Organic semiconductor molecular nanolaminate structure and method of making same
By self-assembling organic semiconductor molecules on a highly oriented pyrolytic graphite interface and using STM imaging, the problem of preparing large-area regular layered structures on solid-liquid interfaces was solved, and the application of organic semiconductor molecular nanolayered structures in optoelectronic devices was realized.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- QINGDAO UNIV OF SCI & TECH
- Filing Date
- 2022-07-12
- Publication Date
- 2026-06-19
AI Technical Summary
Existing technologies struggle to achieve the self-assembly of large-area, structurally regular organic semiconductor molecular layered structures at solid-liquid interfaces, and the growth of tunable layered structures from two-dimensional to three-dimensional remains challenging.
Organic semiconductor molecular nanolayer structures were prepared on the interface of highly oriented pyrolytic graphite (HOPG) using a self-assembly method. High-resolution imaging was performed using scanning tunneling microscopy (STM). By depositing organic semiconductor molecules on the solid-liquid interface and scanning, a regular nanolayer structure was formed.
The prepared organic semiconductor molecular nanolayer structure is well-organized, with single-layer or multi-layer structures, and is suitable for light-emitting diodes, solar cells and transistors, exhibiting good stability and order.
Smart Images
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Abstract
Description
Technical Field
[0001] This invention relates to the field of new materials, specifically to an organic semiconductor molecular nanolayer structure and its preparation method. Background Technology
[0002] The self-assembly property of molecules provides a simple pathway to obtaining controllable, functional, long-range ordered layered structures at solid-liquid interfaces. Designing and realizing functionalized long-range ordered layered structures on solid-liquid surfaces requires understanding how to balance non-covalent forces between molecules and between molecules and substrates, guiding molecular assembly into a well-defined ordered layered structure. The self-assembly method for fabricating large-area, structurally regular layered structures is a challenging problem in cutting-edge crystal engineering, and achieving tunable layered structure growth from two-dimensional to three-dimensional is also a significant challenge in current layered structure growth research. Due to the high reproducibility of self-assembly techniques, self-assembled materials can be easily applied to the development of large-scale devices. Organic semiconductor crystal engineering at interfaces has attracted considerable attention due to its potential applications in nanoelectronics and devices.
[0003] Scanning tunneling microscopy (STM) is specifically designed for working under a wide range of conditions, including ultra-high vacuum (UHV), ambient conditions, and at solid-liquid interfaces. STM is an excellent choice for high-resolution imaging of molecules on conductive surfaces. Over the past few decades, STM has been used to study a wide range of systems, including liquid crystals, self-assembled monolayers, and conductive molecular crystals, in diverse experimental environments ranging from ultra-high vacuum to ambient conditions and various liquids (organic solvents, aqueous electrolytes, ionic liquids, etc.). The invention of STM opened a door to exploring self-assembled layered structures at atomic resolution, becoming an important tool in supramolecular chemistry and a crucial means of studying the self-assembled layered structures of molecules at liquid-solid interfaces. Summary of the Invention
[0004] This invention proposes an organic semiconductor molecular nanolayer structure and its preparation method. We have, for the first time, successfully prepared a structurally regular organic semiconductor molecular nanolayer structure material at the interface of highly oriented pyrolytic graphite (HOPG) using a self-assembly method. This organic semiconductor molecular nanolayer structure material shows great promise for applications in light-emitting diodes, solar cells, and transistors.
[0005] This invention provides an organic semiconductor molecule of formula (I):
[0006]
[0007] R is selected from different types of flexible chains, including alkyl chains of different lengths. n H 2n+1X is selected from alkynyl, methylene, and heterocyclic groups; the selected self-assembled organic semiconductor molecules are not limited to those containing perylene imide groups, but also include different kinds of aromatic conjugated systems, and the substitution sites of the linkage groups on the aromatic ring include substitution sites on the aromatic ring and other substitution sites.
[0008] The organic semiconductor molecular nanolayer structure described above is simple and easy to prepare, has a regular structure, and can have a single layer or multiple layers. The interlayer height of the multilayer structure is about 0.6 nm, and it has good stability.
[0009] The present invention adopts the following technical solution:
[0010] An organic semiconductor molecular nanolayer structure is characterized by its regular structure and having a single-layer or multi-layer structure.
[0011] Furthermore, the organic semiconductor molecular nanolayer structure exhibits a parallel stripe pattern under a scanning tunneling microscope.
[0012] Furthermore, the organic semiconductor molecular nanolayer structure is a layered organic semiconductor material that can be used in light-emitting diodes, solar cells, and transistors.
[0013] Furthermore, the organic semiconductor molecular nanolayer structure is grown in a layered manner, consisting of one or more monolayers.
[0014] Furthermore, the organic semiconductor molecular nanolayer structure is prepared by self-assembly.
[0015] This invention provides a method for preparing the organic semiconductor molecular nanolayer structure as described above, comprising the following steps:
[0016] Step 1: Select organic semiconductor molecules and dissolve them in solvents at concentrations ranging from 0.01 to 10 mM;
[0017] Step 2: Heat to fully dissolve;
[0018] Step 3: The substrate used is processed to make it flat; wherein, the substrate selected for growing the organic semiconductor molecular nanolayer structure is a substrate with an inert surface and no strong interaction with the organic semiconductor molecules. The substrate is one or more of highly oriented pyrolytic graphite (HOPG), Au(111), Cu(000), Cu(100), Cu(111), and Si(111).
[0019] Step 4: Level the operating table and perform shockproofing.
[0020] Step 5: Fix the substrate and deposit organic semiconductor molecules on the substrate;
[0021] Step 6: Deposition for 5 to 60 minutes yields an organic semiconductor molecular nanolayer structure;
[0022] Step 7: Use a scanning tunneling microscope to scan the prepared organic semiconductor molecular nanolayer structure to obtain an image. The scanning conditions are a bias voltage of -100 to -1000 mV and a tunneling current of 0 to 100 pA.
[0023] Furthermore, in step one, the selected organic semiconductor molecules are high-purity organic semiconductor molecules.
[0024] Furthermore, in step one, the solvent selected includes one or more of butyric acid, valeric acid, hexanoic acid, octanoic acid, octanol, 1-phenyloctane, and 1,2,4-trichlorobenzene.
[0025] Furthermore, in step two, the selected heating temperature is between 0 and 100 degrees Celsius.
[0026] Furthermore, in step five, the substrate must be maintained at a temperature of 10 to 40 degrees Celsius during the formation of the organic semiconductor molecular nanolayer structure.
[0027] The present invention has the following beneficial effects:
[0028] 1. The method of this invention is carried out at the solid-liquid interface, and the self-assembled organic semiconductor molecular nanolayer structure prepared is convenient for subsequent application research in optoelectronics, energy storage and other fields;
[0029] 2. The organic semiconductor molecular nanolayer structure prepared by this invention has a regular structure and has a single-layer or multi-layer structure. Attached Figure Description
[0030] Appendix Figure 1 These are schematic diagrams of the organic semiconductor molecular structures of Examples 1-3 of the present invention;
[0031] Appendix Figure 2 This is a schematic diagram of the growth method for preparing organic semiconductor molecular nanolayer structures according to the present invention;
[0032] Appendix Figure 3 This is a scanning tunneling microscope image of the organic semiconductor molecule PEP nanolayer structure from Example 1 of the present invention;
[0033] Appendix Figure 4 This is a scanning tunneling microscope image of the organic semiconductor molecule PBP nanolayer structure from Example 2 of the present invention;
[0034] Appendix Figure 5 This is a scanning tunneling microscope image of the organic semiconductor PHP nanolayer structure of Example 3 of the present invention;
[0035] Appendix Figure 6 This is a scanning tunneling microscope image of the organic semiconductor PHP nanolayer structure of Example 3 of the present invention; Detailed Implementation
[0036] The embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood that the embodiments described herein are for illustration and explanation only and are not intended to limit the present invention. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.
[0037] Unless otherwise specified, the three organic semiconductor molecules are named PEP, PBP, and PHP in the instruction manual.
[0038] Example 1
[0039] The specific implementation steps are as follows:
[0040] Step 1: Dissolve PEP in 1-phenyloctane solvent;
[0041] Step 2: Heat to 60 degrees Celsius until fully dissolved;
[0042] Step 3: Highly oriented pyrolytic graphite (HOPG) is selected as the substrate for growing organic semiconductor molecular layered structures. Under atmospheric room temperature conditions, the surface is cleaved by adhesive tape to obtain an atomically smooth surface.
[0043] Step 4: Leveling and vibration damping of the operating stage. Fix the cleaved HOPG substrate onto the STM sample stage, add sample solution to the substrate, deposit PEP molecules, and then maintain these conditions to grow the organic semiconductor molecule PEP nanolayer structure.
[0044] Step 5: The STM tip is made of platinum-iridium wire and processed using a mechanical forming method to obtain an atomic-level tip.
[0045] Step Six: After 5 to 60 minutes of sample deposition, begin scanning the prepared organic semiconductor molecular PEP nanolayer structure. Figure 3 This is a high-resolution scanning tunneling microscope (STM) image of the organic semiconductor molecule PEP nanolayer structure obtained in Example 1, with an image size of 20 nm × 20 nm. The bias voltage used for scanning was -700 mV, and the tunneling current was 60 pA. It can be seen that the obtained organic semiconductor molecule PEP nanolayer structure is of very high quality, with a high degree of order in the surface molecular arrangement, and large-area ordered organic semiconductor molecule PEP nanolayer structures can be obtained. The high-resolution STM image shows parallel stripe patterns on the surface of the organic semiconductor molecule PEP nanolayer structure.
[0046] Example 2
[0047] The specific implementation steps are as follows:
[0048] Step 1: Dissolve PBP in 1-phenyloctane solvent;
[0049] Step 2: Heat to 60 degrees Celsius until fully dissolved;
[0050] Step 3: Highly oriented pyrolytic graphite (HOPG) is selected as the substrate for growing organic semiconductor molecular layered structures. Under atmospheric room temperature conditions, the surface is cleaved by applying adhesive tape to obtain an atomically smooth surface.
[0051] Step 4: Leveling and vibration damping of the operating stage. Fix the cleaved HOPG substrate onto the STM sample stage, add sample solution to the substrate, deposit PBP molecules, and then maintain these conditions to grow the organic semiconductor molecule PBP nanolayer structure.
[0052] Step 5: The STM tip is made of platinum-iridium wire and processed using a mechanical forming method to obtain an atomic-level tip.
[0053] Step Six: After 5 to 60 minutes of sample deposition, begin scanning the prepared organic semiconductor molecular PBP nanolayer structure. Figure 4 This is a high-resolution scanning tunneling microscope (STM) image of the organic semiconductor molecular PBP nanolayer structure obtained in Example 2, with an image size of 15 nm × 15 nm. The bias voltage used for scanning was -650 mV, and the tunneling current was 65 pA. It can be seen that the obtained organic semiconductor molecular PBP nanolayer structure is of very high quality, with a high degree of order in the surface molecular arrangement, and a large-area ordered organic semiconductor molecular PBP nanolayer structure can be obtained. The high-resolution STM image shows parallel stripe patterns on the surface of the organic semiconductor molecular PBP nanolayer structure.
[0054] Example 3
[0055] The specific implementation steps are as follows:
[0056] Step 1: Dissolve PHP in 1-phenyloctane solvent;
[0057] Step 2: Heat to 60 degrees Celsius until fully dissolved;
[0058] Step 3: Highly oriented pyrolytic graphite (HOPG) is selected as the substrate for growing organic semiconductor molecular layered structures. Under atmospheric room temperature conditions, the surface is cleaved by applying adhesive tape to obtain an atomically smooth surface.
[0059] Step 4: Level the operating stage and perform shockproofing. Fix the cleaved HOPG substrate onto the STM sample stage, add sample solution to the substrate, deposit PHP molecules, and then maintain these conditions to grow the organic semiconductor PHP nanolayer structure.
[0060] Step 5: The STM tip is made of platinum-iridium wire and processed using a mechanical forming method to obtain an atomic-level tip.
[0061] Step Six: After sample deposition for 5 to 60 minutes, begin scanning the prepared organic semiconductor molecular PHP nanolayer structure. Figure 5 This is a high-resolution scanning tunneling microscope (STM) image of the organic semiconductor PHP nanolayer structure obtained in Example 3, with an image size of 15 nm × 15 nm. The bias voltage used for scanning was -550 mV, and the tunneling current was 55 pA. It can be seen that the obtained organic semiconductor PHP nanolayer structure is of very high quality, with a high degree of order in the surface molecular arrangement, and a large-area ordered organic semiconductor PHP nanolayer structure can be obtained. The high-resolution STM image shows parallel stripe patterns on the surface of the organic semiconductor PHP nanolayer structure. (See attached image.) Figure 6 This is a high-resolution scanning tunneling microscope image of the organic semiconductor PHP nanolayer structure obtained in Example 3, with an image size of 80 nm × 80 nm. The bias voltage used for scanning was -500 mV, and the tunneling current was 55 pA. Measurements of the layer height revealed that the interlayer height of the multilayer structure ranged from 0.4 to 0.8 nm.
[0062] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. It should be noted that those skilled in the art can prepare organic semiconductor molecular nanolayer structures by simply changing the molecules or different parameters without departing from the technical principles of the present invention. The present invention can self-assemble organic semiconductor molecular nanolayer structures at the solid-liquid interface, with a simple process and regular structure. The prepared self-assembled organic semiconductor molecular nanolayer structure material is of great significance for applications in optoelectronics, energy storage, and other fields.
Claims
1. An organic semiconductor molecular nanolayered structure, characterized by, The structure is regular and has a multilayer structure; the organic semiconductor molecule has the structure shown in Formula 1: ； wherein R is selected from alkyl chains of varying length C n H 2n+1 ; X is selected from alkynyl; The organic semiconductor molecular nanolayer structure is grown by self-assembly layered growth and consists of several monolayers; its preparation method includes the following steps: Step 1: Select a solvent for dissolving organic semiconductor molecules with a concentration ranging from 0.01 mM to 10 mM; Step 2: Heat to 60℃ to fully dissolve; Step 3: The substrate used is processed to make it flat; wherein, the substrate selected for growing the organic semiconductor molecular nanolayer structure is a substrate with an inert surface and no strong interaction with the organic semiconductor molecules, and the substrate is one or more of highly oriented pyrolytic graphite (HOPG), Au(111), Cu(000), Cu(100), Cu(111), and Si(111); Step 4: Level the operating table and perform shockproofing. Step 5: Fix the substrate and deposit organic semiconductor molecules on the substrate; Step 6: Deposition for 60 minutes yields an organic semiconductor molecular nanolayer structure; Step 7: Use a scanning tunneling microscope to scan the prepared organic semiconductor molecular nanolayer structure to obtain an image. The scanning conditions are a bias voltage of -100mV to -1000mV and a tunneling current of 0pA to 100pA.
2. The organic semiconductor molecular nanolayered structure according to claim 1, characterized in that, It exhibits a parallel stripe pattern under a scanning tunneling microscope.
3. The organic semiconductor molecular nanolayered structure according to claim 1, wherein It is a layered organic semiconductor material that can be used in light-emitting diodes, solar cells, and transistors.
4. The organic semiconductor molecular nanolayered structure according to claim 1, wherein In step one, the selected organic semiconductor molecules are high-purity organic semiconductor monomers.
5. The organic semiconductor molecular nanolayered structure according to claim 1, wherein In step one, the selected solvent includes one or more of butyric acid, valeric acid, hexanoic acid, octanoic acid, octanol, 1-phenyloctane, and 1,2,4-trichlorobenzene.
6. The organic semiconductor molecular nanolayer structure according to claim 1, characterized in that, In step five, the substrate must be maintained at a temperature of 10 to 40 degrees Celsius during the formation of the organic semiconductor molecular nanolayer structure.