A method for growing high-throughput thin film materials using a rotating mask

Abstract

The present invention belongs to the technical field of material preparation, and particularly relates to a method for growing high-throughput thin film materials by using a rotating mask. The present invention includes the following steps: Under ultra-high vacuum conditions, a substrate is placed in a mask structure, wherein the mask structure is provided with an opening, and the substrate is located directly below the opening; The mask structure is placed in an ultra-high vacuum evaporation equipment, and the vacuum evaporation method is adopted. According to the components of the thin film material, the corresponding components are sequentially evaporated and deposited on the substrate in the mask structure through the opening. After evaporation and deposition, the mask structure is rotated, and then the next evaporation and deposition is carried out; wherein, the components of the next evaporation and deposition partially overlap with all the components of the previous evaporation and deposition until all the components are evaporated and deposited, and a thin film material is obtained. The rotating mask method of the present invention is simple to operate. By depositing thin film materials with various component combinations on one substrate, the repeated manual operation is reduced, and the experimental success rate is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of material preparation, and particularly relates to a method for growing high-throughput thin film materials by using a rotating mask. Background Art

[0002] Surface science research is usually carried out in an ultra-high vacuum environment, mainly because the ultra-high vacuum environment can precisely control surface chemical experiments.

[0003] Low-dimensional nanostructures refer to materials with at least one dimension in the nanoscale range. Due to size effects and quantum effects, they exhibit properties significantly different from those of macroscopic materials in aspects such as acoustics, optics, electricity, and magnetism. With the support of surface science methods, such materials are precisely controlled and synthesized in an ultra-high vacuum environment through a "bottom-up" approach, and are precisely designed and controlled at the molecular or atomic level, thereby endowing them with unique performance advantages.

[0004] However, due to the complexity of the molecular structure itself, its design often requires a series of trial and error experiments, and growing thin film materials in ultra-high vacuum often requires a large amount of time and effort from experimental personnel to prepare samples and conduct characterizations. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides a method for growing high-throughput thin film materials by using a rotating mask.

[0006] The present invention designs a mask rotation masking method and a mask structure, places the mask structure with a substrate in an ultra-high vacuum evaporation device; adopts the vacuum evaporation method, and sequentially evaporates and deposits the corresponding components on the substrate in the mask structure according to the components of the thin film material. After each evaporation and deposition, the mask structure is rotated so that the components for the next evaporation and deposition partially overlap with all the components of the previous evaporation and deposition; through the cross-mixing of multiple components on the substrate, new materials with multiple component combinations are prepared. The present invention can quickly synthesize and test materials with various different component combinations through high-throughput experiments and characterizations, accelerating the discovery process of new materials; and can significantly reduce the number of trial and error experiments and time in traditional material research methods, improving the accuracy and efficiency of material design. At the same time, the present invention can accelerate the number of experiments required for growing thin film materials in an ultra-high vacuum environment, reduce manpower requirements and improve efficiency, and enhance the repeatability and reliability of experiments.

[0007] The object of the present invention is to provide a method for growing high-throughput thin film materials by using a rotating mask, including the following steps:

[0008] Step 1: Under ultra-high vacuum conditions, place the substrate in the mask structure, wherein the mask structure is provided with an opening, and the substrate is located directly below the opening.

[0009] It should be noted that in the present invention, obtaining the ultra-high vacuum condition requires pumping by a pump group including a mechanical pump, a vacuum pump, a titanium pump, and an ion pump, and through baking and degassing the internal components of the vacuum chamber. Before obtaining the ultra-high vacuum in the present invention, the equipment should be leak-tested, and the specific operation is as follows: Turn on the mechanical pump. After the mechanical pump stabilizes, turn on the vacuum pump. Wait for the current of the vacuum pump to stabilize and then wait for a period of time. When the pressure of the equipment is 1E -6 mbar, the equipment is well-sealed. The specific operation for obtaining the ultra-high vacuum in the present invention is as follows: Confirm that the equipment is well-sealed, start baking and turn on the ion pump; When the pressure of the equipment reaches 3E -7 mbar, stop baking; Then use the ion pump and the titanium pump in sequence to degas the equipment until the pressure is lower than 1E - 9 mbar.

[0010] Preferably, the temperature of the baking is 110°C to 120°C.

[0011] It should also be noted that under ultra-high vacuum conditions, each operation needs to be manipulated by an in-built manipulator; Before the present invention places the substrate in the mask structure for molecular evaporation deposition, the substrate needs to be pretreated. After ion sputtering the substrate with an ion gun, annealing is carried out to obtain a clean and flat substrate surface. Preferably, the substrate is a single crystal metal. The present invention then places the pretreated substrate in the mask structure by manipulating the in-built manipulator; Among them, the mask structure is provided with an opening, and the substrate is located directly below the opening, so as to ensure that the molecules evaporated in vacuum can be deposited on the substrate through the opening of the mask structure.

[0012] Step 2: Place the mask structure in the ultra-high vacuum evaporation equipment. Using the vacuum evaporation method, according to the components of the thin film material, the corresponding components are sequentially evaporated and deposited on the substrate in the mask structure through the opening. After evaporation and deposition, rotate the mask structure, and then carry out the next evaporation and deposition; Among them, the components of the next evaporation and deposition partially overlap with all the components of the previous evaporation and deposition until all the components are evaporated and deposited, and the thin film material is obtained.

[0013] It should be noted that the component evaporation source in the ultra-high vacuum evaporation equipment includes three or more component evaporation ports, and three or more components can be loaded at one time. Each evaporation port is controlled by a separate DC power supply for component evaporation. The evaporation temperatures of different components are different, and the required current magnitudes are also different. When carrying out evaporation and deposition of multiple components, load multiple component evaporation sources at the component evaporation ports and control the evaporation of each component at the component evaporation ports in sequence. In addition, it is necessary to use a quartz crystal microbalance to detect whether the components are evaporated and calculate the evaporation rate. Preferably, an organic component evaporation source is used for component evaporation.

[0014] After the components are stably distilled, align the substrate in the mask structure with the evaporation orifice of the component being evaporated in the organic component evaporation source; start timing after alignment. After reaching the evaporation time, turn off the component evaporation source, and move the deposited mask structure to one side to complete one component deposition. When the evaporation time is reached, that is, one evaporation deposition is completed, it is necessary to immediately turn off the DC power supply and use the manipulator to move the mask structure to one side. In addition, it is necessary to control the evaporation time to ensure that the coverage rate of each component meets the experimental requirements.

[0015] It should also be noted that after each evaporation deposition is completed, it is necessary to immediately turn off the DC power supply and move the mask structure to one side; then rotate the mask structure, and the rotation angle each time is determined according to the type of thin film material components. Preferably, the rotation angle each time is 360° / the type of components. After the mask structure is rotated, align the mask structure with the evaporation orifice of the component being evaporated in the organic component evaporation source and perform the next evaporation. The components deposited in the next evaporation overlap partially with all the components deposited in the previous evaporation; until all the multi-component evaporation sources at the evaporation orifice are completely evaporated, a thin film material with a combination of multiple components is obtained.

[0016] Preferably, the rotating mask structure includes: a mask cover capable of rotating and a sample holder.

[0017] A through hole is provided at the upper end of the sample holder, and a plurality of annular plates are arranged along the circumference of the through hole for mounting the mask cover on the sample holder through an annular guide rail; a cavity is provided inside the sample holder for placing the substrate.

[0018] An annular groove is provided at the bottom of the mask cover, and the structure of the annular groove matches the structure of the plurality of annular plates; a small hole is provided at the center of the bottom of the mask cover for depositing the molecules during evaporation onto the substrate of the sample holder through the small hole.

[0019] Preferably, a plurality of paddles are circumferentially distributed on the outer side of the mask cover to facilitate the manipulator to grip and rotate the mask cover.

[0020] Preferably, a mark is provided above one of the paddles of the mask cover for observing the rotation of the mask cover.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The present invention places a mask structure with a substrate in an ultra-high vacuum evaporation equipment. Among them, the mask structure is provided with an opening, and the substrate is located directly below the opening. According to the components of the thin film material, the corresponding components are sequentially evaporated and deposited on the substrate in the mask structure through the opening. After evaporation and deposition, the mask structure is rotated, and then the next evaporation and deposition is carried out, so that the components of the next evaporation and deposition partially overlap with all the components of the previous evaporation and deposition. Through the cross-mixing of multiple components on the substrate, a thin film material with multiple component combinations is prepared. The present invention realizes the deposition of multiple components on the surface of a single substrate in an ultra-high vacuum environment through the rotating mask method, can quickly prepare a high-quality thin film material with multiple component combinations, accelerates the discovery process of new materials, and effectively improves the experimental efficiency of the growth of surface thin film materials. The present invention can greatly reduce the number of trial-and-error experiments and time in traditional material research methods, and improve the accuracy and efficiency of material design.

[0023] The rotating mask method provided by the present invention has simple operation. By depositing multiple components on one substrate, it can accelerate the number of experiments required for the growth of thin film materials in an ultra-high vacuum environment, reduce manpower requirements and improve efficiency, and improve the repeatability and reliability of experiments.

[0024] The mask device provided by the present invention has a simple design and is easy to use, and can be widely applied to the growth of thin film materials in various situations. Brief Description of the Drawings

[0025] Figure 1 It is a schematic structural diagram of the mask structure of the present invention.

[0026] Figure 2 It is a schematic structural diagram of the sample holder of the present invention.

[0027] Figure 3 It is a schematic structural diagram of the mask cover of the present invention.

[0028] Figure 4 It is a schematic structural diagram of the bottom of the mask cover of the present invention.

[0029] Figure 5 It is a scanning probe microscopic image of the thin film material prepared in Example 1 of the present invention.

[0030] Figure 6 It is a scanning probe microscopic image of the thin film material prepared in Example 2 of the present invention.

[0031] Reference Signs: 1 - mask cover; 2 - sample holder; 3 - through hole; 4 - annular plate; 5 - cavity; 6 - annular groove; 7 - small hole; 8 - dial; 9 - mark. Detailed Description of the Embodiments

[0032] To enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention will be further described below in conjunction with specific embodiments and the accompanying drawings. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0033] The following will be combined with Figures 1 to 4 to further illustrate a specific implementation manner of the mask structure of the present invention.

[0034] The mask structure provided in this embodiment is as Figure 1 shown. The mask structure includes a rotatable mask cover 1 and a sample holder 2.

[0035] As Figure 1 and Figure 2 shown, a through hole 3 is opened at the upper end of the sample holder 2, and a plurality of annular plates 4 are arranged along the circumference of the through hole 3; a cavity 5 is provided inside the sample holder 2 for placing a substrate.

[0036] As Figure 4 shown, an annular groove 6 is provided at the bottom of the mask cover 1. The structure of the annular groove 6 matches the structure of the plurality of annular plates 4 for inserting the plurality of annular plates 4 into the annular groove 6; a small hole 7 is provided at the center of the bottom of the mask cover 1 for depositing molecules during evaporation onto the substrate of the sample holder 2 through the small hole 7.

[0037] As Figure 3 shown, a plurality of paddles are circumferentially distributed on the outer side of the mask cover 1 to facilitate the manipulator to grip and rotate the mask cover 1. A mark 9 is provided above one of the paddles 8 of the mask cover 1 for observing the rotation of the mask cover 1.

[0038] The following will provide two embodiments of using the mask structure to grow high-throughput thin film materials by rotating the mask.

[0039] It should be noted that the following components are the components required for preparing the thin film material: 4,4'-(2',4',5',6'-tetrakis(4-(pyridin-4-yl)phenyl)-[1,1':3',1''-terphenyl]-4,4''-diyl)bipyridine, denoted as component A; 1,3,5-tris[4-(pyridin-4-yl)phenyl]benzene, denoted as component B; 2,4,6-tris(pyridin-4-yl)-1,3,5-triazine, denoted as component C; 4,4'-di(pyridin-4-yl)-1,1'-biphenyl, denoted as component D; 3,3',5,5'-tetrakis(pyridin-4-yl)-1,1'-biphenyl, denoted as component E; 4,4'-(1,3-benzenedimethylene)bipyridine, denoted as component F.

[0040] Example 1

[0041] This example provides a method for growing high-throughput thin film materials using a rotating mask.

[0042] In this example, component A, component B, and component C are selected as the components for preparing the thin film material.

[0043] Step 1: Prepare the mask-substrate:

[0044] (1.1) Seal the equipment and turn on the vacuum pump to start leak detection; after determining that the equipment is well-sealed, bake it and turn on the ion pump; stop baking when the equipment pressure reaches 3E -7 mbar.

[0045] (1.2) Degas the equipment successively using the ion pump and the titanium pump until the pressure is below 1E -9 mbar to obtain an ultra-high vacuum environment.

[0046] (1.3) Select a Cu(111) single crystal as the substrate, perform argon ion sputtering treatment on Cu(111) using an ion gun, and then perform annealing treatment on Cu(111) to obtain a pretreated Cu(111) substrate. Among them, the parameter settings for argon ion sputtering are as follows: preset low-energy mode; the ion acceleration voltage is 1500V, the emission current of the ion gun is 10mA, the working time is 10min, and the argon gas concentration in the cavity during operation is 1E -5 mbar. The parameter settings for annealing are as follows: the current is 3.8A, the voltage is 8.0V, and the annealing time is 10min.

[0047] (1.4) Manipulate the built-in manipulator to install the mask cover 1 on the sample holder 2 to obtain a mask-sample holder.

[0048] (1.5) Place the pretreated Cu(111) substrate in the cavity 5 of the mask-sample holder to obtain a mask-Cu(111) substrate.

[0049] S2: Vacuum evaporation deposition:

[0050] (2.1) Turn on the DC power supply for component evaporation and detect the evaporation rate of each component through a quartz crystal microbalance.

[0051] (2.2) Set the evaporation parameters of component A as follows: the current is 1.901A, the voltage is 3.38V, and the component evaporation rate is 2.5A / min.

[0052] (2.3) After component A is stably evaporated, align the small hole 7 in the mask-Cu(111) substrate with the evaporation port of component A in the organic component evaporation source; start timing after alignment, close the component evaporation source after reaching the evaporation time; and move the mask-Cu(111) substrate to one side. The evaporation time is 4 s, and the evaporation of component A is completed, that is, the first deposition is completed, and the first component mask-substrate is obtained, denoted as the first assembly.

[0053] (2.4) Rotate the mask cover 1 by 120° through the built-in manipulator.

[0054] (2.5) Set the evaporation parameters of component B as follows: current is 1.369 A, voltage is 2.51 V, and the component evaporation rate is 2.3 A / min.

[0055] (2.6) After component B is stably evaporated, align the small hole 7 in the first assembly with the evaporation port of component B in the organic component evaporation source; start timing after alignment, close the component evaporation source after reaching the evaporation time, and move the first assembly to one side. The evaporation time is 10.5 s, and the evaporation of component B is completed, that is, the second deposition is completed. The component of the second deposition partially overlaps with the component of the first deposition, and the second component mask-substrate composed of three combinations of component A, component B, and the cross-component of component A and component B is obtained, denoted as the second assembly.

[0056] (2.7) Continue to rotate the mask cover 1 by 120° through the built-in manipulator.

[0057] (2.8) Set the evaporation parameters of component C as follows: current is 1.349 A, voltage is 2.48 V, and the component evaporation rate is 2 A / min.

[0058] (2.9) After component C is stably evaporated, align the small hole 7 in the second assembly with the evaporation port of component C in the organic component evaporation source; start timing after alignment, close the component evaporation source after reaching the evaporation time; and move the second assembly to one side. The evaporation time is 2 s, and the evaporation of component C is completed, that is, the third deposition is completed. The component of the third deposition partially overlaps with the component of the first deposition and the component of the second deposition, and the third component mask-substrate composed of four combinations of component C, the cross-component of component A and component C, the cross-component of component B and component C, and the cross-component of component A, component B, and component C is obtained, denoted as the third assembly.

[0059] (2.10) After all component evaporations are completed, take out the prepared Cu(111) single crystal substrate from the third assembly to obtain a thin film material with three components and seven combinations.

[0060] Example 2

[0061] This embodiment provides a method for growing high-throughput thin film materials using a rotating mask.

[0062] This embodiment selects component A, component B, component C, component D, component E, and component F as the components for preparing the thin film material.

[0063] The difference between this embodiment and Embodiment 1 is that this embodiment adds component D, component E, and component F on the basis of Embodiment 1. The evaporation parameters of component D, component E, and component F are as follows:

[0064] Component D: current is 1.507 A, voltage is 2.23 V, component evaporation rate is 2.5 A / min, and evaporation time is 2 s; Component E: current is 1.271 A, voltage is 1.89 V, component evaporation rate is 2 A / min, and evaporation time is 2 s; Component F: current is 0.847 A, voltage is 1.28 V, component evaporation rate is 1 A / min, and evaporation time is 2 s; A thin film material with 63 combinations of six components is obtained.

[0065] For the thin film materials prepared in Embodiment 1 and Embodiment 2, the thin film materials that meet the requirements of subsequent experiments are annealed by heating. The sample is annealed by a DC power supply, and the real-time temperature of annealing is detected by an infrared thermometer for easy control. Among them, the current is 1.7 A, the voltage is 2.7 V, the annealing temperature is 150 °C, and the annealing time is 5 min, and the annealed thin film material is obtained.

[0066] Experimental test:

[0067] 1. The thin film materials prepared in Embodiment 1 and Embodiment 2 are characterized by a scanning probe microscope. The coverage rate of each component on the Cu(111) single crystal substrate is scanned by a probe, and the scanning parameters are set as: I t is 100 pA, V b is -1.50 V, and the results are as Figure 5 shown.

[0068] Figure 5 is the scanning probe microscope image of the thin film material with 7 combinations of three components prepared in Embodiment 1. Figure 5 It shows the disordered network formed by the coordination of component A, component B, and component C, and shows the possible component combinations at different substrate positions. In addition, the single-component networks of the three components are all coordinated with copper atoms.

[0069] Figure 6 is the scanning probe microscope image of the thin film material with 63 combinations of six components prepared in Embodiment 2. Figure 6It shows the overall structure of the six-component network and is shown as an amorphous phase, in which various components are evenly distributed and randomly coordinated at random angles.

[0070] It should be noted that the connection relationships of the components not specifically mentioned in the present invention are defaulted to adopt the prior art. Since they do not involve the inventive points and are widely used in the prior art, the structural connection relationships will not be described in detail.

[0071] It should be noted that when the present invention involves numerical ranges, it should be understood that any one of the two endpoints of each numerical range and any value between the two endpoints can be selected. Since the adopted step methods are the same as those of the embodiments, in order to prevent repetition, the present invention describes the preferred embodiments. Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications to these embodiments once they know the basic creative concepts, and these changes and modifications all fall within the scope of the present invention.

[0072] 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. If these modifications and variations of the present invention fall within the scope of the equivalent technology of the present invention, the present invention also intends to include these changes and variations.

Claims

1. A method for growing high-throughput thin film materials using a rotating mask, characterized in that: The following steps are involved: Under ultra-high vacuum conditions, placing a substrate in a mask structure, wherein the mask structure is provided with a small hole, and the substrate is located directly below the small hole; The mask structure is placed in an ultra-high vacuum evaporation device, and a plurality of components are sequentially evaporated and deposited on the substrate in the mask structure through the opening by a vacuum evaporation method. After each component is evaporated and deposited, the mask structure is rotated, and then the next evaporation and deposition is performed; wherein the components of the next evaporation and deposition partially overlap with all the components of each previous evaporation and deposition, until the evaporation and deposition of all components are completed, thereby obtaining a thin film material; The mask structure comprises: a rotatable mask cover (1) and a sample holder (2); A through hole (3) is provided at the upper end of the sample holder (2), a plurality of annular plates (4) are arranged along the circumference of the through hole (3), and a cavity (5) is provided inside the sample holder (2) for placing a substrate; The bottom of the mask cover is provided with an annular groove (6), the structure of the annular groove (6) matches the structure of the plurality of annular plates (4), and is used for inserting the plurality of annular plates (4) into the annular groove (6); the center of the bottom of the mask cover (1) is provided with a small hole (7), which is used for depositing molecules in the evaporation process onto the substrate of the sample holder (2) through the small hole.

2. The method for growing high-throughput thin film materials using a rotating mask according to claim 1, characterized in that: The angle of each rotation is determined by the number of component types of the film material.

3. The method for growing high-throughput thin film materials using a rotating mask according to claim 2, characterized in that: The angle of each rotation is 360° / number of component types.

4. The method for growing high-throughput thin film materials using a rotating mask according to claim 1, characterized in that: The outer side of the mask cover (1) is provided with a plurality of paddles (8) distributed in the circumferential direction, so as to facilitate a robot to clamp and rotate the mask cover (1).

5. The method for growing high-throughput thin film materials using a rotating mask according to claim 1, characterized in that: The small hole (7) is a gourd-shaped hole.

6. The method for growing high-throughput thin film materials using a rotating mask according to claim 1, characterized in that: The substrate needs to be pre-treated before being placed on the mask structure. The pre-treatment process is: ion sputtering and annealing the substrate to obtain a clean and smooth substrate surface.

7. The method for growing high-throughput thin film materials using a rotating mask according to claim 1, characterized in that: The substrate is a metal single crystal substrate.

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