A method for preparing an array of organic semiconductor materials

Abstract

The present invention discloses a method for preparing an array of organic semiconductor materials. According to a preset array form, a silicon wafer including a silicon column array is prepared; the surface of the silicon column is chemically modified to make the surface of the silicon column reach a super-hydrophobic state; the organic semiconductor material is thermally evaporated under vacuum conditions to make the organic molecules of the organic semiconductor material crystallize on the top surface of the silicon column in a super-hydrophobic state, and an organic semiconductor material sample of a preset thickness is formed on the top surface of the silicon column; the organic semiconductor material sample formed on the silicon wafer is transferred to the substrate, and an organic semiconductor material array having the preset array form is obtained on the substrate. On the one hand, due to the use of a thermal evaporation method, it is particularly suitable for organic semiconductor materials that are difficult to process in liquid phase micro-nano processing; on the other hand, the micro-nano processing quality of the array is ensured by using a method of crystallizing the surface of the super-hydrophobic silicon column and transferring it in parallel.

Description

Technical Field

[0001] The present invention relates to the field of semiconductor technology, and in particular to a method for preparing an array of organic semiconductor materials. Background Art

[0002] At present, liquid phase micro-nano processing technology has made great technological breakthroughs, especially the capillary liquid bridge induction method has made great achievements in controllable arrays and patterning. However, for some high-mobility and high-stability organic semiconductor materials, liquid phase processing cannot be achieved due to their stable chemical properties. Therefore, how to use these organic semiconductor materials for array processing to prepare high-quality organic semiconductor devices is an urgent problem to be solved. Summary of the invention

[0003] In view of the above problems, the present invention provides a method for preparing an array of organic semiconductor materials that overcomes the above problems or at least partially solves the above problems.

[0004] On the one hand, the present application provides the following technical solution through an embodiment of the present application:

[0005] A method for preparing an array of organic semiconductor materials, the method comprising:

[0006] According to a preset array form, a silicon wafer including a silicon pillar array is prepared;

[0007] Chemically modifying the surface of the silicon column to make the surface of the silicon column reach a super-hydrophobic state;

[0008] Thermally evaporate the organic semiconductor material under vacuum conditions to allow organic molecules of the organic semiconductor material to crystallize on the top surface of the silicon pillar in a super-hydrophobic state, thereby forming an organic semiconductor material sample of a preset thickness on the top surface of the silicon pillar;

[0009] The surface of the silicon wafer on which the organic semiconductor material sample is formed is attached to a substrate, so that the organic semiconductor material sample is transferred to the substrate, and an organic semiconductor material array having the preset array form is obtained on the substrate.

[0010] Optionally, the chemical modification of the surface of the silicon pillar specifically includes:

[0011] Under vacuum conditions, a hydrophobic treatment agent is attached to the surface of the silicon column;

[0012] The silicon column to which the hydrophobic treatment agent has been attached is heated to 80-120° C. and maintained for 2-4 hours.

[0013] Optionally, the hydrophobic treatment agent is fluorosilane or octadecyltrichlorosilane.

[0014] Optionally, thermal evaporation of the organic semiconductor material under vacuum conditions specifically includes:

[0015] The thermal evaporation rate of the organic semiconductor material is controlled by adjusting the thermal evaporation temperature according to the properties of the organic semiconductor material.

[0016] Optionally, thermally evaporating the organic semiconductor material under vacuum conditions to allow organic molecules of the organic semiconductor material to crystallize on the top surface of the silicon pillar in a super-hydrophobic state, thereby forming an organic semiconductor material sample of a preset thickness on the top surface of the silicon pillar, specifically includes:

[0017] Based on the thermal evaporation rate and thermal evaporation time of the organic semiconductor material, an organic semiconductor material sample with a preset thickness is formed on the top surface of the silicon pillar.

[0018] Optionally, the substrate is a flexible substrate.

[0019] Optionally, the substrate comprises polydimethylsiloxane;

[0020] Before laminating the surface of the silicon wafer on which the organic semiconductor material sample is formed to a substrate, the method further comprises:

[0021] Mixing polydimethylsiloxane and a hardener in a ratio of 10:1 to obtain a mixture;

[0022] The mixture was heated to 60-100°C and maintained for 2-4 hours to soften the substrate.

[0023] Optionally, laminating the surface of the silicon wafer on which the organic semiconductor material sample is formed to a substrate, transferring the organic semiconductor material sample to the substrate, and obtaining an organic semiconductor material array having the preset array form on the substrate specifically includes:

[0024] When the substrate is in an unsolidified state, the surface of the silicon wafer on which the organic semiconductor material sample is formed is bonded to the substrate, a preset pressure is applied and maintained for a preset time;

[0025] After the substrate is solidified, the silicon pillars are separated from the substrate, and an organic semiconductor material array having the preset array form is obtained on the substrate.

[0026] Optionally, the organic semiconductor material is an organic semiconductor material that cannot be processed in liquid phase.

[0027] On the other hand, the present application provides an organic semiconductor material array through another embodiment of the present application, and the organic semiconductor material array is prepared according to the above method.

[0028] Optionally, the aluminum-doped gallium oxide film has a bandgap of 4.9-8.8 eV.

[0029] One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:

[0030] In order to obtain an organic semiconductor material having a preset array form on a substrate, first, a silicon wafer including a silicon column array is prepared according to the preset array form; the surface of the silicon column is chemically modified to make the surface of the silicon column reach a super-hydrophobic state, so as to facilitate the subsequent separation of the semiconductor material attached to the silicon column; the organic semiconductor material is thermally evaporated under vacuum conditions by a thermal evaporation method, so that the organic molecules of the organic semiconductor material are crystallized on the top surface of the silicon column in a super-hydrophobic state, and an organic semiconductor material sample of a preset thickness is formed on the top surface of the silicon column; the surface of the organic semiconductor material sample formed on the silicon wafer is bonded to the substrate, so that the organic semiconductor material sample is transferred to the substrate, and an organic semiconductor material array having the preset array form is obtained on the substrate. On the one hand, due to the use of the thermal evaporation method, it is particularly suitable for organic semiconductor materials with stable chemical properties that are difficult to process in liquid phase micro-nano; on the other hand, the micro-nano processing quality of the array is ensured by using the method of crystallization and parallel transfer of the super-hydrophobic treated silicon column surface; thereby providing a new method for preparing an organic semiconductor material array, which can prepare high-quality organic semiconductor devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0032] Figure 1 It is a schematic flow chart of a method for preparing an array of organic semiconductor materials according to an embodiment of the present invention;

[0033] Figure 2 yes Figure 1 Schematic diagram of the process of thermal evaporation of organic semiconductor materials on the surface of silicon pillars;

[0034] Figure 3 yes Figure 1 Schematic diagram of the process of transferring the organic semiconductor material sample from the surface of the silicon pillar to the substrate;

[0035] Figure 4 yes Figure 1 Schematic diagram of the bonding of the organic semiconductor material sample on the surface of the silicon pillar and the substrate;

[0036] Figure 5 yes Figure 1 Schematic diagram of the organic semiconductor material sample after being transferred to the substrate. DETAILED DESCRIPTION

[0037] The embodiment of the present application provides a method for preparing an array of an organic semiconductor material, and realizes array processing using organic semiconductor materials that cannot be processed in liquid phase.

[0038] The technical solution of the embodiment of the present application is to solve the above technical problems, and the overall idea is as follows:

[0039] A method for preparing an array of organic semiconductor materials comprises preparing a silicon wafer including a silicon pillar array according to a preset array form; chemically modifying the surfaces of the silicon pillars so that the surfaces of the silicon pillars reach a super-hydrophobic state; thermally evaporating the organic semiconductor material under vacuum conditions so that the organic molecules of the organic semiconductor material are crystallized on the top surfaces of the silicon pillars in a super-hydrophobic state, thereby forming an organic semiconductor material sample of a preset thickness on the top surfaces of the silicon pillars; and laminating the surface of the silicon wafer on which the organic semiconductor material sample is formed to a substrate so that the organic semiconductor material sample is transferred to the substrate, thereby obtaining an organic semiconductor material array having the preset array form on the substrate.

[0040] On the one hand, due to the use of thermal evaporation method, it is particularly suitable for organic semiconductor materials with stable chemical properties that are difficult to process in liquid phase micro-nano process; on the other hand, the micro-nano process quality of the array is ensured by using the method of crystallization and parallel transfer of silicon pillar surface treated with super-hydrophobicity; thus, a new method for preparing organic semiconductor material arrays is provided, which can be used to prepare high-quality organic semiconductor devices.

[0041] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the accompanying drawings and specific implementation methods.

[0042] First of all, the term "and / or" in this article is only a description of the association relationship of the associated objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0043] In addition, the “inside” and “outside” that appear in the text are inside and outside in the conventional sense, which are for the convenience of clear description and are not any limitation.

[0044] Embodiment 1

[0045] See also Figure 1As shown, this embodiment provides a method for preparing an array of organic semiconductor materials, the preparation method comprising:

[0046] S200, preparing a silicon wafer including a silicon pillar array according to a preset array form;

[0047] S400, chemically modifying the surface of the silicon pillar to make the surface of the silicon pillar reach a super-hydrophobic state;

[0048] S600, thermally evaporating the organic semiconductor material under vacuum conditions to allow organic molecules of the organic semiconductor material to crystallize on the top surface of the silicon pillar in a super-hydrophobic state, thereby forming an organic semiconductor material sample of a preset thickness on the top surface of the silicon pillar;

[0049] S800, attaching the surface of the silicon wafer on which the organic semiconductor material sample is formed to a substrate, transferring the organic semiconductor material sample to the substrate, and obtaining an organic semiconductor material array having the preset array form on the substrate.

[0050] In the prior art, conventional processing methods generally use conventional liquid phase micro-nano processing methods for organic semiconductor materials that can be processed in liquid phase, such as capillary liquid bridge induction method, printing, inkjet printing, etc. However, this method is not suitable for processing organic semiconductor materials with high mobility and high stability that cannot be processed in liquid phase, such as C 60 , rubrene, DNTT, etc.

[0051] Although thermal evaporation can solve the problem of not being able to implement liquid phase processing, the array quality obtained by the array processing method based on thermal evaporation is poor. For example, if a mask is used, organic materials will grow on the mask after repeated use and it will be difficult to clean, resulting in a decrease in the accuracy of the mask. In addition, the cost of processing a new mask is too high.

[0052] This embodiment provides a novel method for preparing an array of organic semiconductor materials, which can utilize high-mobility and high-stability organic semiconductor materials that cannot be processed in liquid phase to prepare high-quality organic semiconductor arrays.

[0053] First, S200 is executed to prepare a silicon wafer including a silicon pillar array according to a preset array form.

[0054] It should be noted that in the semiconductor field, due to functional requirements, array processing or pattern processing of organic semiconductor materials on a substrate is often involved. Therefore, the array in this embodiment includes not only the conventionally defined regularly arranged patterns, but also regular or irregular patterns formed by arrays, and even patterns not formed by arrays.

[0055] Specifically, in S200, the silicon wafer including the silicon pillar array is prepared in order to subsequently attach the organic semiconductor material to the surface of the silicon pillars and realize the transfer. Therefore, it is necessary to prepare a silicon wafer including the silicon pillar array matching the preset array form according to the preset array form to be processed in the design. Among them, the number, size, and spacing of the silicon pillars all need to be processed according to the preset array form.

[0056] For example, a single crystal silicon wafer, 4 inches, N-doped, <100> , 525μm thick, each silicon wafer is cut into small silicon wafers of size 1cm×1cm, and each wafer has a silicon column array in a preset array form. Among them: the spacing between each column of silicon columns is 5μm, each column of silicon columns is 2μm wide and 20μm deep.

[0057] Next, S400 is performed to chemically modify the surface of the silicon pillar so that the surface of the silicon pillar reaches a super-hydrophobic state.

[0058] The superhydrophobic state has the characteristics of self-cleaning and low adhesion, so that the surface of the silicon column can not only attach crystalline organic molecules to form organic semiconductor material samples, but also facilitate the subsequent transfer of organic semiconductor material samples.

[0059] As an optional implementation, chemically modifying the surface of the silicon pillar specifically includes:

[0060] Under vacuum conditions, a hydrophobic treatment agent is attached to the surface of the silicon column;

[0061] The silicon column to which the hydrophobic treatment agent has been attached is heated to 80-120° C. and maintained for 2-4 hours.

[0062] Specifically, the hydrophobic treatment agent is fluorosilane or octadecyltrichlorosilane. For example, after the enclosed space is evacuated for 30 minutes, the silicon column is placed in the vacuum enclosed space, and 1-2 μl of medium-fluorosilane is introduced to allow the fluorosilane to adhere to the surface of the silicon column under a vacuum environment, and then heated to 80-120°C and maintained for 2-4 hours, so that the surface of the silicon column reaches a super-hydrophobic state.

[0063] Next, S600 is performed to thermally evaporate the organic semiconductor material under vacuum conditions to allow organic molecules of the organic semiconductor material to crystallize on the top surface of the silicon pillar in a super-hydrophobic state, thereby forming an organic semiconductor material sample of a preset thickness on the top surface of the silicon pillar.

[0064] In the specific implementation process, S600 can be completed with the help of vacuum evaporation equipment. Specifically, the back of the silicon wafer is pasted on a glass sheet of the same size as the sample stage with high-temperature tape, and the silicon column is placed in the sample stage with the surface facing down. When the size of the sample stage does not match the size of the silicon wafer, a glass sheet can be used for transition to improve the fixing effect of the silicon wafer. In this embodiment, since the size of each sample stage in the vacuum evaporation chamber is 2cm×2cm and the size of the silicon wafer is 1cm×1cm, it is necessary to paste the back of the silicon wafer on the glass sheet and fix the glass sheet on the sample stage. Next, keep the sample stage horizontal and place it in the vacuum evaporation chamber. It should be noted that when placing it in the vacuum evaporation chamber, avoid touching the probe station used to detect the thermal evaporation rate. Next, the organic semiconductor material to be processed is placed in the quartz dish of the vacuum evaporation chamber and heated. Among them, the silicon wafer is above the quartz dish, the rotation of the sample stage is controlled by the machine, and the baffle is controlled below the sample stage. The organic semiconductor material is heated to reach the evaporation temperature of the organic semiconductor material, the stable rate is controlled, the baffle is opened, and the thermally evaporated organic molecules are crystallized on the surface of the silicon column. Figure 2 As shown in the figure, it is a schematic diagram of the process of thermal evaporation of organic semiconductor materials on the surface of silicon pillars. After thermal evaporation, the organic molecules move to the surface of the silicon pillars and adhere to and crystallize. Since the organic semiconductor material evaporates vertically upward and the top of the silicon pillar is vertically downward, the organic molecules of the organic semiconductor material just crystallize on the top surface of the silicon pillar, and there are very few organic molecules left on the side walls of the silicon pillars, which forms a clear organic semiconductor material array and obtains a high-quality organic semiconductor material array on the substrate after transfer.

[0065] Among them, different organic semiconductor materials have different evaporation temperatures, and the temperature can be selected according to the properties of the organic semiconductor material. However, no matter which organic semiconductor material is used, the evaporation rate needs to be controlled, and the evaporation rate is controlled by controlling the temperature to control the degree of crystallization on the surface of the silicon column. In this way, an organic semiconductor material sample with a precise preset thickness can be obtained on the top of the silicon column, and the crystallization quality is good.

[0066] To this end, as an optional implementation, thermal evaporation of the organic semiconductor material under vacuum conditions specifically includes:

[0067] The thermal evaporation rate of the organic semiconductor material is controlled by adjusting the thermal evaporation temperature according to the properties of the organic semiconductor material.

[0068] Furthermore, thermal evaporation of the organic semiconductor material under vacuum conditions so that the organic molecules of the organic semiconductor material are crystallized on the top surface of the silicon pillar in a super-hydrophobic state, and an organic semiconductor material sample of a preset thickness is formed on the top surface of the silicon pillar, specifically comprising:

[0069] Based on the thermal evaporation rate and thermal evaporation time of the organic semiconductor material, an organic semiconductor material sample with a preset thickness is formed on the top surface of the silicon pillar.

[0070] Next, S800 is performed to bond the surface of the silicon wafer on which the organic semiconductor material sample is formed to a substrate, so that the organic semiconductor material sample is transferred to the substrate, and an organic semiconductor material array having the preset array form is obtained on the substrate.

[0071] In the specific implementation process, the substrate can be a common substrate or a wearable flexible substrate.

[0072] As an optional embodiment, the substrate is a flexible substrate. Since the surface of the silicon pillar is chemically modified, it is easier to transfer the attached organic semiconductor material, especially to a polymer with good toughness. Therefore, a flexible substrate is more conducive to the transfer of organic semiconductor materials, and semiconductor array processing on a flexible substrate provides an important advancement idea for the field of wearable electronic devices.

[0073] As an optional embodiment, the substrate includes polydimethylsiloxane;

[0074] Before bonding the surface of the silicon wafer on which the organic semiconductor material sample is formed to the substrate, the method further comprises:

[0075] Mixing polydimethylsiloxane and a hardener in a ratio of 10:1 to obtain a mixture;

[0076] The mixture was heated to 60-100°C and maintained for 2-4 hours to soften the substrate.

[0077] Specifically, polydimethylsiloxane (PDMS) is a type of silicone with good adhesion and good chemical inertness. After polydimethylsiloxane and a hardener are mixed in a ratio of 10:1 to obtain a mixture, the mixture is heated to 60-100°C and maintained for 2-4 hours to soften the substrate. When the substrate is in an unsolidified state, the surface of the organic semiconductor material sample formed on the silicon wafer is bonded to the substrate, and a preset pressure is applied and maintained for a preset time. After the substrate solidifies, the organic semiconductor material sample just adheres to the substrate. At this time, the silicon column is separated from the substrate. The surface of the silicon column and the substrate can be separated from all sides to prevent the array from being torn off, thereby obtaining an organic semiconductor material array in the form of the preset array on the substrate. For the specific process, see Figure 3 and 4 , obtaining an organic semiconductor material array having the predetermined array form on the substrate, see Figure 5 .

[0078] The transfer process can be carried out in a vacuum or atmospheric environment. When it is judged to be in an unsolidified state, tweezers can be used to judge the indentation and viscosity. The preset pressure is 40N-80N, which can be achieved by placing an appropriate glass sheet on the back of the silicon wafer, and the duration is about 30 minutes.

[0079] In addition, after obtaining the organic semiconductor material array having the preset array form on the substrate, the obtained sample is observed and tested by electron microscopy. Specifically, the array is observed by optical microscopy, the thickness and array crystallization are measured by AFM, and the surface morphology is measured by SEM.

[0080] Embodiment 2

[0081] This embodiment provides an organic semiconductor material array, which is prepared according to the method of Embodiment 1. Please refer to Embodiment 1 for the specific implementation, which will not be described in detail here.

[0082] Although the preferred embodiments of the present invention have been described, those skilled in the art may make other changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0083] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A method for preparing an array of organic semiconductor materials, characterized in that: The preparation method comprises: According to a preset array form, a silicon wafer including a silicon pillar array is prepared; Chemically modifying the surface of the silicon column to make the surface of the silicon column reach a super-hydrophobic state; Thermally evaporating the organic semiconductor material under vacuum conditions to allow organic molecules of the organic semiconductor material to crystallize on the top surface of the silicon pillar in a super-hydrophobic state, thereby forming an organic semiconductor material sample of a preset thickness on the top surface of the silicon pillar; Laminating the surface of the silicon wafer on which the organic semiconductor material sample is formed to a substrate, so that the organic semiconductor material sample is transferred to the substrate, and obtaining an organic semiconductor material array having the preset array form on the substrate; The organic semiconductor material is an organic semiconductor material that cannot be processed in liquid phase; The chemical modification of the surface of the silicon pillar specifically includes: Under vacuum conditions, a hydrophobic treatment agent is attached to the surface of the silicon column; The silicon column to which the hydrophobic treatment agent has been attached is heated to 80-120° C. and maintained for 2-4 hours; The thermal evaporation of the organic semiconductor material under vacuum conditions specifically includes: The thermal evaporation rate of the organic semiconductor material is controlled by adjusting the thermal evaporation temperature according to the properties of the organic semiconductor material.

2. The method according to claim 1, characterized in that The hydrophobic treatment agent is fluorosilane or octadecyltrichlorosilane.

3. The method according to claim 1, characterized in that The step of thermally evaporating the organic semiconductor material under vacuum conditions so that the organic molecules of the organic semiconductor material are crystallized on the top surface of the silicon pillar in a super-hydrophobic state, and forming an organic semiconductor material sample of a preset thickness on the top surface of the silicon pillar, specifically comprises: Based on the thermal evaporation rate and thermal evaporation time of the organic semiconductor material, an organic semiconductor material sample with a preset thickness is formed on the top surface of the silicon pillar.

4. The method according to claim 1, characterized in that The substrate is a flexible substrate.

5. The method according to claim 1, characterized in that The substrate includes polydimethylsiloxane; Before laminating the surface of the silicon wafer on which the organic semiconductor material sample is formed to a substrate, the method further comprises: Mixing polydimethylsiloxane and a hardener in a ratio of 10:1 to obtain a mixture; The mixture was heated to 60-100°C and maintained for 2-4 hours to soften the substrate.

6. The method according to claim 5, characterized in that The step of laminating the surface of the silicon wafer on which the organic semiconductor material sample is formed to a substrate, transferring the organic semiconductor material sample to the substrate, and obtaining an organic semiconductor material array having the preset array form on the substrate specifically includes: When the substrate is in an unsolidified state, the surface of the silicon wafer on which the organic semiconductor material sample is formed is bonded to the substrate, a preset pressure is applied and maintained for a preset time; After the substrate is solidified, the silicon pillars are separated from the substrate, and an organic semiconductor material array having the preset array form is obtained on the substrate.

7. An organic semiconductor material array, characterized in that: The organic semiconductor material array is prepared according to the method according to any one of claims 1-6.

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