A halogen bond-assisted molecular self-assembly method, a method for preparing a eutectic film, and its application

Abstract

The present invention discloses a method for assisted molecular self-assembly by halogen bonding, comprising the following steps: selecting an organic multi-ary small molecule material containing a pyridine group at the end as a halogen bond acceptor; selecting a derivative of 1,4-diiodobenzene as a halogen bond donor; dissolving the halogen bond acceptor and the halogen bond donor in a solvent, heating, stirring, and ultrasonicating, and obtaining an assembly liquid after the solution becomes clear and transparent, and slowly evaporating the solvent by controlling the ambient temperature to obtain a eutectic. The present invention discloses a method for preparing a eutectic thin film, and by regulating the reduced pressure sublimation film-forming process, the eutectic system is prepared into a eutectic thin film that matches the device structure. The halogen bond-assisted molecular self-assembly method described in the present invention can not only significantly reduce the molecular synthesis process but also greatly improve the controlled stacking between molecules, and can be applied to ultra-high-density information storage.

Description

Technical Field

[0001] The present invention belongs to the field of functional semiconductor materials and electronic information, and relates to a halogen bond-assisted molecular self-assembly method, a preparation method of a eutectic thin film and applications thereof. Background Art

[0002] The packing state of molecules significantly influences the efficient transport of charge carriers in thin films and the electrical performance of devices. Small molecule materials offer advantages such as a single component, well-defined structure, highly reproducible synthesis, excellent film crystallinity, and consistent optical / electrical properties across batches. Therefore, the current focus is on manipulating the structure of small molecules to understand their interactions and packing state within thin films. However, currently designed small molecule materials are becoming increasingly complex, and the increasing number of covalent single bonds in the molecular backbone significantly causes rotation of individual functional fragments, greatly hindering researchers' ability to accurately determine the spatial conformation of the molecules. Furthermore, the difficulty in predicting the spatial conformation significantly hinders the formation of overall molecular consistency, thereby affecting intermolecular interactions and resulting in poor overall packing consistency. Furthermore, there are challenges in matching the molecular packing orientation with the "sandwich" device structure. Furthermore, the tedious and demanding molecular preparation process significantly limits the practical application of small molecule materials in multi-binary storage.

[0003] In summary, the key reasons for the problems of existing ternary memory devices include the following three points: first, the time-consuming and laborious molecular structure design still makes it difficult to accurately determine the interaction and stacking state between molecules in the film; second, the consistency of the stacking between all molecules in the film and the overall consistency of the film's external morphology are poor; third, the matching problem between the molecular stacking direction in the film and the "sandwich" device structure makes it impossible to guarantee the effective transmission of charge carriers in the device. Summary of the Invention

[0004] Purpose of the invention: The purpose of the present invention is to provide a method for halogen-assisted molecular self-assembly to overcome the problems of unclear molecular stacking, inconsistent morphology, poor device stability and reproducibility in existing multi-binary memory devices.

[0005] The present invention provides a method for preparing a eutectic thin film.

[0006] The present invention provides an application of the eutectic thin film as ultra-high density information storage.

[0007] Technical solution: A halogen bond-assisted molecular self-assembly method of the present invention comprises the following steps:

[0008] (1) Selecting organic polyfunctional small molecule materials containing a pyridine group at the end as halogen bond acceptors;

[0009] The molecular structure of an organic multi-ary small molecule material is shown in formula (I). When the terminal group R1 is a carbon atom, R2 is a nitrogen atom; when R1 is a nitrogen atom, R2 is a carbon atom. Pyridine is not only a Lewis acid, but its derivatives also exhibit weak electron-withdrawing functional groups, acting as "charge traps" to facilitate charge transfer under electric fields, thereby altering the device's electrical response and achieving information storage performance.

[0010]

[0011] (2) Selecting a derivative of 1,4-diiodobenzene as a halogen bond donor;

[0012] (3) Dissolving the halogen bond acceptor and the halogen bond donor in steps (1) and (2) in a solvent, heating, stirring, and ultrasonicating, and obtaining an assembly solution after the solution becomes clear and transparent, and evaporating the solvent to obtain a co-crystal.

[0013] Furthermore, in step (1), the terminal group of the organic polyvalent small molecule material is one of a 4-pyridyl group and a 2-pyridyl group.

[0014] Furthermore, the second functional group of the organic polyvalent small molecule material is one of 1,2,4,5-tetrazine, thiazole and naphthaleneimide, and the molecular structural formulas are as follows (II), (III) and (IV).

[0015]

[0016] Furthermore, in step (2), the halogen bond donor is one of 1,4-diiodo-2-fluorobenzene, 1,3-difluoro-2,5-diiodobenzene, 1,4-difluoro-2,5-diiodobenzene, and 1,4-diiodotetrafluorobenzene.

[0017] Furthermore, in step (3), the molar ratio of the halogen bond acceptor to the halogen bond donor is 1:(1-4).

[0018] Furthermore, in step (3), the concentration of the halogen bond acceptor in the assembly solution is 10 -3 -10 -2 mol / L.

[0019] Furthermore, in step (3), the solvent is one of anhydrous ethanol, tetrahydrofuran, dichloromethane, and chloroform.

[0020] Furthermore, in step (3), the ambient temperature for volatilizing the solvent is 25-35°C.

[0021] A method for preparing a eutectic thin film, using the eutectic prepared above to prepare the eutectic thin film, comprises the following steps:

[0022] (1) placing the eutectic in a heating zone;

[0023] (2) Place the substrate in the cooling zone;

[0024] (3) After evacuation, the heating zone is slowly heated to 130-200°C and nitrogen is introduced at a flow rate of 30-50 ml / min. Heating is continued for 10-30 minutes at a stable nitrogen flow rate. After cooling to room temperature, a eutectic film is obtained.

[0025] An application of the above eutectic thin film as ultra-high density information storage.

[0026] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The organic polycyclic halogen bond acceptor described in the present invention not only introduces two electron-withdrawing groups into the molecular skeleton, but the pyridine group at the end of the molecule can also act as a Lewis acid to form an intermolecular CN...I halogen bond with the halogen bond donor.

[0027] (2) The additional fluorine atoms introduced into the halogen bond donor of the present invention can not only improve the polarizability of the iodine atom, but its smallest atomic radius and largest electronegativity can also induce intermolecular CH...F hydrogen bonding. In addition, the strong electron-withdrawing ability of fluorobenzene can also produce intermolecular charge transfer (CT) effects with the halogen bond acceptor, which is more conducive to molecular interaction and close stacking mode.

[0028] (3) The halogen bond-assisted molecular self-assembly method described in the present invention can not only greatly reduce the molecular synthesis process but also greatly improve the controlled stacking between molecules. The raw materials are simple and easy to obtain, the operation is simple, and it is conducive to large-scale application.

[0029] (4) Compared with the solution spin coating film forming technology, the reduced pressure co-sublimation film forming technology described in the present invention is less restricted by factors such as solvent type and assembly ratio. It can also achieve a tightly controlled face-to-face or one-dimensional π-π stacking mode between the components in the film, which is beneficial to the efficient and rapid transmission of charge carriers in the eutectic film. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is the molecular structural formula of the halogen bond acceptor;

[0031] Figure 2 is the molecular structural formula of the halogen bond donor;

[0032] Figure 3 This is the theoretical simulation diagram of the halogen bond acceptor;

[0033] Figure 4 (a) is a schematic diagram of the halogen bond effect of Example 1, Figure 4(b) is the crystal stacking structure of the eutectic obtained in Example 1, Figure 4 (c) is the length of the halogen bond CN…I bond in the co-crystal obtained in Example 1;

[0034] Figure 5 (a) is a theoretical calculation diagram of the charge transfer effect of the co-crystal obtained in Example 1, Figure 5 (b) shows the intermolecular interaction pattern of the co-crystal obtained in Example 1.

[0035] Figure 6 is the crystal structure of the co-crystal obtained in Example 11;

[0036] Figure 7 is the crystal structure of the co-crystal obtained in Example 13;

[0037] Figure 8 Schematic diagram of the reduced pressure co-sublimation film forming apparatus used in Examples 14-22;

[0038] Figure 9 (a) is an atomic force microscope image of the organic eutectic film prepared in Example 14, Figure 9 (b) is an X-ray diffraction pattern of the organic eutectic thin film prepared in Example 14;

[0039] Figure 10 (a) is a structural diagram of a "sandwich" electrical storage device based on an organic eutectic thin film. Figure 10 (b) is the electrical performance diagram of a single organic multi-halogen bond acceptor. Figure 10 (c) is the electrical performance diagram of the eutectic film. Figure 10 (d) is a statistical diagram of the device efficiency of a single organic polycyclic halogen bond acceptor and a eutectic system. DETAILED DESCRIPTION

[0040] The present invention will be further described below with reference to the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it. However, the embodiments are not intended to limit the present invention.

[0041] like Figure 1 、 2 As shown in FIG, the molecular structures of the organic polycyclic halogen bond acceptor and the halogen bond donor based on 1,4-diiodobenzene used in the assembly process; Figure 3 The theoretical simulation diagram of the organic multi-ary halogen bond receptor shown in the figure shows that there are two electron-withdrawing groups of different strengths in the molecular skeleton, which satisfy the multiple transfer of charge carriers under the action of the electric field and thus realize multi-ary storage. Example 1

[0042] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0043] 2,5-Di(pyridin-4-yl)thiazolothiazole (29.6 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (40.1 mg, 0.1 mmol) were dispersed in 10 ml of chloroform solvent at a molar ratio of 1:1, and the concentration of 2,5-di(pyridin-4-yl)thiazolothiazole was controlled to be 10 -2 mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. The room temperature is controlled at 25°C, and the chloroform solvent is slowly evaporated to form several prismatic yellow crystals.

[0044] like Figure 4 As shown in Figure 2, the length of the halogen bond CN…I bond in the prepared co-crystal is 2.84 Å. Figure 5 As shown in (a), the theoretical calculation diagram shows that there is a charge transfer effect between the molecular terminal pyridine and 1,4-diiodotetrafluorobenzene in the prepared co-crystal, which is beneficial to the interaction and close stacking mode of the molecules; Figure 5 As shown in (b), in addition to the non-covalent interaction of halogen bonds, the organic multi-ary halogen bond acceptor and halogen bond donor also cooperate with charge transfer (CT) interaction, π-π stacking and CH...F hydrogen bonding to form a compact and ordered intermolecular stacking pattern. Example 2

[0045] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0046] 2,5-Di(pyridin-4-yl)thiazolothiazole (29.6 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (80.2 mg, 0.2 mmol) were dispersed in 10 ml of chloroform solvent at a molar ratio of 1:2, and the concentration of 2,5-di(pyridin-4-yl)thiazolothiazole was controlled to be 10 -2 mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. The room temperature is controlled at 25°C, and the chloroform solvent is slowly evaporated to form several prismatic yellow crystals. Example 3

[0047] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0048] 2,5-Di(pyridin-4-yl)thiazolothiazole (29.6 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (160.4 mg, 0.4 mmol) were dispersed in 10 ml of chloroform solvent at a molar ratio of 1:4, and the concentration of 2,5-di(pyridin-4-yl)thiazolothiazole was controlled to be 10 -2mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. The room temperature is controlled at 25°C, and the chloroform solvent is slowly evaporated to form several prismatic yellow crystals. Example 4

[0049] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0050] 2,5-Di(pyridin-4-yl)thiazolothiazole (29.6 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (40.1 mg, 0.1 mmol) were dispersed in 100 ml of chloroform solvent at a molar ratio of 1:1, and the concentration of 2,5-di(pyridin-4-yl)thiazolothiazole was controlled to be 10 -3 mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. The room temperature is controlled at 25°C, and the chloroform solvent is slowly evaporated to form several prismatic yellow crystals. Example 5

[0051] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0052] 2,5-Di(pyridin-4-yl)thiazolothiazole (29.6 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (40.1 mg, 0.1 mmol) were dispersed in 50 ml of chloroform solvent at a molar ratio of 1:1, and the concentration of 2,5-di(pyridin-4-yl)thiazolothiazole was controlled to be 2*10 -3 mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. The room temperature is controlled at 25°C, and the chloroform solvent is slowly evaporated to form several prismatic yellow crystals. Example 6

[0053] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0054] 2,5-Di(pyridin-4-yl)thiazolothiazole (29.6 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (40.1 mg, 0.1 mmol) were dispersed in 10 ml of dichloromethane solvent at a molar ratio of 1:1, and the concentration of 2,5-di(pyridin-4-yl)thiazolothiazole was controlled to be 10 -2 mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. The room temperature is controlled at 25°C, and the chloroform solvent is slowly evaporated to form several prismatic yellow crystals. Example 7

[0055] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0056] 2,5-Di(pyridin-4-yl)thiazolothiazole (29.6 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (40.1 mg, 0.1 mmol) were dispersed in 10 ml of anhydrous ethanol solvent at a molar ratio of 1:1, and the concentration of 2,5-di(pyridin-4-yl)thiazolothiazole was controlled to be 10 -2 mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. The room temperature is controlled at 25°C, and the chloroform solvent is slowly evaporated to form several prismatic yellow crystals. Example 8

[0057] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0058] 2,5-Di(pyridin-4-yl)thiazolothiazole (29.6 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (40.1 mg, 0.1 mmol) were dispersed in 10 ml of tetrahydrofuran solvent at a molar ratio of 1:1, and the concentration of 2,5-di(pyridin-4-yl)thiazolothiazole was controlled to be 10 -2 mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. The room temperature is controlled at 25°C, and the chloroform solvent is slowly evaporated to form several prismatic yellow crystals. Example 9

[0059] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0060] 2,5-Di(pyridin-4-yl)thiazolothiazole (29.6 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (40.1 mg, 0.1 mmol) were dispersed in 10 ml of chloroform solvent at a molar ratio of 1:1, and the concentration of 2,5-di(pyridin-4-yl)thiazolothiazole was controlled to be 10 -2 mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. The room temperature is controlled at 35°C, and the chloroform solvent is slowly evaporated to form several prismatic yellow crystals.

[0061] Example 10:

[0062] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0063] 2,5-Di(pyridin-4-yl)thiazolothiazole (29.6 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (40.1 mg, 0.1 mmol) were dispersed in 10 ml of chloroform solvent at a molar ratio of 1:1, and the concentration of 2,5-di(pyridin-4-yl)thiazolothiazole was controlled to be 10 -2mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. Control the room temperature to 30°C and wait for the chloroform solvent to evaporate slowly to form several prismatic yellow crystals.

[0064] Example 11:

[0065] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0066] 3,6-Di(pyridin-4-yl)tetrazine (23.6 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (40.1 mg, 0.1 mmol) were dispersed in 10 ml of chloroform solvent at a molar ratio of 1:1, and the concentration of 3,6-di(pyridin-4-yl)tetrazine was controlled to be 10 -2 mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. Control the room temperature to 25°C and wait for the chloroform solvent to evaporate slowly to form several prismatic purple-red crystals.

[0067] like Figure 6 As shown in the internal stacking structure diagram of the obtained co-crystal, it can be seen that the length of the halogen bond CN...I bond in the co-crystal prepared from 3,6-di(pyridin-4-yl)tetrazine and 1,4-diiodotetrafluorobenzene is 2.976 Å, and a face-to-face layer-by-layer stacking pattern is formed between the molecules.

[0068] Example 12:

[0069] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0070] 2,7-Di(pyridin-4-yl)naphthalimide (42.0 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (40.1 mg, 0.1 mmol) were dispersed in 10 ml of chloroform solvent at a molar ratio of 1:1, and the concentration of 2,7-di(pyridin-4-yl)naphthalimide was controlled to be 10 -2 mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. Control the room temperature to 25°C and wait for the chloroform solvent to evaporate slowly to form several blocky yellow crystals.

[0071] Example 13:

[0072] The self-assembly of organic multi-ary halogen bond acceptors and halogen bond donors is as follows:

[0073] 3,6-Di(pyridin-2-yl)tetrazine (23.6 mg, 0.1 mmol) and 1,4-diiodotetrafluorobenzene (40.1 mg, 0.1 mmol) were dispersed in 10 ml of chloroform solvent at a molar ratio of 1:1, and the concentration of 3,6-di(pyridin-2-yl)tetrazine was controlled to be 10-2 mol / L, and completely dissolve it under ultrasonication to form a clear and transparent solution. Control the room temperature to 25°C and wait for the chloroform solvent to evaporate slowly to form several blocky purple-red crystals.

[0074] like Figure 7 As shown in the internal stacking structure diagram of the obtained co-crystal, it can be seen that the length of the halogen bond CN...I bond in the co-crystal prepared from 3,6-di(pyridin-2-yl)tetrazine and 1,4-diiodotetrafluorobenzene is 3.05 Å, and a fishbone-shaped side-slip stacking pattern is formed between the molecules.

[0075] The following examples are based on Figure 8 The vacuum reduced pressure co-sublimation film forming device based on a tube furnace shown is used to prepare a eutectic film. The prepared eutectic is placed in the heating zone 2 of the tube furnace, and an indium tin oxide (ITO) glass sheet is placed in the cooling zone 3 of the tube furnace. A vacuum pumping device 1 is used for vacuuming, and the arrow indicates the direction of nitrogen introduction.

[0076] Example 14:

[0077] The co-assembled eutectic system is used to prepare an organic eutectic semiconductor thin film using a reduced pressure thermal sublimation technique. The specific steps are as follows:

[0078] 50 mg of the eutectic from Examples 1-13 was weighed and placed in the heating zone of a tube furnace. Several cleaned ITO glass sheets were then placed in the cooling zone of the tube furnace. Finally, all valves were tightened to ensure airtightness. After this operation, the tube furnace was evacuated using a mechanical pump for 30 minutes. The temperature was then slowly increased until it reached and stabilized at 130°C. A nitrogen gas flow rate of 30 ml / min was then activated. While maintaining a steady nitrogen flow rate, the eutectic was heated for 10 minutes. The heat source was then turned off and the tube furnace cooled to room temperature to obtain an organic eutectic film.

[0079] like Figure 9 As shown, from the AFM and XRD patterns of the eutectic film, it can be seen that: the AFM pattern shows that the eutectic film prepared by the reduced pressure co-sublimation method exhibits an obvious granular morphology, indicating that the film obtained by this method still has a high degree of crystallinity; the XRD pattern shows that the stacking pattern of the formed eutectic film is different from that of a single halogen bond acceptor or halogen bond donor, and the XRD diffraction peaks exhibited by the eutectic film are basically consistent with the XRD pattern of the crystal simulation.

[0080] Example 15:

[0081] The co-assembled eutectic system is used to prepare an organic eutectic semiconductor thin film using a reduced pressure thermal sublimation technique. The specific steps are as follows:

[0082] 80 mg of the eutectic from Examples 1-13 was weighed and placed in the heating zone of a tube furnace. Several cleaned ITO glass sheets were then placed in the cooling zone of the tube furnace. Finally, all valves were tightened to ensure airtightness. After this operation, the tube furnace was evacuated using a mechanical pump for 30 minutes. The temperature was then slowly increased until it reached and stabilized at 130°C. A nitrogen gas flow rate of 30 ml / min was then activated. While maintaining a steady nitrogen flow rate, the eutectic was heated for 10 minutes. The heat source was then turned off and the eutectic was allowed to cool to room temperature to obtain an organic eutectic film.

[0083] Example 16:

[0084] The co-assembled eutectic system is used to prepare an organic eutectic semiconductor thin film using a reduced pressure thermal sublimation technique. The specific steps are as follows:

[0085] 120 mg of the eutectic from Examples 1-13 was weighed and placed in the heating zone of a tube furnace. Several cleaned ITO glass sheets were then placed in the cooling zone of the tube furnace. Finally, all valves were tightened to ensure airtightness. After this operation, the tube furnace was evacuated using a mechanical pump for 30 minutes. The temperature was then slowly increased until it reached and stabilized at 130°C. A nitrogen gas flow rate of 30 ml / min was then activated. While maintaining a steady nitrogen flow rate, the eutectic was heated for 10 minutes. The heat source was then turned off and the eutectic was allowed to cool to room temperature to obtain an organic eutectic film.

[0086] Example 17:

[0087] The co-assembled eutectic system is used to prepare an organic eutectic semiconductor thin film using a reduced pressure thermal sublimation technique. The specific steps are as follows:

[0088] Weigh 50 mg of the eutectic from Examples 1-13 and place it in the heating zone of a tube furnace. Then, place several cleaned ITO glass sheets in the cooling zone of the tube furnace. Finally, tighten all valves to ensure airtightness. After this operation, evacuate the tube furnace using a mechanical pump for 30 minutes. Then, slowly increase the temperature until the temperature reaches and stabilizes at 150°C. Then, start nitrogen flow at a constant rate of 30 ml / min. Heat the eutectic for 10 minutes, then turn off the heat source and allow it to cool to room temperature to obtain an organic eutectic film.

[0089] Example 18:

[0090] The co-assembled eutectic system is used to prepare an organic eutectic semiconductor thin film using a reduced pressure thermal sublimation technique. The specific steps are as follows:

[0091] 50 mg of the eutectic from Examples 1-13 was weighed and placed in the heating zone of a tube furnace. Several cleaned ITO glass sheets were then placed in the cooling zone of the tube furnace. Finally, all valves were tightened to ensure airtightness. After this operation, the tube furnace was evacuated using a mechanical pump for 30 minutes. The temperature was then slowly increased until it reached a stable temperature of 220°C. A nitrogen gas flow rate of 30 ml / min was then activated. While maintaining a steady nitrogen flow rate, the eutectic was heated for 10 minutes. The heat source was then turned off and the eutectic was allowed to cool to room temperature to obtain an organic eutectic film.

[0092] Example 19:

[0093] The co-assembled eutectic system is used to prepare an organic eutectic semiconductor thin film using a reduced pressure thermal sublimation technique. The specific steps are as follows:

[0094] Weigh 50 mg of the eutectic from Examples 1-13 and place it in the heating zone of a tube furnace. Then, place several cleaned ITO glass sheets in the cooling zone of the tube furnace. Finally, tighten all valves to ensure airtightness. After this operation, evacuate the tube furnace using a mechanical pump for 30 minutes. Then, slowly increase the temperature until the temperature reaches and stabilizes at 130°C. Then, start nitrogen flow at a constant rate of 40 ml / min. Heat the eutectic for 10 minutes, then turn off the heat source and allow it to cool to room temperature to obtain an organic eutectic film.

[0095] Example 20:

[0096] The co-assembled eutectic system is used to prepare an organic eutectic semiconductor thin film using a reduced pressure thermal sublimation technique. The specific steps are as follows:

[0097] Weigh 50 mg of the eutectic from Examples 1-13 and place it in the heating zone of a tube furnace. Then, place several cleaned ITO glass sheets in the cooling zone of the tube furnace. Finally, tighten all valves to ensure airtightness. After this operation, evacuate the tube furnace using a mechanical pump for 30 minutes. Then, slowly increase the temperature until the temperature reaches and stabilizes at 130°C. Then, start nitrogen flow at a constant rate of 50 ml / min. Heat the eutectic for 10 minutes, then turn off the heat source and allow it to cool to room temperature to obtain an organic eutectic film.

[0098] Example 21:

[0099] The co-assembled eutectic system is used to prepare an organic eutectic semiconductor thin film using a reduced pressure thermal sublimation technique. The specific steps are as follows:

[0100] 50 mg of the eutectic from Examples 1-13 was weighed and placed in the heating zone of a tube furnace. Several cleaned ITO glass sheets were then placed in the cooling zone of the tube furnace. Finally, all valves were tightened to ensure airtightness. After this operation, the tube furnace was evacuated using a mechanical pump for 30 minutes. The temperature was then slowly increased until it reached and stabilized at 130°C. A nitrogen system was then activated at a flow rate of 30 ml / min. While maintaining a steady nitrogen flow rate, the eutectic was heated for 20 minutes. The heat source was then turned off and the eutectic was allowed to cool to room temperature to obtain an organic eutectic film.

[0101] Example 22:

[0102] The co-assembled eutectic system is used to prepare an organic eutectic semiconductor thin film using a reduced pressure thermal sublimation technique. The specific steps are as follows:

[0103] Weigh 50 mg of the eutectic from Examples 1-13 and place it in the heating zone of a tube furnace. Then, place several cleaned ITO glass sheets in the cooling zone of the tube furnace. Finally, tighten all valves to ensure airtightness. After this operation, evacuate the tube furnace using a mechanical pump for 30 minutes. Then, slowly increase the temperature until the temperature reaches and stabilizes at 130°C. Then, start nitrogen flow at a constant rate of 30 ml / min. After heating the eutectic for 30 minutes, turn off the heat source, and allow it to cool to room temperature to obtain an organic eutectic film.

[0104] Test example:

[0105] The preparation of organic eutectic devices and their electrical performance testing are as follows:

[0106] like Figure 10 As shown in (a), the prepared organic eutectic film is placed in a vacuum evaporation apparatus, and a 100-nanometer-thick aluminum electrode is deposited on its surface, resulting in a "sandwich" memory device. This device is then placed in a semiconductor parameter analyzer, and a sweep voltage of 0 to -5 V and 0 to 5 V is applied to it, and its electrical properties are recorded.

[0107] like Figure 10 (b), 10(c), 10(d): Figure 10 (b) is the electrical performance diagram of a single halogen bond acceptor without halogen bond interaction. Figure 10 (c) is the electrical performance diagram of the eutectic film assembled by halogen bonding, from which it can be seen that Figure 10 Although the halogen bond acceptor in (b) can also show a certain amount of ternary storage performance, Figure 10As can be seen from (d), its reproducibility is only about 5%; Figure 10 The eutectic film (c) not only exhibits typical ternary storage performance, but also has a device unit reproducibility of over 80%, which has great practical application value.

[0108] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A method for assisted molecular self-assembly by halogen bonding, characterized in that: The following steps are involved: (1) Selecting 3,6-di(pyridin-2-yl)tetrazine or 3,6-di(pyridin-4-yl)tetrazine as the halogen bond acceptor; (2) selecting a 1,4-diiodobenzene derivative containing a fluorine atom as a halogen bond donor; the halogen bond donor is one of 1,4-diiodo-2-fluorobenzene, 1,3-difluoro-2,5-diiodobenzene, 1,4-difluoro-2,5-diiodobenzene, and 1,4-diiodotetrafluorobenzene; (3) Dissolving the halogen bond acceptor and the halogen bond donor in steps (1) and (2) in a solvent, heating, stirring, and ultrasonicating, and obtaining an assembly solution after the solution becomes clear and transparent, and evaporating the solvent to obtain a co-crystal.

2. The halogen bond-assisted molecular self-assembly method according to claim 1, characterized in that: In step (3), the molar ratio of the halogen bond acceptor to the halogen bond donor is 1:(1-4).

3. The halogen bond-assisted molecular self-assembly method according to claim 1, characterized in that: In step (3), the concentration of the halogen bond acceptor in the assembly solution is 10 -3 -10 -2 mol / L.

4. The halogen bond-assisted molecular self-assembly method according to claim 1, characterized in that: In step (3), the solvent is one of anhydrous ethanol, tetrahydrofuran, dichloromethane, and chloroform.

5. The halogen bond-assisted molecular self-assembly method according to claim 1, characterized in that: In step (3), the ambient temperature for volatilizing the solvent is 25-35°C.

6. A method for preparing a eutectic thin film, characterized in that: The method of preparing a eutectic thin film using the eutectic prepared by the halogen bond-assisted molecular self-assembly method according to any one of claims 1 to 5 comprises the following steps: (1) placing the eutectic in a heating zone; (2) Place the substrate in the cooling zone; (3) After evacuation, the heating zone is slowly heated to 130-200°C and nitrogen is introduced at a flow rate of 30-50 ml / min. Heating is continued for 10-30 minutes at a stable nitrogen flow rate. After cooling to room temperature, a eutectic film is obtained.

7. An application of the eutectic thin film prepared by the preparation method of the eutectic thin film as claimed in claim 6 as ultra-high density information storage.

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