Molecular assembly method of d-a type blending system and application thereof
By using a molecular assembly method based on DA-type blending systems, the problem of irregular molecular stacking in organic storage devices has been solved, achieving high-stability and high-density information storage, simplifying molecular structure regulation, and reducing manufacturing costs.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHANGSHU INSTITUTE OF TECHNOLOGY
- Filing Date
- 2026-04-13
- Publication Date
- 2026-07-03
AI Technical Summary
The irregular molecular packing in existing organic storage devices leads to poor device stability, low repeatability, and unclear storage mechanism, which limits the practical application of multi-level electrical storage.
A molecular assembly method using a DA-type blend system was adopted, with indo[3,2-B]carbazole as an electron donor and N,N'-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic diimide as an electron acceptor. After heating and ultrasonic dissolution, the DA-type assembled film was formed on a conductive substrate through self-assembly. The close intermolecular packing was achieved by utilizing π-π stacking and hydrogen bonding.
It improves intermolecular interactions and orderly compact packing, enhances device stability and repeatability, enables information storage functions of different proportions, such as binary and ternary storage, and reduces manufacturing costs.
Smart Images
Figure CN122054890B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the fields of functional semiconductor materials and electronic information, and relates to a molecular assembly method for a DA-type blend system and its application in the field of ultra-high density information storage. Background Technology
[0002] With the explosive growth of information storage, the storage devices currently on the market are far from meeting the demand. The extremely high demand for storage density creates a significant contradiction with the physical limitations of traditional materials and the constraints of device fabrication processes. Currently, there are two main approaches to address this contradiction: one is to develop new fabrication processes to further reduce device unit size and increase storage density; the other is to attempt to overcome the limitations of traditional binary storage and develop multi-level storage devices. Therefore, achieving a qualitative breakthrough in information storage density requires innovative material systems and innovative storage mechanisms.
[0003] Currently, the development of organic materials in the field of electrical storage still faces some challenges, such as poor device stability, low repeatability, and unclear storage mechanisms. These significantly limit the future practical application of organic multi-level electrical storage. The fundamental solution lies in achieving a more orderly stacking of the active storage layer material in the memory. As is well known, the molecular stacking in thin films is one of the most important factors affecting device performance, significantly influencing the effective transport of charge carriers and consequently impacting the device's stability, repeatability, and reliability. Furthermore, orderly and ordered intermolecular structures in thin films are beneficial for clarifying the device's conductivity mechanism, providing theoretical guidance for designing reliable ternary memory devices. The stacking in organic small molecules and polymer thin films mainly depends on two non-covalent forces: van der Waals forces (such as π-π stacking interactions) and the formation of non-covalent bonds (such as hydrogen bonding). Therefore, enhancing intermolecular π-π stacking interactions and introducing hydrogen bonding have become the main design strategies for controlling intermolecular stacking. Summary of the Invention
[0004] Purpose of the invention: The purpose of this invention is to overcome the problems of molecular stacking and poor device stability in existing memory devices, and to provide a molecular assembly method for DA-type blend systems.
[0005] Another objective of this invention is to provide a DA-type assembled thin film prepared by a molecular assembly method using a DA-type blend system and its application as an ultra-high density information storage device.
[0006] Technical solution: The present invention provides a molecular assembly method for a DA-type blend system, comprising the following steps:
[0007] (1) Using indo[3,2-B]carbazole as electron donor (D) and N,N'-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic diimide as electron acceptor (A), the electron donor (D) and electron acceptor (A) were dispersed in an organic solvent and dissolved by heating and sonication to obtain a clear and transparent DA-type blend system assembly solution;
[0008] (2) Insert the cleaned conductive substrate vertically into the DA type blend system assembly liquid, soak it for a period of time, and then use a lifting device to lift the conductive substrate at a constant speed until the conductive substrate is completely removed from the liquid surface. Place it horizontally and let the solvent evaporate naturally until it is completely dry to obtain a fully assembled DA type assembly film.
[0009] The structural formula of the electron donor (D) is shown in Equation 1:
[0010]
[0011] Formula 1;
[0012] The structural formula of the electron acceptor (A) is shown in Formula 2:
[0013]
[0014] Formula 2;
[0015] The structural formula of the DA type assembly is shown in Formula 3:
[0016]
[0017] Formula 3.
[0018] Furthermore, the conductive substrate is indium tin oxide (ITO) glass.
[0019] Further, in step (1), the molar ratio of the electron donor (D) to the electron acceptor (A) is (0.5~2):1;
[0020] Furthermore, the organic solvent is selected from one of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), trifluoroacetic acid (TFA), diphenylmethane, and propylene carbonate.
[0021] Furthermore, in step (1), the heating temperature is controlled at 60 ℃~80 ℃; the ultrasound time is controlled at 2 h~4 h.
[0022] Further, in step (1), the concentration of the assembly solution of the DA-type blend system is 10. -2 ~10 -1 mol / L.
[0023] Further, in step (2), the immersion time of the conductive substrate in the DA-type blend system assembly solution is 2 min to 10 min.
[0024] Furthermore, in step (2), the lifting speed of the conductive substrate is 1~5 mm / min.
[0025] This invention provides a DA-type assembled thin film, which is prepared by the molecular assembly method of the above-mentioned DA-type blend system.
[0026] This invention provides an application of the above-mentioned DA-type assembled film as an ultra-high density information storage.
[0027] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The electron donor (D) and electron acceptor (A) described in the present invention can be purchased directly, which provides a good material guarantee for large-scale practical application in the later stage;
[0028] (2) The electron donor (D) and electron acceptor (A) selected in this invention both have large conjugated planes, which is beneficial to enhance the π-π stacking interaction between the electron donor (D) and electron acceptor (A), thereby enhancing the close packing mode between molecules; secondly, the NH bond in the backbone of the electron donor (D) and the pyridine at the end of the electron acceptor (A) also have a certain hydrogen bond interaction, which further enhances the interaction between molecules and the orderly close packing between molecules; at the same time, thanks to the distinct electron-donating and electron-withdrawing properties of the electron donor (D) and electron acceptor (A), the electron donor (D) and electron acceptor (A) also have additional charge transfer (CT) effect, which further enhances the interaction between molecules and is beneficial to the effective transport of charge carriers between films;
[0029] (3) The method for forming a DA-type self-assembled thin film system by the blend of electron donor (D) and electron acceptor (A) of the present invention is simple and easy to implement. It can be achieved by immersing the conductive substrate in the DA blend and then pulling it out at a uniform speed. During the evaporation of the solution, the electron donor (D) and electron acceptor (A) can obtain a DA-type assembled thin film with a close and orderly stack under the synergistic effect of various intermolecular forces—π-π stacking, non-covalent hydrogen bonding, and charge transfer (CT) interaction.
[0030] (4) By adjusting the different ratios of electron donor (D) and electron acceptor (A), the DA-type self-assembled thin film system prepared by this invention can exhibit different information storage functions (such as binary and ternary). Compared with molecular structure regulation, it is simpler and easier to implement, and provides a simple and efficient strategy for subsequent manufacturing of storage devices with low cost, good molecular stacking and high storage density. Attached Figure Description
[0031] Figure 1 The image shows a device with a "sandwich" structure prepared based on the thin film of Example 1 and its cross-sectional view.
[0032] Figure 2 This is a graph showing the electrical storage performance of the storage device in Example 1;
[0033] Figure 3 This is a graph showing the electrical storage performance of the storage device in Example 7;
[0034] Figure 4 This is a graph showing the electrical storage performance of the storage device in Example 6;
[0035] Figure 5 Theoretical simulation diagram of electron donor (D);
[0036] Figure 6 This is a theoretical simulation diagram of the electron acceptor (A).
[0037] Figure 7 Energy level diagram for electron donor (D) and electron acceptor (A);
[0038] Figure 8 The image shows the X-ray diffraction (XRD) pattern of the thin film in Example 6. Detailed Implementation
[0039] 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 and implement the present invention. However, the embodiments described are not intended to limit the present invention.
[0040] Example 1:
[0041] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0042] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of 1:1. Then add this mixture to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution. The heating temperature is 60 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixture again through a 0.22 μm diameter organic filter and transfer it to a glass dish used for the dip tracing apparatus.
[0043] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0044] Example 2:
[0045] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0046] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of electron donor (D) to electron acceptor (A) of 1:1. Next, add them to 10 mL of dimethyl sulfoxide (DMSO) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution system. The heating temperature is 60 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution system again through a 0.22 μm diameter organic filter and transfer it to a glass container used for a dipstick.
[0047] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0048] Example 3:
[0049] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0050] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of 1:1. Next, add them to 10 mL of trifluoroacetic acid (TFA) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution. The heating temperature is 60 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution again through a 0.22 μm diameter organic filter and transfer it to a glass container used for a dipstick.
[0051] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0052] Example 4:
[0053] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0054] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of 1:1. Add these to 10 mL of diphenylmethane to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution. The heating temperature is 60 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear solution again through a 0.22 μm diameter organic filter and transfer it to a glass dish used for the dip tracing apparatus.
[0055] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0056] Example 5:
[0057] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0058] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of 1:1. Add these to 10 mL of propylene carbonate to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution. The heating temperature is 60 °C, and the sonication time is 2 h. Finally, filter the dissolved and transparent mixture again through a 0.22 μm diameter organic filter and transfer it to a glass dish used for a dipstick.
[0059] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0060] Example 6:
[0061] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0062] Weigh out 52 mg (0.20 mmol) of electron donor (D) and 42 mg (0.10 mmol) of electron acceptor (A), with a molar ratio of electron donor (D) to electron acceptor (A) of 2:1. Next, add this mixture to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution system. The heating temperature is 60 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution system again through a 0.22 μm diameter organic filter and transfer it to a glass container used for a dipstick.
[0063] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0064] Example 7:
[0065] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0066] Weigh out 26 mg (0.10 mmol) of electron donor (D) and 84 mg (0.20 mmol) of electron acceptor (A), with a molar ratio of electron donor (D) to electron acceptor (A) of 1:2. Next, add them to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution system. The heating temperature is 60 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution system again through a 0.22 μm diameter organic filter and transfer it to a glass container used for a dipstick.
[0067] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0068] Example 8:
[0069] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0070] Weigh out 13 mg (0.05 mmol) of electron donor (D) and 21 mg (0.05 mmol) of electron acceptor (A), with a molar ratio of 1:1. Next, add this mixture to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.01 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution. The heating temperature is 60 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution again through a 0.22 μm diameter organic filter and transfer it to a glass container used for a dipstick.
[0071] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0072] Example 9:
[0073] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0074] Weigh out 128 mg (0.5 mmol) of electron donor (D) and 210 mg (0.5 mmol) of electron acceptor (A), with a molar ratio of electron donor (D) to electron acceptor (A) of 1:1. Next, add this mixture to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.1 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution system. The heating temperature is 60 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution system again through a 0.22 μm diameter organic filter and transfer it to a glass container used for a dipstick.
[0075] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0076] Example 10:
[0077] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0078] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of 1:1. Next, add them to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution system. The heating temperature is 70 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution system again through a 0.22 μm diameter organic filter and transfer it to a glass container used for a dipstick.
[0079] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0080] Example 11:
[0081] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0082] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of electron donor (D) to electron acceptor (A) of 1:1. Next, add them to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution system. The heating temperature is 80 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution system again through a 0.22 μm diameter organic filter and transfer it to a glass container used for a dipstick.
[0083] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0084] Example 12:
[0085] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0086] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of 1:1. Then add this mixture to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution. The heating temperature is 70 °C, and the sonication time is 3 h. Finally, filter the dissolved and clear mixed solution again through a 0.22 μm diameter organic filter and transfer it to a glass dish used for a dipstick.
[0087] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0088] Example 13:
[0089] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0090] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of 1:1. Next, add this mixture to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution. The heating temperature was 70 °C, and the sonication time was 4 h. Finally, filter the dissolved and clear mixed solution again through a 0.22 μm diameter organic filter and transfer it to a glass container used for a dipstick.
[0091] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 1 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0092] Example 14:
[0093] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0094] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of 1:1. Next, add this mixture to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution. The heating temperature is 70 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution again through a 0.22 μm diameter organic filter and transfer it to a glass dish used for a dipstick.
[0095] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 2 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0096] Example 15:
[0097] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0098] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of 1:1. Next, add this mixture to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution. The heating temperature is 70 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution again through a 0.22 μm diameter organic filter and transfer it to a glass dish used for a dipstick.
[0099] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 2 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 5 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0100] Example 16:
[0101] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0102] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of 1:1. Next, add this mixture to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution. The heating temperature is 70 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution again through a 0.22 μm diameter organic filter and transfer it to a glass dish used for a dipstick.
[0103] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 5 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 2 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0104] Example 17:
[0105] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0106] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of 1:1. Next, add this mixture to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution. The heating temperature is 70 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution again through a 0.22 μm diameter organic filter and transfer it to a glass dish used for a dipstick.
[0107] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 8 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 2 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0108] Example 18:
[0109] The specific steps for preparing the assembly solution of the DA-type blend system and the self-assembly of the DA-type thin film system are as follows:
[0110] Weigh out 38 mg (0.15 mmol) of electron donor (D) and 63 mg (0.15 mmol) of electron acceptor (A), with a molar ratio of 1:1. Next, add this mixture to 10 ml of N,N-dimethylformamide (DMF) to achieve a concentration of 0.03 mol / L. Heat and sonicate until completely dissolved, forming a clear and transparent solution. The heating temperature is 70 °C, and the sonication time is 2 h. Finally, filter the dissolved and clear mixed solution again through a 0.22 μm diameter organic filter and transfer it to a glass dish used for a dipstick.
[0111] A clean ITO glass was vertically inserted into the assembly solution of the DA-type blend system prepared above until the ITO glass was completely submerged below the liquid surface. After the ITO glass was left to stand in the DA-type blend system assembly solution for 10 minutes, a puller was used to slowly pull the ITO glass until it was completely removed from the liquid surface, controlling the pulling speed at 2 mm / min. Then, the pulled-out ITO glass was placed horizontally in a fume hood to ensure that the solvent slowly evaporated at room temperature, so as to ensure that the electron donor (D) and electron acceptor (A) were fully assembled under the synergistic effect of various intermolecular forces. After the solvent had completely evaporated, the fully assembled DA-type thin film system was obtained.
[0112] Test example:
[0113] The specific steps for device fabrication and electrical performance testing of the DA-type assembled thin film system are as follows:
[0114] The prepared organic eutectic film was placed in a vacuum evaporation apparatus, and an aluminum electrode with a thickness of 100 nanometers and a diameter of 120 micrometers was deposited on its surface to obtain the following result: Figure 1 The memory device shown has a "sandwich" structure. This device was then placed on a semiconductor parameter analyzer, and scan voltages of 0 to -5 V and 0 to 5 V were applied to record its electrical performance.
[0115] like Figure 2 , 3 As shown in Figure 4: Figure 2 The electrical performance graph is obtained from testing the device prepared by the blend of electron donor (D) and electron acceptor (A) in Example 1 with a molar ratio of 1:1. Figure 3 The graph shows the electrical performance of the device prepared by the blend of electron donor (D) and electron acceptor (A) in Example 7 with a molar ratio of 1:2. As can be seen from the graph, when the molar ratio of electron donor (D) and electron acceptor (A) is 1:1 and 1:2, the device exhibits conventional binary storage performance. Figure 4The graph shows the electrical performance of the device prepared by the blend of electron donor (D) and electron acceptor (A) in Example 6 with a molar ratio of 2:1. As can be seen from the graph, the device exhibits typical ternary storage performance, which greatly improves the storage density of the device. Different information storage performances can be achieved simply by adjusting the ratio of electron donor (D) and electron acceptor (A), which is much simpler and faster than through complex and cumbersome structural design.
[0116] like Figure 5 and 6 As shown, the electron donor indo[3,2-B]carbazole exhibits a continuous positive electrostatic potential (red) open channel across its entire molecular surface, indicating that charge carriers can move freely through this open channel. Additionally, the electron acceptor N,N'-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylate diimide possesses an extra negative electrostatic potential region (blue), primarily attributed to the pyridine and carbonyl electron-withdrawing groups in N,N'-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylate diimide. These blue regions act as "charge traps," hindering the free movement of charge carriers within the film, thus resulting in a low conductivity state for the device in its initial state. Meanwhile, as... Figure 7 As shown in the simulation results, the energy level difference of a single electron donor is 2.80 eV, and the energy level difference of a single electron acceptor is 2.50 eV, both of which are greater than the energy level difference between the HOMO level of N,N'-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic diimide and the LUMO level of indo[3,2-B]carbazole. Therefore, there is a significant charge transfer interaction between the electron donor and the electron acceptor.
[0117] Figure 8 The image shows the X-ray diffraction (XRD) pattern of the thin film in Example 6. As can be seen from the image, the thin film exhibits obvious crystal diffraction peaks, indicating that the electron donor and electron acceptor form a highly ordered intermolecular stacking mode in the thin film, which is beneficial to the effective transport of charge carriers within the thin film.
[0118] For the DA-type blend film assembled in Example 6, under the influence of the electric field, charge carriers are directly injected from the electrode into the "charge traps" of the N,N'-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide molecule. Once the electron acceptor-based "charge traps" are filled, the device can transition from a low conductivity state (OFF state) to an intermediate conductivity state (ON1 state). However, due to the highly ordered arrangement formed in the D / A=2:1 film, as the scanning electric field further increases, the charge transfer between the electron donor and electron acceptor molecules causes charge carriers in the electron donor to be further injected into the electron acceptor, resulting in a transition similar to that from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO), forming a new conductive channel. The device can then transition from the intermediate conductivity ON1 state to a high conductivity state (ON2 state). Once the device completes the transition from the OFF state to the ON2 state, the electron density shifts from the electron-donating groups to the electron-withdrawing groups and becomes more stable. Therefore, the charge carriers do not easily dissociate under the stimulation of a closed electric field or a reverse electric field, and thus the device exhibits typical ternary WORM-type storage performance.
[0119] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
Claims
1. A molecular assembly method for a DA-type blend system, characterized in that, Includes the following steps: (1) Using indo[3,2-B]carbazole as electron donor (D) and N,N'-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic diimide as electron acceptor (A), the electron donor (D) and electron acceptor (A) were dispersed in an organic solvent and dissolved by heating and sonication to obtain a clear and transparent DA-type blend system assembly solution; (2) Insert the cleaned conductive substrate vertically into the DA type blend system assembly liquid, soak it for a period of time, and then use a lifting device to lift the conductive substrate at a constant speed until the conductive substrate is completely removed from the liquid surface. Place it horizontally and let the solvent evaporate naturally until it is completely dry to obtain a fully assembled DA type assembly film.
2. The molecular assembly method for the DA-type blend system according to claim 1, characterized in that, The conductive substrate is indium tin oxide glass.
3. The molecular assembly method for the DA-type blend system according to claim 1, characterized in that, In step (1), the molar ratio of the electron donor (D) to the electron acceptor (A) is (0.5~2):
1.
4. The molecular assembly method for the DA-type blend system according to claim 1, characterized in that, In step (1), the organic solvent is selected from N,N-dimethylformamide, dimethyl sulfoxide, trifluoroacetic acid, diphenylmethane and propylene carbonate.
5. The molecular assembly method for the DA-type blend system according to claim 1, characterized in that, In step (1), the heating temperature is controlled at 60 ℃~80 ℃; the ultrasound time is controlled at 2 h~4 h.
6. The molecular assembly method for the DA-type blend system according to claim 1, characterized in that, In step (1), the concentration of the assembly solution of the DA-type blend system is 10. -2 ~10 -1 mol / L.
7. The molecular assembly method for the DA-type blend system according to claim 1, characterized in that, In step (2), the immersion time of the conductive substrate in the DA-type blend system assembly solution is 2 min to 10 min.
8. The molecular assembly method for the DA-type blend system according to claim 1, characterized in that, In step (2), the lifting speed of the conductive substrate is 1~5 mm / min.
9. A DA-type assembled thin film, characterized in that, It was prepared by the molecular assembly method of the DA-type blend system according to any one of claims 1-8.
10. An application of the DA-type assembled film of claim 9 as an ultra-high density information storage device.