Acridone-based organic storage material, preparation method and application thereof

Abstract

The present invention discloses an acridone-based organic storage material, a preparation method, and its application, belonging to the technical field of organic storage materials. The acridone-based organic storage material has the general structural formula: #imgabs0#, wherein n is 1-22, and Ar is any one of the following structural formulas: #imgabs1#. The present invention utilizes a simple, low-cost process to prepare the organic storage material, which can serve as a charge-trapping layer for memory devices. It can be applied to OFET memories and exhibits excellent storage capacity and response speed.

Description

Technical Field

[0001] The invention relates to an acridone-based organic storage material, a preparation method and application thereof, and belongs to the technical field of organic storage materials. Background Art

[0002] Memory devices enable information storage, data processing and transmission, and intelligent switching, playing a vital role in modern technology. Organic field-effect transistor memory uses organic materials as the active material, forming a sandwich structure with other functional materials. Information is stored by applying a forward or reverse voltage to the gate electrode, causing a reversible shift in the threshold voltage. Key parameters of memory devices include the memory window, retention time, read / write / erase cycle count, operating voltage, mobility, on / off current ratio, and threshold voltage.

[0003] Compared to traditional organic field-effect transistors, existing organic field-effect transistor memories incorporate a carrier-trapping layer between the semiconductor layer and the gate. These layers can be categorized into three types based on their trapping characteristics: ferroelectric, floating gate, and electret, each with its own advantages and disadvantages.

[0004] Ferroelectric materials include PZT, MXD6 or P(VDF / TrFE). Their field-effect transistor memories are not affected by external conditions and can store data for a long time. However, they have problems such as large leakage current, poor tolerance and poor polarization retention.

[0005] The floating gate materials are mainly nanoparticles of Au, Ag, Cu, organic materials, two-dimensional materials, etc. Its OFET memory has high storage density and can be processed on a large area on a flexible substrate, but there are problems such as high erase and write voltage, storage stability, complex processing technology and device structure.

[0006] Organic electret OFET memory can semi-permanently maintain the polarization state of the dielectric in the absence of an external electric field, capture and stably store charges, and has storage characteristics and insulation properties. However, it has problems such as excessively high operating voltage, slow read and write speeds, poor tolerance, and unclear relationship between storage mechanism and molecular structure.

[0007] Currently, existing organic field-effect transistors still face the following problems: (1) excessively high operating voltage, slow read / write speed, poor device tolerance, low storage density, and poor device stability (short retention time). (2) The relationship between the storage mechanism and the molecular structure is unclear, and the storage performance is also highly dependent on the quality of the spin film. How to control the uniformity of the film quality to stabilize the quality of the same batch of products; (3) The preparation process is complex and the cost is high.

[0008] In view of this, it is indeed necessary to propose an acridone-based organic storage material to solve the above problems. Summary of the Invention

[0009] The object of the present invention is to provide an acridone-based organic storage material, a preparation method and its application, so as to solve at least one of the problems in the prior art of organic field-effect transistors, namely, poor performance, complex preparation process and inability to be mass-produced.

[0010] To achieve the above objectives, the present invention provides an acridone-based organic storage material having the general structural formula:

[0011]

[0012] Wherein, n is 1-22, and Ar is any one of the following structural formulas:

[0013]

[0014] To achieve the above object, the present invention also provides a method for preparing an acridone-based organic storage material, comprising:

[0015] S1, compound A and acridone are mixed and subjected to a substitution reaction to generate compound B;

[0016]

[0017] S2. Compound B and Compound C are mixed to undergo a substitution reaction, so that Compound B replaces the hydrogen on one side of the amino group of Compound C to obtain the target compound D;

[0018]

[0019] As a further improvement of the present invention, in S1, the molar ratio of compound A, acridone and catalyst is 6:1:10 to 10:1:20.

[0020] As a further improvement of the present invention, in S1: the reaction time is 24 to 36 hours, and the reaction temperature is 90 to 100°C.

[0021] As a further improvement of the present invention, in S2, the molar ratio of compound B, compound C and catalyst is 1.1:1:10 to 1.2:1:20.

[0022] As a further improvement of the present invention, in S2: the reaction time is 12 to 24 hours, and the reaction temperature is 90 to 100°C.

[0023] As a further improvement of the present invention, the catalyst is any one of NaH, NaOH, and K2CO3.

[0024] To achieve the above-mentioned object, the present invention also provides an application of an acridone-based organic storage material in an organic field-effect transistor memory.

[0025] As a further improvement of the present invention, an acridone-based organic storage material is dissolved and spin-coated on a clean substrate, and then dried to obtain an organic storage material film for making a charge trapping layer of an organic field effect transistor memory.

[0026] As a further improvement of the present invention, an organic semiconductor layer is evaporated on the surface of the organic storage material film, followed by patterning, and then metal is evaporated as source and drain electrodes to prepare an organic field effect transistor memory.

[0027] The beneficial effects of the present invention are: the present invention adopts a simple and low-cost process to prepare an organic storage material, which can serve as a charge trapping layer of a memory, can be applied to an OFET memory, and has good storage capacity and response speed. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a hydrogen nuclear magnetic resonance spectrum of the acridone-based organic storage material in Example 1 of the present invention.

[0029] Figure 2 is a mass spectrum of the acridone-based organic storage material in Example 1.

[0030] Figure 3 1 is the ultraviolet absorption and fluorescence emission spectra of the acridone-based organic storage material in dichloromethane in Example 1.

[0031] Figure 4 1 is a transfer characteristic curve of the organic field effect transistor memory test in Example 1.

[0032] Figure 5 This is the output characteristic curve of the organic field effect transistor memory test in Example 1.

[0033] Figure 6 1 is a negative memory window characteristic curve of the organic field effect transistor memory test in Example 1. DETAILED DESCRIPTION

[0034] In order to make the objectives, technical solutions and advantages of the present invention more clear, the present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0035] The present invention provides an acridone-based organic storage material, a preparation method, and an application thereof. Specifically, the acridone-based organic storage material has the general structural formula:

[0036]

[0037] Wherein, n is 1-22, and Ar is any one of the following structural formulas:

[0038]

[0039] The present invention provides a method for preparing an acridone-based organic storage material, comprising:

[0040] S1, compound A and acridone are mixed and subjected to a substitution reaction to generate compound B;

[0041]

[0042] The molar ratio of compound A, acridone and catalyst is 6:1:10-10:1:20, the reaction time is 24-36 hours, and the reaction temperature is 90-100°C.

[0043] S2. Compound B and Compound C are mixed to undergo a substitution reaction, so that Compound B replaces the hydrogen on one side of the amino group of Compound C to obtain the target compound D;

[0044]

[0045] The molar ratio of compound B, compound C and catalyst is 1.1:1:10-1.2:1:20, the reaction time is 12-24 hours, and the reaction temperature is 90-100°C.

[0046] THF solution needs to be added to both S1 and S2 as a solvent. The amount of the solvent can be adjusted according to actual conditions and is not limited here.

[0047] Both S1 and S2 require the addition of a catalyst during the reaction, wherein the catalyst is any one of NaH, NaOH, and K2CO3. Of course, in other embodiments, the catalyst can also be selected according to actual conditions and is not limited here.

[0048] The present invention also provides an application of an acridone-based organic storage material in an organic field-effect transistor memory.

[0049] First, an acridone-based organic storage material is dissolved and spin-coated onto a clean substrate. After drying, an organic storage material film is obtained, which can be used to make a charge-trapping layer for an organic field-effect transistor memory. Second, an organic semiconductor layer is evaporated on the surface of the organic storage material film, followed by patterning. Finally, metal is evaporated as source and drain electrodes to prepare an organic field-effect transistor memory.

[0050] Example 1

[0051] The structure of acridone-based organic storage materials is:

[0052]

[0053] Wherein, n=4, Ar is Of course, in other embodiments, n can be any integer between 1 and 22, and Ar can also be Any one or more of the above, not limited here.

[0054] The synthetic route of organic storage materials based on acridone is:

[0055]

[0056] The preparation method is:

[0057] S1, acridone (1g, 5.12mmol) and 60% sodium hydride (0.41g, 10.24mmol) are added to a 50ml three-necked flask, the three-necked flask is assembled with a condenser, a 25mL constant pressure dropping funnel and a sealing device, and then nitrogen ventilation is carried out by the sealing device to realize the nitrogen atmosphere protection in the three-necked flask. Under 0°C ice-water bath conditions, dry THF (20mL) is added and the reactant is fully dissolved. After stirring for 1.5h, the reaction unit is transferred to an oil bath. 4mL of compound A (6.6g, 30.73mmol) is added to a constant pressure dropping funnel, and under 90°C conditions, compound A is added dropwise to continue the reaction, and the control drop rate is 1 drop / 5s, and the reaction is heated at reflux for 24h. The reaction solution was quenched with water, then extracted with dichloromethane several times, dried over anhydrous Na2SO4, and rotary evaporated to obtain a crude product of compound B. The crude product was chromatographed on a 300-400 mesh silica gel column with petroleum ether:ethyl acetate = 6:1 as the chromatographic solution, and rotary evaporated and recrystallized to obtain compound B.

[0058] S2, compound C (200mg, 0.174mmol) and 60% sodium hydride (70mg, 1.74mmol) are added in the three-necked flask of 25ml, and three-necked flask is connected with condenser tube, 25mL constant pressure funnel and sealing device, carry out nitrogen ventilation by sealing device subsequently, to realize the nitrogen atmosphere protection in the three-necked flask.Under 0 ℃ ice-water bath condition, add dry THF (10mL) that reactant is fully dissolved, after stirring 1.5h, reaction unit is transferred in oil bath pot.Compound B (63mg, 0.19mmol) being dissolved in 5mL tetrahydrofuran (THF) is added in constant pressure funnel, at 90 ℃, compound B is added dropwise and continues reaction, and control rate of addition is 1 drop / 5s, is heated to reflux 12 hours. After the reaction is completed, the reaction solution is quenched with water, then extracted multiple times with dichloromethane, dried over anhydrous Na2SO4, and then rotary evaporated to obtain a crude product of compound D. The crude product is chromatographed on a 200-300 mesh silica gel column with a chromatographic solution of petroleum ether: ethyl acetate = 5:1. Rotary evaporation and recrystallization give a light green solid compound D, which is an acridone-based organic storage material.

[0059] See also Figure 1 As shown, compound D was subjected to 1 H NMR detection uses tetramethylsilane (TMS) as the internal standard and a deuterated reagent as the test solvent. The test concentration of the hydrogen spectrum is generally 5 mg / mL, and the volume of the deuterated reagent required during the test is about 0.4 mL.

[0060] 1 The H NMR detection data are: 1 H NMR(400MHz, CDCl3)δ8.57-8.50(d,J=8.0Hz,2H),8.06(s,1H),7.96(s,2H),7.83(s,2H),7.54 -7.50(t,J=8.8Hz,2H),7.40-7.38(d,J=6.8Hz,2H),7.28-7.27(t,J=6.4Hz,2H),7.25-7.24(d ,J=7.2Hz,2H),7.22-7.21(d,J=6.8Hz,4H),7.19-7.18(d,J=4.8Hz,2H),7.16-7.10(m,24H),6 .99-6.88(m,24H),4.39-4.36(t,J=6.8Hz,2H),4.25-4.21(t,J=8.0Hz,2H),2.16-2.01(m,4H).

[0061] See also Figure 2As shown, compound D was subjected to mass spectrometry detection in a linear mode, and the mass spectrum data of compound D was obtained as follows: m / z calcd for C 105 H 77 N3O:1397.468[M + ]; found:1397.612.

[0062] See also Figure 3 As shown, compound D was subjected to spectroscopic titration detection. At room temperature, a solution of 1.0×10 -5 A dilute dichloromethane solution of compound D was prepared and flushed with nitrogen to remove oxygen, followed by absorption and emission spectrum tests. As can be seen from the figure, the UV absorption spectrum peaks of compound D in dichloromethane are 305nm, 381nm and 400nm, and the fluorescence spectrum peaks are 407nm and 427nm.

[0063] The present invention also provides an application of compound D in an organic field effect transistor memory. Compound D is prepared into a thin film, and the thin film is used to prepare a charge storage layer of the organic field effect transistor memory.

[0064] The specific steps of preparing compound D into a thin film are as follows:

[0065] a. Prepare a molecular solution of compound D.

[0066] The solution concentration is 3 mg / mL, and the solvent is chloroform (CHCl3) or toluene without additional water removal treatment. After the preparation is completed, it is allowed to stand for 24 hours to allow compound D to be evenly dispersed.

[0067] b. Pre-treat the substrate.

[0068] A heavily doped silicon substrate with a 300 nm thick layer of silicon dioxide on its surface was ultrasonically cleaned with acetone, ethanol, and deionized water for 15 minutes each, at a frequency of 100 kHz. High-purity nitrogen was then used to blow dry the liquid on the substrate surface to ensure a clean surface. The substrate was then dried in an oven at 120°C. Of course, in other embodiments, a clean substrate may also be used directly, and this is not a limitation here.

[0069] c. Place the dried substrate in a UV ozone machine for 3 minutes.

[0070] d. Prepare compound D thin film by spin coating.

[0071] In air with a humidity of 40%, the surface of the substrate treated in step c was spin-coated with the solution prepared in step a at a spin-coating speed of 3000 r / min and a spin-coating time of 30 s, with the film thickness controlled to be approximately 20 nm. Subsequently, the spin-coated substrate was dried and annealed in a drying oven at 80°C for 30 min to remove the solvent, thereby obtaining a film of compound D.

[0072] The preparation method of the organic field effect transistor memory is as follows: vacuum evaporation of an organic semiconductor layer on the surface of the compound D film, with the evaporation rate being controlled at a vacuum degree of 5×10 -4 pa or less, and control the thickness of the evaporated film to 50nm to prepare a porous organic semiconductor layer. Subsequently, a mask is added to the surface of the film and patterned, and then a conductive metal is vacuum evaporated to serve as a source and drain electrode, and the evaporation thickness is controlled at 60-80nm; the channel width of the mask is 2000μm and the length is 100μm to prepare an organic field-effect transistor memory including a compound D film.

[0073] In this embodiment, the organic semiconductor layer is pentacene. Of course, in other embodiments, the organic semiconductor layer may also be triphenylamine, fullerene, phthalocyanine, perylene derivatives, cyanine, etc., which is not limited here.

[0074] In this embodiment, the conductive metal is gold. Of course, in other embodiments, the conductive metal may be copper, silver, etc., which is not limited here.

[0075] See also Figure 4 As shown in the figure, the electrical performance of the prepared organic field effect transistor memory is tested. It can be seen from the figure that the mobility of the memory reaches 0.11cm 2 / Vs, the switching ratio is 1×10 5 , the mobility of existing memory is 0.05cm 2 / Vs, the on / off ratio is 2×10 4 That is, the memory prepared by this technical solution is superior to the existing memory in terms of electrical performance.

[0076] See also Figure 5 As shown in the figure, the output characteristics of the prepared organic field effect transistor memory are tested. It can be seen from the figure that the relationship between the source-drain current and the source-drain voltage changes under different gate voltages (0, -10, -20, -30, -40V). It can be concluded that the memory prepared by this technical solution has a good field effect.

[0077] See also Figure 6As shown in the figure, the negative storage window test is performed on the prepared organic field-effect transistor memory. It can be seen from the figure that the negative write window of the device is very large, reaching a storage window of 43.82V, and the write speed is very fast, taking only 20ms, and it can be completely erased back to the initial position. The storage window of the existing memory is 39.30V and the write speed is 30ms. That is to say, the memory prepared by this technical solution has good storage capacity and response speed, which exceeds the existing memory.

[0078] In summary, the present invention adopts a simple and low-cost process to prepare an organic storage material, which can serve as a charge-trapping layer of a memory, can be applied to an OFET memory, and has good storage capacity and response speed; the preparation method of the organic storage material is simple, the synthesis method is single, and it has good scalability; at the same time, compared with the existing preparation method, the preparation method provided by this technical solution can be processed in a large-area solution, thereby reducing the production cost of the organic storage material.

[0079] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. An acridone-based organic storage material, characterized in that: The general structural formula is: Where n is 4 and Ar is:

2. A method for preparing an acridone-based organic storage material according to claim 1, characterized in that: include: S1, compound A and acridone are mixed and subjected to a substitution reaction to generate compound B; S2. Compound B and Compound C are mixed to undergo a substitution reaction, so that Compound B replaces the hydrogen on one side of the amino group of Compound C to obtain the target compound D; 3. The method for preparing an acridone-based organic storage material according to claim 2, wherein: In S1, the molar ratio of compound A, acridone and catalyst is 6:1:10 to 10:1:

20.

4. The method according to claim 2, wherein: In S1: the reaction time is 24 to 36 hours, and the reaction temperature is 90 to 100°C.

5. The method for preparing an acridone-based organic storage material according to claim 2, wherein: In S2, the molar ratio of compound B, compound C and catalyst is 1.1:1:10 to 1.2:1:

20.

6. The method for preparing an acridone-based organic storage material according to claim 2, wherein: In S2: the reaction time is 12 to 24 hours, and the reaction temperature is 90 to 100°C.

7. The method for preparing an acridone-based organic storage material according to claim 2, wherein: The catalyst is any one of NaH, NaOH, and K2CO3.

8. Use of the acridone-based organic storage material according to claim 1 in an organic field-effect transistor memory.

9. The use of the acridone-based organic storage material in an organic field-effect transistor memory according to claim 8, characterized in that: An acridone-based organic storage material is dissolved and spin-coated on a clean substrate, and an organic storage material film is obtained after drying, which is used to make a charge trapping layer of an organic field-effect transistor memory.

10. The use of the acridone-based organic storage material in an organic field-effect transistor memory according to claim 9, characterized in that: An organic semiconductor layer is evaporated on the surface of the organic storage material film, followed by patterning, and then metal is evaporated as source and drain electrodes to prepare an organic field effect transistor memory.

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