaptic device under negative voltage scanning and positive voltage scanning, respectively.

[0042] Figure 4 Schematic diagram of the structure of the optoelectronic dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) optoelectronic synapse

[0043] Figure 5 Schematic diagram of the solid-state NMR of the photoelectric dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp)

[0044] Figure 6 Schematic diagram of the stability of 32 resistive states of the optoelectronic dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) DETAILED DESCRIPTION

[0045] The present invention is further described in detail below in conjunction with the accompanying drawings and its implementation methods. It should be noted that the described implementation methods are preferred implementation methods of the present invention, and the actual structure is not limited thereto. Based on the embodiments described in the present invention, if ordinary technicians in the field obtain embodiments similar to the technical solution without departing from the design purpose of the present invention, they should all fall within the protection scope of the present invention.

[0046] Example 1

[0047] 1. The preparation method of the photoelectric dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) active layer is as follows:

[0048] Preparation of COF-DaT thin films by interfacial polymerization: Figure 1As shown, 1,3,5-trihydroxy-2,4,6-triformylbenzene (Tp) (0.05mmol) was dissolved in 90mL of mesitylene in the upper layer, while 2,6-diaminoanthracene (Da) (0.075mmol) was dissolved in a mixture of 90mL of 1,4-dioxane (60mL) and water (30mL) in the bottom layer. In addition, p-toluenesulfonic acid (0.25mmol) was added to the bottom solution. The upper liquid was gradually added while keeping the bottle liquid phase stable. The density difference between the two solutions produced a clear liquid-liquid interface. At this interface, the two functional monomers underwent imine polycondensation and dehydration. After 3 days at room temperature, the reaction continued. After a 3-day reaction period, a reddish-brown COF-DaTp film was isolated and transferred to an ITO substrate. The COF DaTp on the ITO substrate was washed with 30mL of DMF, water, and ethanol, respectively, to remove excess unpolymerized monomers. It was dried in a vacuum at 50°C. The cleaned film will be used for subsequent characterization and device preparation. Figure 5 It is solid-state nuclear magnetic.

[0049] Effect Example 2

[0050] 2. Preparation method of anthracene-based two-dimensional covalent organic framework (COF-DaTp) material device with photoelectric dual response:

[0051] 1) Wash the ITO-coated glass substrate 1.5 cm×1.5 cm with detergent and deionized water, then wash in ethanol, acetone and isopropanol for 15 minutes respectively and dry.

[0052] 2) Using a spin coating method to cover a COF-DaTp polymer layer with a thickness of 100nm-200nm on the ITO glass;

[0053] 3) vacuum drying the obtained device overnight to remove excess solution;

[0054] 4) Use a vacuum coating apparatus to coat the Al top electrode (thickness 100-200nm, area about 0.4×0.4mm 2 ) is plated on the active layer through a mask, and finally the device Al / COF-DaTp / ITO is obtained.

[0055] Device structure such as Figure 4 Shown

[0056] Effect Example 1

[0057] like Figure 2As shown in Figure 1, upon irradiation with 365 nm light, the anthracene units dimerize. Initially, anthracene is in a monomeric state, which is characterized by high conjugation and enhanced intramolecular conductivity compared to the dimerized state. This leads to a significant change in the current after 365 nm illumination. Due to the reversibility of anthracene dimerization, the resistance state returns to the initial state after a 254 nm light pulse. Figure 2 As shown in Figure 2, the Al / COF DaTp / ITO device can exhibit 32 different conductive states when exposed to 365nm light pulses. After subsequent exposure to 254nm light pulses, the conductive state of the device gradually returns to the initial level.

[0058] Effect Example 2

[0059] like Figure 3 As shown in Figure 2, a continuous 32-cycle (0→-1→0V) negative voltage scan shows that the device current gradually increases from -6.34×10-4A to -9.56×10-4A ( Figure 5 b), and the subsequent 32 cycles of positive voltage sweep (0→1→0V) reduced the current from 9.98×10-4A to 6.67×10-4A. These changes indicate that the device can adjust its conductivity under continuous voltage sweeps, showing history-dependent memristive behavior. Therefore, changing the voltage can effectively and continuously regulate the conductivity of the device, which is a major feature of the synapse and is called nonlinear transmission characteristics.

[0060] The above-mentioned preparation steps, effect examples and attached data are preferred embodiments of the present invention. Other embodiments within the protection scope can also obtain the above-mentioned beneficial effects, which will not be described in detail here. It should be pointed out that for ordinary technicians in this technical field, without departing from the concept of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as within the protection scope of the present invention.

Claims

1. A photoelectric dual-response anthracene-based two-dimensional covalent organic framework device, characterized in that: Its structure from bottom to top is: (1) Glass substrate; (2) Indium tin oxide electrode (ITO); (3) COF-DaTp thin film active layer; (4) Aluminum electrode.

2. The optoelectronic dual-response anthracene-based two-dimensional covalent organic framework device according to claim 1, characterized in that: The device has dual photoelectric modulation functions: the device exhibits significantly different resistance states under different light pulses, exhibits significant photoresistance switching to light pulses, and realizes 32 photoconductivity states.

3. The optoelectronic dual-response anthracene-based two-dimensional covalent organic framework device according to claim 1, characterized in that: The structure of COF-DaTp in the active layer of the covalent organic framework film is shown in the following formula:

4. The optoelectronic dual-response anthracene-based two-dimensional covalent organic framework device according to claim 1, characterized in that: The thickness of COF-DaTp in the covalent organic framework thin film active layer is 30-200nm.

5. A method for preparing the active layer of the photoelectric dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) material according to claim 1 is as follows: Preparation of COF-DaT film by interfacial polymerization: 0.05-0.09 mmol of 2,6-diaminoanthracene (Da) was dissolved in a mixture of 40-140 mL of 1,4-dioxane and water in the bottom layer, and 0.2-0.5 mmol of toluenesulfonic acid was added to complete the mixing; 0.02-0.08 mmol of 1,3,5-trihydroxy-2,4,6-triformylbenzene (Tp) was then dissolved in 90 mL of mesitylene in the upper layer; the upper layer liquid was gradually added dropwise to the surface of the lower layer liquid using a dropper while keeping the lower liquid phase stable; the density difference between the two solutions produced an obvious liquid-liquid interface; the mixture was kept at room temperature for 3 days; and a reddish-brown COF-DaTp film was obtained by separation.

6. A method for preparing the active layer of the photoelectric dual-responsive anthracene-based two-dimensional covalent organic framework (COF-DaTp) material according to claim 5, characterized in that: After the obtained COF-DaTp film was transferred to an ITO substrate; the COF-DaTp on the ITO substrate was washed with 30 mL DMF, water and ethanol respectively to remove excess unpolymerized monomers; and vacuum dried at 50°C.

7. A method for preparing an anthracene-based two-dimensional covalent organic framework device with a photoelectric dual response, comprising the following steps: 1) Clean the glass substrate coated with ITO and dry it; 2) COF-DaT film was prepared by interfacial polymerization, and a reddish-brown COF-DaTp film was separated and transferred to an ITO substrate; the COF DaTp on the ITO substrate was washed with 30 mL of DMF, water, and ethanol, respectively, to remove excess unpolymerized monomers; 3) vacuum drying the obtained device overnight to remove excess solution; 4) Finally, an Al top electrode is plated on the active layer to obtain the device Al / COF-DaTp / ITO.

8. Use of the anthracene-based two-dimensional covalent organic framework (COF-DaTp) device with optoelectronic dual response according to any one of claims 1 to 4 in optoelectronic synapse devices.

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