An inorganic chloride-doped polymer electrolyte hybrid dielectric film material, a preparation method and application thereof

Abstract

The application relates to an inorganic chloride-doped polymer electrolyte hybrid dielectric film material and a preparation method and application thereof, and belongs to the technical field of dielectric film materials and devices. The inorganic chloride-doped polymer electrolyte hybrid dielectric film material has significantly enhanced capacitance and ion migration capacity, can be used for developing an organic transistor memory with multi-level response to different pulse voltages, and can realize a wide memory window of 0.548 volts at a low working voltage of-1.5 volts. The memory also has good static and dynamic storage characteristics, and can realize accurate regulation and identification of different sizes of memory windows through programming gate pulse voltage. The novel polymer electrolyte hybrid dielectric film material and the organic transistor memory with multi-level storage characteristics thereof have the advantages of simple structure, excellent performance, easy scale-up manufacturing and the like, and will have good popularization and application prospects in the field of low-power-consumption optoelectronic devices and storage technologies.

Description

Technical Field

[0001] This invention belongs to the technical field of dielectric thin film materials and devices, and relates to a polymer electrolyte hybrid dielectric thin film material based on inorganic chloride doping, its preparation method and application. Background Technology

[0002] The continuous development of IoT and AI technologies has led to an explosive growth in data volume, creating an urgent need for high-performance advanced storage materials and devices. Memory is a component in digital communication, computer equipment, and electronic instruments used to temporarily or permanently store program execution data and instructions for easy access and processing. Organic field-effect transistors (OFETs), due to the easily modulated characteristics of their key components such as organic semiconductors and gate dielectric layers, can achieve functions such as synaptic plasticity, data storage, and in-memory computation, and are gradually developing into a new generation of storage devices with broad application prospects in the field of advanced storage technology.

[0003] Recent research on organic transistor memory devices has primarily focused on the selection of dielectric layer materials and the design of floating-gate device structures. Compared to floating-gate device structures, organic transistor memories based on functional dielectric layer materials are attracting increasing attention due to the diverse material choices and the ability to control the structure and properties of the materials through multiple pathways to adjust device parameters and achieve storage characteristics. However, current research on organic transistor memories largely concentrates on widening the memory window, with few studies achieving multi-level storage characteristics while maintaining flexibility and low operating voltage. For applications such as wearable devices, developing flexible, low-voltage organic transistor memories capable of meeting multi-level storage requirements is crucial. Currently, a common approach is to fabricate functional materials with charge transfer properties as the dielectric layer of organic transistor memories, achieving storage functionality through precise control of device performance. However, this method struggles to reduce the device's operating voltage. Furthermore, using dielectric layer materials with ferroelectric polarization properties can also achieve storage functionality in organic transistors, but the ferroelectric properties in organic material systems are susceptible to external interference affecting storage performance, thus limiting the application of organic transistor memories.

[0004] Polymer electrolyte materials can utilize the ion migration capabilities of the electrolyte to alter the capacitance and dielectric constant of the dielectric layer, potentially enabling the storage function of organic transistor memories. However, simultaneously achieving flexible, low-voltage operation and multi-level storage characteristics in organic transistor memories remains extremely challenging. Therefore, it is necessary to develop a novel polymer electrolyte hybrid dielectric material system based on inorganic chloride-doped polymer electrolytes, which is of great significance for the design and optimization of high-performance organic transistor memories. Summary of the Invention

[0005] In view of this, one objective of the present invention is to provide a polymer electrolyte hybrid dielectric thin film material based on inorganic chloride doping; a second objective of the present invention is to provide a method for preparing a polymer electrolyte hybrid dielectric thin film material based on inorganic chloride doping; a third objective of the present invention is to provide an application of a polymer electrolyte hybrid dielectric thin film material based on inorganic chloride doping in the preparation of organic transistor memories, optoelectronic devices, or electrical equipment; a fourth objective of the present invention is to provide an organic transistor memory; a fifth objective of the present invention is to provide a method for preparing an organic transistor memory; and a sixth objective of the present invention is to provide an application of an organic transistor memory in static and dynamic storage, as well as in optoelectronic devices or electrical equipment.

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

[0007] 1. According to one aspect of the present invention, a polymer electrolyte hybrid dielectric thin film material based on inorganic chloride doping is provided, the polymer electrolyte hybrid dielectric thin film material comprising a polymer electrolyte material and doped inorganic chloride, wherein the inorganic chloride accounts for 0.05 to 20 wt.% of the total mass of the inorganic chloride and the polymer electrolyte material;

[0008] The polymer electrolyte material is at least one of the following: acrylamide polymer electrolyte or its derivatives, acrylic polymer electrolyte or its derivatives, acrylic polymer electrolyte or its derivatives, polymer electrolyte composite dielectric material formed by blending polyacrylic acid and polyethylene glycol, and polymer electrolyte composite dielectric material formed by blending polyacrylic acid and polyvinyl alcohol.

[0009] Preferably, the inorganic chloride is any one or more of zinc chloride, calcium chloride, ferric chloride, copper chloride, cobalt chloride, magnesium chloride, lithium chloride, sodium chloride, or potassium chloride.

[0010] Preferably, the mass ratio of polyacrylic acid to polyethylene glycol in the polymer electrolyte composite dielectric material formed by blending polyacrylic acid and polyethylene glycol is 1:0.1 to 1:0.6, and the mass ratio of polyacrylic acid to polyvinyl alcohol in the polymer electrolyte composite dielectric material formed by blending polyacrylic acid and polyvinyl alcohol is 1:0.1 to 1:0.7.

[0011] 2. According to another aspect of the present invention, a method for preparing the above-mentioned polymer electrolyte hybrid dielectric thin film material based on inorganic chloride doping is provided, the method comprising the following steps:

[0012] (1) Dissolve the polymer electrolyte in a solvent and stir at room temperature to obtain a precursor solution of the polymer electrolyte;

[0013] (2) Add inorganic chloride to the precursor solution of the polymer electrolyte and stir evenly at room temperature to obtain a solution of inorganic chloride-doped polymer electrolyte;

[0014] (3) After spin-coating the solution of the inorganic chloride-doped polymer electrolyte into a film, annealing it at 50-200°C for more than 30 minutes, a polymer electrolyte hybrid dielectric thin film material based on inorganic chloride doping can be obtained.

[0015] Preferably, in step (1), the solvent is any one or more of water, methanol, ethanol or isopropanol, and the concentration of the polymer electrolyte in the precursor solution of the polymer electrolyte is 3 to 60 mg / mL.

[0016] In step (2), the stirring time at room temperature is 3 to 24 hours.

[0017] More preferably, in step (1), the solvent is any one of methanol, ethanol or isopropanol, and the concentration of the polymer electrolyte in the precursor solution of the polymer electrolyte is 10-50 mg / mL;

[0018] More preferably, in step (1), the solvent is methanol or ethanol, and the concentration of the polymer electrolyte in the precursor solution of the polymer electrolyte is 15-45 mg / mL.

[0019] 3. According to another aspect of the present invention, the application of the above-described polymer electrolyte hybrid dielectric thin film material based on inorganic chloride doping is provided in the fabrication of organic transistor memories, optoelectronic devices or electrical equipment.

[0020] 4. According to another aspect of the present invention, an organic transistor memory is provided, the organic transistor memory comprising, from bottom to top, a substrate, a semiconductor layer, a double dielectric layer formed by an interface passivation dielectric layer and a polymer electrolyte hybrid dielectric layer, and a gate, wherein a source and a drain are respectively disposed between the surface of the substrate and the semiconductor layer;

[0021] The material of the polymer electrolyte hybrid dielectric layer includes the aforementioned polymer electrolyte hybrid dielectric film material based on inorganic chloride doping.

[0022] 5. According to another aspect of the present invention, a method for fabricating the above-described organic transistor memory is provided, the method comprising the following steps:

[0023] (1) Source and drain materials are prepared on the substrate surface by any one of magnetron sputtering, vacuum thermal evaporation, atomic layer deposition, inkjet printing or drop coating to form source and drain, respectively, wherein a conductive channel with micro-nano scale spacing is formed between the source and drain.

[0024] (2) On the source, drain and substrate surfaces, an organic semiconductor material is prepared to form a semiconductor layer by any one of spin coating, blade coating or inkjet printing.

[0025] (3) On the surface of the semiconductor layer, the material of the interface passivation dielectric layer is prepared by any one of atomic layer deposition, vacuum thermal evaporation, magnetron sputtering, spin coating, blade coating or inkjet printing to form an interface passivation dielectric layer.

[0026] (4) On the surface of the interface passivation dielectric layer, the above-mentioned polymer electrolyte hybrid dielectric film material based on inorganic chloride doping is coated by any one of the solution processing methods of spin coating, blade coating or inkjet printing and then annealed to prepare the polymer electrolyte hybrid dielectric layer based on inorganic chloride doping.

[0027] (5) On the surface of the inorganic chloride-doped polymer electrolyte hybrid dielectric layer, a gate material is prepared by any one of magnetron sputtering, vacuum thermal evaporation, atomic layer deposition, inkjet printing or drop coating to form a gate, thereby obtaining an organic transistor memory.

[0028] Preferably, in step (1), the substrate material is any one or more of polyethylene terephthalate, polyethylene naphthalate, polyimide, polydimethylsiloxane, polycarbonate, polyvinyl alcohol, glass, silicon dioxide / silicon, or sapphire, and the source and drain materials are any one or more of gold, silver, aluminum, copper, chromium, platinum, titanium, nickel, indium tin oxide, fluorine-doped tin oxide, zinc aluminum oxide, carbon nanotubes, graphene, or conductive polymers.

[0029] In step (2), the material of the semiconductor layer is an organic conjugated polymer or an organic small molecule semiconductor material. The material of the semiconductor layer includes any one or more of poly(3-hexylthiophene), indole-dithiophene-benzothiadiazole copolymer, polythiophene derivative, polyfluorene derivative, poly(p-phenylene acetylene) derivative, pentaphenyl, 7,7,8,8-tetracyano-p-benzodiquinone dimethane, or copper phthalocyanine.

[0030] In step (3), the material of the interface passivation dielectric layer is any one or more of polymethyl methacrylate, polystyrene, polymers with a dielectric constant greater than 3, metal oxide dielectrics, or silicon dioxide.

[0031] In step (4), when spin coating is used as a solution processing method, the spin coating speed is 200-5000 rpm, the spin coating time is 20-150 s, the annealing temperature after spin coating is 50-200℃, and the annealing time is not less than 30 min.

[0032] In step (5), the gate material is any one or more of gold, silver, aluminum, copper, chromium, platinum, titanium, nickel, indium tin oxide, fluorine-doped tin oxide, zinc aluminum oxide, carbon nanotubes, graphene, or conductive polymers.

[0033] More preferably, in step (1), the material of the substrate is any one or more of polyethylene naphthalate, polyethylene terephthalate, polyimide or polydimethylsiloxane, and the source and drain materials are any one of gold, silver, aluminum or copper.

[0034] In step (2), the material of the semiconductor layer is an organic conjugated polymer material, including any one or more of poly(3-hexylphen), indahedron-dithiophene-benzothiadiazole copolymer, polyfluorene derivative, and poly(p-phenylacetylene) derivative;

[0035] In step (3), the material of the interface passivation dielectric layer is any one or more of polymethyl methacrylate or polystyrene;

[0036] In step (4), when spin coating is used as a solution processing method, the annealing temperature after spin coating is 80-150℃;

[0037] In step (5), the gate material is any one of gold, silver, aluminum or copper.

[0038] 6. According to another aspect of the invention, the above-described organic transistor memory is provided for use in static and dynamic storage, as well as in optoelectronic devices or electrical equipment.

[0039] The beneficial effects of this invention are as follows:

[0040] 1. This invention discloses a polymer electrolyte hybrid dielectric film material based on inorganic chloride doping, mainly comprising a polymer electrolyte material and doped inorganic chlorides, which has the following advantages: (1) It can achieve the regulation of ion migration under an applied voltage, thereby changing the capacitance of the polymer electrolyte hybrid dielectric film. It not only successfully realizes the enhancement and tuning of capacitance, but can also be used to conveniently adjust the storage properties of organic transistors. In addition, different inorganic chlorides doped into the polymer electrolyte dielectric film will significantly increase the number of free ions in the film, enhance the ion conductivity of the film, and affect the electrical properties of the film, providing an effective way to regulate and optimize the electrical properties of the polymer electrolyte dielectric film material and its organic transistors. (2) This type of material is abundant, inexpensive, thickness-insensitive, and easy to process and manufacture on a large scale, giving it unique advantages in constructing high-performance flexible low-power organic transistors and their memories. (3) The inorganic chloride doping effect of this type of dielectric thin film material can greatly enhance the ion migration ability and double layer effect in the polymer electrolyte dielectric thin film material, so that organic transistors and their memories can work more effectively under low voltage conditions and the threshold voltage is also greatly reduced, which helps the design and development of low power electronic devices.

[0041] 2. This invention also discloses an organic transistor memory. This novel memory uses an inorganic chloride-doped polymer electrolyte hybrid dielectric film as the constituent material of its double dielectric layer, achieving excellent static and dynamic storage characteristics. Under the influence of the programming gate pulse voltage, ions within the inorganic chloride-doped polymer electrolyte hybrid dielectric film migrate to different positions on the film, enabling multi-level storage characteristics of the organic transistor memory. Furthermore, this memory can be effectively written using the programming gate pulse voltage and erased using the reverse programming gate pulse voltage and ultraviolet light irradiation. It also enables rapid writing via electrical pulses to meet the application requirements of convenient storage. These technologies overcome the limitations of traditional organic transistor memory strategies that use floating gate device structures to achieve storage functions, providing new options and beneficial ideas for the construction of high-performance organic transistor memories.

[0042] Other advantages, objectives, and features of the invention will be set forth in part in the description which follows, and in part will be apparent to those skilled in the art from the following examination, or may be learned from practice of the invention. The objectives and other advantages of the invention can be realized and obtained through the following description. Attached Figure Description

[0043] To make the objectives, technical solutions, and advantages of the present invention clearer, the preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings, wherein:

[0044] Figure 1 This is a schematic diagram of the organic transistor memory structure based on zinc chloride-doped polymer electrolyte hybrid dielectric thin film material prepared in Example 4;

[0045] Figure 2 The image shows the EDS elemental distribution of the zinc chloride-doped polymer electrolyte hybrid dielectric thin film material prepared in Example 1 after initial and voltage application.

[0046] Figure 3 The transfer (a) and output (b) characteristic curves of the organic transistor memory based on zinc chloride-doped polymer electrolyte hybrid dielectric thin film material prepared in Example 4 are shown.

[0047] Figure 4 The multilevel write characteristics of the organic transistor memory based on zinc chloride-doped polymer electrolyte hybrid dielectric thin film material prepared in Example 4 are shown, wherein the gate pulse voltage application times in a, b and c are 2s, 10s and 30s, respectively;

[0048] Figure 5 The erase characteristics of the organic transistor memory based on the zinc chloride-doped polymer electrolyte hybrid dielectric thin film material prepared in Example 4;

[0049] Figure 6 The positive bias (a) and negative bias (b) electrical impulse response characteristics of the organic transistor memory based on zinc chloride-doped polymer electrolyte hybrid dielectric thin film material prepared in Example 4;

[0050] Figure 7 The positive bias (a) and negative bias (b) electrical impulse response characteristics of the organic transistor memory based on the copper chloride-doped polymer electrolyte hybrid dielectric thin film material prepared in Example 5;

[0051] Figure 8 The positive bias (a) and negative bias (b) electrical impulse response characteristics of the organic transistor memory based on the ferric chloride-doped polymer electrolyte hybrid dielectric thin film material prepared in Example 6;

[0052] In the schematic diagram of the organic transistor memory, 1 is the substrate, 2 is the source, 3 is the drain, 4 is the semiconductor layer, 5 is the interface passivation dielectric layer, 6 is the inorganic chloride-doped polymer electrolyte hybrid dielectric layer, and 7 is the gate. Detailed Implementation

[0053] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the illustrations provided in the following embodiments are only schematic representations of the basic concept of the present invention. Unless otherwise specified, the following embodiments and features can be combined with each other.

[0054] The inorganic chloride-doped polymer electrolyte films used in the following examples employ organic polymer electrolyte materials (PAA and PEG);

[0055] The structural formulas of the PAA and PEG are as follows: Where n is a positive integer.

[0056] The inorganic chlorides used for doping are zinc chloride, calcium chloride, copper chloride, and ferric chloride.

[0057] Unless otherwise specified, the following examples were conducted under conventional conditions or conditions recommended by the manufacturer. Unless otherwise stated, the raw materials and solvents used in the examples of this invention were purchased commercially.

[0058] The organic polymer semiconductor material, benzothiophene-benzothiadiazole copolymer, was purchased from Shenzhen Ruixun Optoelectronic Materials Technology Co., Ltd.

[0059] Chlorobenzene and methanol solvents were purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.

[0060] Polyacrylic acid and polyethylene glycol were purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.

[0061] Zinc chloride, calcium chloride, copper chloride, and ferric chloride were purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0062] The polystyrene was purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.

[0063] Butyl acetate solvent was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0064] Example 1

[0065] A polymer electrolyte hybrid dielectric thin film material based on zinc chloride doping is prepared by solution spin coating, the specific method of which is as follows:

[0066] (1) Polyacrylic acid and polyethylene glycol in a mass ratio of 7:3 were dissolved in methanol to obtain a precursor solution of polymer electrolyte. The concentration of polyacrylic acid in the precursor solution of polymer electrolyte was 30 mg / mL. Zinc chloride was added to the precursor solution of polymer electrolyte (the added zinc chloride accounted for 2.62 wt.% of the total solute (polyacrylic acid, polyethylene glycol and zinc chloride)). The mixture was stirred at room temperature for 5 h to make it uniform, and a solution of zinc chloride-doped polymer electrolyte was obtained.

[0067] (2) In a glove box under a nitrogen atmosphere, spin-coat a 5 mg / mL interface passivation dielectric layer solution (5 mg of polystyrene was dissolved in 1 mL of butyl acetate and stirred at room temperature for 5 h to obtain the interface passivation dielectric layer solution) onto a polyethylene naphthalate substrate (spin-coating speed was 2000 rpm and spin-coating time was 30 s) to form an interface passivation dielectric layer. Then spin-coat a solution of zinc chloride-doped polymer electrolyte prepared in step (1) onto the interface passivation dielectric layer film (spin-coating speed was 500 rpm and spin-coating time was 30 s, spin-coating was done twice). Annealing was performed on a heating stage at 80 °C for 20 min to obtain a polymer electrolyte hybrid dielectric film material based on zinc chloride doping.

[0068] Example 2

[0069] A polymer electrolyte hybrid dielectric thin film material based on copper chloride doping, the specific preparation method of which is as follows:

[0070] In Example 1, “zinc chloride” was replaced with “copper chloride”, and the rest was the same as in Example 1.

[0071] Example 3

[0072] A polymer electrolyte hybrid dielectric thin film material based on calcium chloride doping, the specific preparation method of which is as follows:

[0073] In Example 1, “zinc chloride” was replaced with “calcium chloride”, and the rest was the same as in Example 1.

[0074] Example 4

[0075] A schematic diagram of an organic transistor memory is shown below. Figure 1 As shown, the structure from bottom to top includes: a substrate 1, a semiconductor layer 4, a double dielectric layer (wherein an interface passivation dielectric layer 5 is located on the semiconductor layer 4, and an inorganic chloride-doped polymer electrolyte hybrid dielectric layer 6 is located on the interface passivation dielectric layer 5), and a gate 7. A source 2 and a drain 3 with channel patterns are located on the surfaces at both ends of the substrate 1. The fabrication method of this organic transistor memory based on an inorganic chloride-doped polymer electrolyte hybrid dielectric thin film material is as follows:

[0076] (1) A 125 μm thick polyethylene naphthalate was used as the substrate;

[0077] (2) On the surfaces at both ends of the above substrate, gold is deposited through a mask using a vacuum thermal evaporation process (vacuum degree approximately 2×10⁻⁶). -4 Pa, evaporation rate is approximately A 50 nm thick source and drain electrode were fabricated, with a channel with a width of 22.5 mm and a length of 0.15 mm between the fabricated source and drain electrode, respectively, to obtain a substrate with source and drain electrode.

[0078] (3) In a glove box under a nitrogen atmosphere, prepare a chlorobenzene solution of indahedron dithiophene-benzothiadiazole copolymer with a concentration of 5 mg / mL and spin coat it onto the substrate with source and drain obtained in step (2) (wherein the spin coating speed is 2000 rpm and the spin coating time is 30 s). After spin coating, anneal it on a heating stage at 90°C for 20 min to prepare a semiconductor layer.

[0079] (4) In a glove box under a nitrogen atmosphere, spin-coat a 5 mg / mL polystyrene butyl acetate solution onto the semiconductor layer obtained in step (3) (the spin-coating speed is 2000 rpm and the spin-coating time is 30 s), and then let it stand for 10 min to prepare the interface passivation dielectric layer.

[0080] (5) In a glove box under a nitrogen atmosphere, the solution of the zinc chloride-doped polyelectrolyte hybrid dielectric film material prepared in Example 1 is spin-coated onto the interface passivation dielectric layer obtained in step (4) (the spin-coating speed is 500 rpm, the spin-coating time is 30 s, and the spin-coating is done twice). Then, the inorganic chloride-doped polymer electrolyte hybrid dielectric layer is prepared by annealing on a heating stage at 90°C for 120 min.

[0081] (6) On the above-mentioned inorganic chloride-doped polymer electrolyte hybrid dielectric layer, a vacuum thermal evaporation process (vacuum degree approximately 2 × 10⁻⁶) is performed using a mask and a vacuum thermal evaporation process. -4 Pa, evaporation rate is approximately An organic transistor memory based on an inorganic chloride-doped polymer electrolyte hybrid dielectric thin film material can be fabricated by preparing a 50nm thick gold gate, in which the gate completely covers the channel formed between the source and drain.

[0082] Examples 5-22

[0083] The differences between the fabrication processes of organic transistor memories based on inorganic chloride-doped polymer electrolyte hybrid dielectric thin film materials in Examples 5-22 and Example 4 are shown in Table 1. The parts not described are the same as in Example 4.

[0084] Table 1. Organic transistor memory based on inorganic chloride-doped polymer electrolyte hybrid dielectric thin film material prepared according to different embodiments.

[0085]

[0086]

[0087] Performance testing

[0088] 1. Characterization of inorganic chloride-doped polymer electrolyte hybrid dielectric thin film materials by ion migration testing

[0089] The elemental distribution of the zinc chloride-doped polymer electrolyte hybrid dielectric film material prepared in Example 1 was tested using a scanning electron microscope (Hitachi SU8010) combined with energy-dispersive X-ray spectroscopy (EDS) elemental imaging. The ion migration phenomenon of zinc chloride doped in the polymer electrolyte dielectric film under different bias voltages was studied. Figure 2 The images show the initial and voltage-treated EDS elemental distributions of the zinc chloride-doped polymer electrolyte hybrid dielectric thin film material prepared in Example 1. Figure 2 The initial elemental mapping confirms the uniform distribution of carbon (C), oxygen (O), zinc (Zn), and chloride (Cl) elements in the polymer electrolyte hybrid dielectric film. After applying a 10V voltage for 3 hours, the elemental mapping of the polymer electrolyte hybrid dielectric film shows that C, O, and Cl elements aggregate near the positive electrode region, indicating the migration of negatively charged polyacrylate ions and chloride ions towards the positive electrode. Simultaneously, the aggregation of Zn elements near the negative electrode region indicates the migration of positively charged zinc ions towards the negative electrode. Furthermore, after applying a 20V voltage for 3 hours, the elemental mapping of the polymer electrolyte hybrid dielectric film shows even more significant aggregation behavior of C, O, Zn, and Cl elements, indicating that more ions migrate towards their respective electrodes. These results demonstrate that applying voltage to inorganic chloride-doped polymer electrolyte hybrid dielectric film materials can effectively promote the migration of charged ions within the film. Therefore, it can be seen that in this type of inorganic chloride-doped polymer electrolyte hybrid dielectric film material, the ion migration capability is adjustable depending on the applied voltage. The stronger the voltage, the more significant the ion migration effect. Thus, it can be used as the dielectric layer of organic transistor memory to meet the storage application requirements.

[0090] 2. Capacitance testing of inorganic chloride-doped polymer electrolyte hybrid dielectric thin film materials.

[0091] Low-frequency (0.1 Hz) capacitance tests were performed on the three inorganic chloride-doped polymer electrolyte hybrid dielectric film materials prepared in Examples 1-3 above using an LCR digital bridge (TH2827C). The results are summarized in Table 2. It can be seen that the initial-state capacitances of the polymer electrolyte hybrid dielectric films doped with zinc chloride, copper chloride, and calcium chloride are 150.21, 160.61, and 160.87 nF cm⁻¹, respectively. -2 After applying a voltage of -4.5V for 30 seconds, the zinc chloride-doped capacitance decreased by 29.40 nF cm⁻¹. -2 Copper chloride doping reduced the capacitance by 15.10 nF cm⁻¹. -2 Calcium chloride doping reduced the capacitance by 31.69 nF cm⁻¹. -2 The results confirmed the mechanism by which ion migration affects capacitance in polymer electrolyte dielectric films, demonstrating that the capacitance can be effectively altered by applying voltage to regulate the ion distribution within the film. Simultaneously, it was also confirmed that copper chloride exhibits the weakest ion migration ability in the film, while calcium chloride demonstrates the strongest.

[0092] Table 2. Comparison of capacitance of different inorganic chloride-doped polymer electrolyte hybrid dielectric film materials under initial conditions and after applying a voltage of -4.5V for 30s.

[0093]

[0094] 3. Performance testing of organic transistor memory based on inorganic chloride-doped polymer electrolyte hybrid dielectric thin film material.

[0095] The electrical performance of the organic transistor memory prepared in Example 4 was tested using an Agilent 4155c semiconductor parameter analyzer. Its transfer and output characteristic curves are shown below. Figure 3 As shown (where a is the transfer characteristic curve and b is the output characteristic curve). From Figure 3 It can be seen that the zinc chloride-doped polymer electrolyte hybrid dielectric thin film material prepared in Example 1 of this invention and the corresponding organic transistor memory (Example 4) have good transistor characteristics and low-voltage operating capability. Using an Agilent 4155c semiconductor parameter analyzer and a UV curing device (UVACUBE 100), the organic transistor memory prepared in Example 4 was tested for multi-level write and erase behavior. Figure 4 The multilevel write characteristics of the organic transistor memory based on zinc chloride-doped polymer electrolyte hybrid dielectric thin film material prepared in Example 4 are shown, wherein the gate pulse voltage application times in a, b and c are 2s, 10s and 30s, respectively; Figure 5 The erase characteristics of the organic transistor memory based on the zinc chloride-doped polymer electrolyte hybrid dielectric thin film material prepared in Example 4 are shown. Figure 4 and Figure 5 It can be seen that the organic transistor memory based on the inorganic chloride-doped polymer electrolyte hybrid dielectric film material of this invention has excellent write and erase characteristics. In particular, under the same programming gate pulse voltage duration, the larger the gate impulse voltage, the larger the memory window of the organic transistor memory, and the effect of negative pulse voltage on the memory window of the organic transistor memory is more significant than that of positive pulse voltage; under the same programming gate pulse voltage, the longer the gate impulse voltage duration, the larger the memory window of the organic transistor memory. Furthermore, after applying programming gate pulse voltages of different amplitudes for the same duration to the organic transistor memory, the threshold voltage of the organic transistor memory will drift to different degrees; similarly, after applying programming gate pulse voltages of the same amplitude for different durations, the threshold voltage of the organic transistor memory will also drift to different degrees; and for each increase in the voltage amplitude or duration of the programming gate voltage, the threshold voltage will undergo a significant readable drift change, thus indicating that the organic transistor memory successfully achieves controllable threshold voltage changes through ion migration in the zinc chloride-doped polymer electrolyte hybrid dielectric film, that is, the organic transistor memory has multi-level storage characteristics. When operating at a low voltage of -1.5V, the maximum memory window of the organic transistor memory is 0.548V, meaning that 36.5% of the scan range is converted into a memory window for writing. Simultaneously, applying a reverse gate pulse voltage enables the erase operation of the organic transistor memory, and rapid erasure can be achieved through ultraviolet light irradiation (e.g., ...). Figure 5 (As shown).

[0096] The electrical pulse response characteristics of the organic transistor memory based on a zinc chloride-doped polymer electrolyte hybrid dielectric film prepared in Example 4 were tested using a relay and an Agilent 4155c semiconductor parameter analyzer. By adjusting the programming gate pulse voltage, its response characteristics to the electrical pulse were as follows: Figure 6 As shown, a represents the positive bias piezoelectric pulse response characteristic, and b represents the negative bias piezoelectric pulse response characteristic. From... Figure 6 It can be seen that the pulse current varies with the applied pulse voltage; the higher the pulse voltage, the larger the pulse current and the longer its duration. When a positive pulse voltage is applied, the organic transistor memory generates a positive drain current lasting more than 14 seconds; while when a negative pulse voltage is applied, the organic transistor memory generates a reverse drain current, and the duration of the current increases with the amplitude of the applied programming gate pulse voltage. Each increase in programming gate pulse voltage leads to a significant increase in the pulse current gradient, further demonstrating that this type of organic transistor memory has multi-level storage characteristics, and further illustrating that the organic transistor memory based on the inorganic chloride-doped polymer electrolyte hybrid dielectric film of this invention has excellent dynamic storage characteristics.

[0097] Using an Agilent 4155c semiconductor parameter analyzer, the electrical performance of the other two types of organic transistor memories with inorganic chloride-doped polymer electrolytes prepared in Examples 5 and 6 above was tested. Their electrical impulse response characteristic curves are shown below. Figure 7 and 8 As shown, a represents the positive bias piezoelectric pulse response characteristic, and b represents the negative bias piezoelectric pulse response characteristic. From... Figure 7 and Figure 8 It can be seen that the organic transistor memory of the present invention is sensitive to different inorganic chlorides doped with it, and can form different amplitudes and ranges of electrical pulse response currents, thus exhibiting adjustable storage characteristics.

[0098] Similarly, the performance of organic transistor memories based on inorganic chloride-doped polymer electrolyte hybrid dielectric film materials prepared in other embodiments was tested according to the above test method. The results were similar to the performance characteristics of the organic transistor memory based on zinc chloride-doped polymer electrolyte prepared in Example 4 above. This indicates that the organic transistor memory based on inorganic chloride-doped polymer electrolyte hybrid dielectric film materials prepared according to the present invention can also realize a flexible memory device with low power consumption and multi-level storage characteristics by utilizing ion migration characteristics. It has good application prospects in the future research of novel solid-state polymer electrolyte hybrid dielectric materials and storage technology.

[0099] In summary, this invention discloses a polymer electrolyte hybrid dielectric film material based on inorganic chloride doping and its application in organic transistor memories. It primarily employs a zinc chloride-doped polyacrylic acid and polyethylene glycol crosslinked electrolyte dielectric film, utilizing voltage-controlled ion migration within the polymer electrolyte dielectric film to successfully develop a low-voltage organic transistor memory with multi-level storage characteristics. The organic transistor memory based on the inorganic chloride-doped polymer electrolyte of this invention leverages the advantages of three-terminal devices, achieving multi-level writing and erasing by applying different programming gate pulse voltages, and enabling rapid storage using ultraviolet light irradiation. Furthermore, it allows for dynamic storage of the organic transistor memory based on the inorganic chloride-doped polymer electrolyte using electrical pulses, meeting the requirements for rapid storage and erasure of information learning and memory-type storage devices.

[0100] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A polymer electrolyte hybrid dielectric thin film material based on inorganic chloride doping, characterized in that, The polymer-electrolyte hybrid dielectric film material comprises a polymer electrolyte material and a doped inorganic chloride, wherein the inorganic chloride accounts for 0.05~20 wt.% of the total mass of the inorganic chloride and the polymer electrolyte material. The polymer electrolyte material is at least one of the following: acrylic polymer electrolyte or its derivatives, polymer electrolyte composite dielectric material formed by blending polyacrylic acid and polyethylene glycol, and polymer electrolyte composite dielectric material formed by blending polyacrylic acid and polyvinyl alcohol. The inorganic chloride is any one or more of zinc chloride, calcium chloride, ferric chloride, copper chloride, cobalt chloride, magnesium chloride, lithium chloride, sodium chloride, or potassium chloride.

2. The polymer electrolyte hybrid dielectric thin film material based on inorganic chloride doping according to claim 1, characterized in that, The polymer electrolyte composite dielectric material formed by blending polyacrylic acid and polyethylene glycol has a mass ratio of polyacrylic acid to polyethylene glycol of 1:0.1 to 1:0.6, and the polymer electrolyte composite dielectric material formed by blending polyacrylic acid and polyvinyl alcohol has a mass ratio of polyacrylic acid to polyvinyl alcohol of 1:0.1 to 1:0.

7.

3. The method for preparing the polymer electrolyte hybrid dielectric thin film material based on inorganic chloride doping according to any one of claims 1 to 2, characterized in that, The preparation method includes the following steps: (1) Dissolve the polymer electrolyte in a solvent and stir at room temperature to obtain a precursor solution of the polymer electrolyte; (2) Add inorganic chloride to the precursor solution of the polymer electrolyte and stir evenly at room temperature to obtain a solution of inorganic chloride-doped polymer electrolyte; (3) After spin-coating the solution of the inorganic chloride-doped polymer electrolyte into a film, anneal it at 50~200℃ for more than 30 minutes to obtain the polymer electrolyte hybrid dielectric film material based on inorganic chloride doping.

4. The preparation method according to claim 3, characterized in that, In step (1), the solvent is any one or more of water, methanol, ethanol or isopropanol, and the concentration of polymer electrolyte in the precursor solution of polymer electrolyte is 3~60 mg / mL; In step (2), the stirring time at room temperature is 3~24h.

5. The application of the polymer electrolyte hybrid dielectric thin film material based on inorganic chloride doping as described in any one of claims 1 to 2 in the fabrication of organic transistor memories, optoelectronic devices or electrical equipment.

6. An organic transistor memory, characterized in that, The organic transistor memory comprises, from bottom to top, a substrate, a semiconductor layer, a double dielectric layer formed by an interface passivation dielectric layer and a polymer electrolyte hybrid dielectric layer, and a gate. A source and a drain are respectively disposed between the surface of the substrate and the semiconductor layer. The material of the polymer electrolyte hybrid dielectric layer comprises the polymer electrolyte hybrid dielectric film material based on inorganic chloride doping as described in any one of claims 1 to 2.

7. The method for fabricating the organic transistor memory according to claim 6, characterized in that, The preparation method includes the following steps: (1) Source and drain materials are prepared on the substrate surface by any one of magnetron sputtering, vacuum thermal evaporation, atomic layer deposition, inkjet printing or drop coating to form source and drain, respectively, wherein a conductive channel with a micro-nano scale spacing is formed between the source and drain. (2) On the source, drain and substrate surfaces, an organic semiconductor material is prepared to form a semiconductor layer by any one of spin coating, blade coating or inkjet printing; (3) On the surface of the semiconductor layer, the material of the interface passivation dielectric layer is prepared by any one of atomic layer deposition, vacuum thermal evaporation, magnetron sputtering, spin coating, blade coating or inkjet printing to form the interface passivation dielectric layer. (4) On the surface of the interface passivation dielectric layer, the polymer electrolyte hybrid dielectric film material based on inorganic chloride doping according to any one of claims 1 to 2 is coated by any one of the solution processing methods of spin coating, blade coating or inkjet printing and then annealed to prepare the polymer electrolyte hybrid dielectric layer based on inorganic chloride doping. (5) On the surface of the inorganic chloride-doped polymer electrolyte hybrid dielectric layer, a gate material is prepared by any one of magnetron sputtering, vacuum thermal evaporation, atomic layer deposition, inkjet printing or drop coating to form a gate, thereby obtaining an organic transistor memory.

8. The preparation method according to claim 7, characterized in that, In step (1), the substrate material is any one or more of polyethylene terephthalate, polyethylene naphthalate, polyimide, polydimethylsiloxane, polycarbonate, polyvinyl alcohol, glass, silicon dioxide / silicon or sapphire, and the source and drain materials are any one or more of gold, silver, aluminum, copper, chromium, platinum, titanium, nickel, indium tin oxide, fluorine-doped tin oxide, zinc aluminum oxide, carbon nanotubes, graphene or conductive polymer; In step (2), the material of the semiconductor layer is an organic conjugated polymer or an organic small molecule semiconductor material. The material of the semiconductor layer includes any one or more of poly(3-hexylthiophene), indole-dithiophene-benzothiadiazole copolymer, polythiophene derivative, polyfluorene derivative, poly(p-phenylene acetylene) derivative, pentaphenyl, 7,7,8,8-tetracyano-p-benzodiquinone dimethane, or copper phthalocyanine. In step (3), the material of the interface passivation dielectric layer is any one or more of polymethyl methacrylate, polystyrene, polymers with a dielectric constant greater than 3, metal oxide dielectrics, or silicon dioxide. In step (4), when spin coating is used as a solution processing method, the spin coating speed is 200~5000 rpm, the spin coating time is 20~150s, the annealing temperature after spin coating is 50~200℃, and the annealing time is not less than 30min; In step (5), the gate material is any one or more of gold, silver, aluminum, copper, chromium, platinum, titanium, nickel, indium tin oxide, fluorine-doped tin oxide, zinc aluminum oxide, carbon nanotubes, graphene, or conductive polymer.

9. The application of the organic transistor memory of claim 6 in static and dynamic storage, as well as in optoelectronic devices or electrical equipment.

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