A vibratory vapor deposition apparatus and vapor deposition method

Abstract

This invention discloses a vibration-type vapor deposition apparatus and method. The method includes the following steps: Step 1: Placing the substrate in a reaction chamber, heating and vibrating the reaction chamber; Step 2: Simultaneously or sequentially directly supplying a first precursor source and a second precursor source into the reaction chamber, using the heat of the reaction chamber to vaporize the first precursor source, causing a reaction between the first and second precursor sources, and / or a reaction between the first precursor source and the substrate, ultimately depositing a film material on the substrate surface; Step 3: After the reaction in Step 2 is completed, connecting a vacuum pump to the reaction chamber to remove excess gas and reaction byproducts from the reaction chamber; wherein the first precursor source is chloride, and the second precursor source is humid air. In this invention, vibration generates significant disturbance to the substrate particles, keeping the substrate in a moving and dispersed state, facilitating sufficient contact between the substrate and the precursor, and achieving large-scale vapor deposition of the substrate.

Description

Technical Field

[0001] This invention relates to the field of vapor deposition technology, specifically to a vibratory vapor deposition apparatus and a vapor deposition method. Background Technology

[0002] Vapor deposition technology is widely used to deposit new materials on substrate surfaces, altering the substrate's properties or endowing it with new functions. For TiO2 substrates, surface deposition of materials such as silica and alumina can adjust photocatalytic activity and pigment properties, and is a core process that determines the application performance of TiO2.

[0003] TiO2 substrates are typically nanoparticles, which are prone to aggregation. Extensive research has focused on promoting particle dispersion and ensuring adequate contact with reactants, thereby achieving a uniform vapor deposition process on the particles.

[0004] For large quantities of particles, the conduction of reactant gases in the particle bed is very slow, which limits the large-scale application of vapor deposition technology. It is often necessary to use methods such as vibration, rotation, stirring, and fluidization to disturb the solid particles and promote contact between the particles and gaseous reactants.

[0005] In the study of pulsed chemical vapor deposition technology, fixed-bed reactors can achieve uniform gas-solid reactions on a small number of particles, but fixed-bed reactors are difficult to scale up.

[0006] Fluidized beds with stirring facilitate particle dispersion, resulting in the deposition of uniform SiO2 and Al2O3 films. However, TiO2 nanoparticles have a high specific surface area while the gas residence time in the fluidized bed is short, so an excessive amount of precursor reactants is often required to achieve the desired coating amount.

[0007] Therefore, there is an urgent need to develop a vapor deposition device and method that can coat a large amount of substrate with a high coating rate. Summary of the Invention

[0008] To address the problems of existing vapor deposition devices being unable to achieve large-scale coating and poor matrix dispersion during the vapor deposition process, resulting in uneven matrix coating, one objective of this invention is to provide a vibratory vapor deposition device.

[0009] The technical solution of the present invention to solve the above-mentioned technical problems is as follows:

[0010] A vibratory vapor deposition apparatus includes: a reaction unit, including a reaction chamber, a heating mechanism for heating the reaction chamber, and a vibration mechanism for providing vertical vibration to the reaction chamber;

[0011] The sample injection unit includes a first interface and a second interface located on the reaction chamber, a first precursor source and a second precursor source connected to the first interface and the second interface respectively through a first valve and a second valve, and a cylinder disposed in the reaction chamber and located below the first interface. The cylinder is used to hold the first precursor source and has air holes on it.

[0012] The pumping unit includes a third port and a fourth port located on the reaction chamber, a vacuum pump connected to the third port via a third valve, and a pressure detector connected to the fourth port.

[0013] Based on the above technical solution, the present invention can be further improved as follows:

[0014] Furthermore, the reaction chamber includes a reaction cylinder, an end cap located at the top of the reaction cylinder and connected to the reaction cylinder via a flange, and a groove located on the bottom wall of the reaction cylinder, the grooves being multiple and concentrically distributed; wherein, the first interface, the second interface, the third interface and the fourth interface are all located on the end cap, one end of the cylinder is connected to the end cap and the other end extends toward the bottom of the reaction cylinder.

[0015] Furthermore, the heating mechanism includes an electric heating plate located at the bottom of the reaction vessel and a temperature controller connected to the electric heating plate.

[0016] Furthermore, the vibration mechanism includes a vibration motor located at the bottom of the electric heating plate and a vibration controller located on the side wall of the vibration motor.

[0017] A second objective of this invention is to provide a method for performing vapor deposition based on the vibratory vapor deposition apparatus described in one objective, comprising the following steps:

[0018] Step 1: Place the substrate in the reaction chamber and heat and vibrate the reaction chamber;

[0019] Step 2: The first precursor source and the second precursor source are simultaneously or sequentially transported directly into the reaction chamber. The heat of the reaction chamber is used to vaporize the first precursor source, causing a reaction between the first and second precursor sources and / or between the first precursor source and the substrate, ultimately depositing a film material on the substrate surface.

[0020] After the reactions in steps 3 and 2 are completed, connect the vacuum pump to the reaction chamber to remove excess gas and reaction byproducts from the reaction chamber to obtain the product.

[0021] The first precursor source is chloride, and the second precursor source is humid air.

[0022] Furthermore, in step 1, the matrix is ​​TiO2, the chloride is SiCl4, and the amount of SiCl4 added per 100 g TiO2 is greater than 9 × 10⁻⁶ g. -3 mol.

[0023] Furthermore, the reaction temperature is 60~240°C, and the reaction time is 5~80 min.

[0024] Furthermore, the vibration conditions are: amplitude of 2~60 mm and frequency of 30~300 times / min.

[0025] The present invention has the following beneficial effects:

[0026] 1. The vertical vibration generated by the vibration motor in this invention causes significant disturbance to the matrix particles located in the reaction chamber, promoting full contact between the matrix particles and the first and second precursors, thereby enabling large-volume vapor deposition.

[0027] Furthermore, the product obtained by using the vibrating vapor deposition device of this invention has relatively uniform performance. According to the subsequent test, the catalytic performance of the samples from the surface and bottom layers of the reaction vessel after the reaction was completed was tested. It was found that the surface sample had a removal rate of 4.6% for the degradation of Rhodamine B, while the bottom sample had a removal rate of 5.1% for the degradation of Rhodamine B. The performance difference between the two was not significant.

[0028] That is, the device in this invention improves the uniformity of substrate coating.

[0029] 2. The present invention sets a cylinder in the reaction cylinder, the side wall of which is provided with air holes. By placing the first precursor in the reaction cylinder, the first precursor is vaporized by heating the reaction cylinder with an electric heating plate. In this way, the vaporization of the first precursor can be achieved while controlling the reaction temperature, and the first precursor source can be quickly introduced, which helps to simplify the precursor feeding method and improve safety.

[0030] 3. The bottom of the reaction cylinder in this invention is provided with grooves. There are multiple grooves and they are distributed in concentric circles. This avoids the accumulation of the substrate at the bottom of the reaction cylinder, facilitates full contact between the substrate and the precursor, improves the uniformity of vapor deposition coating on the substrate, and reduces the difference in product performance between different locations of the device. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the structure of the vibrating vapor deposition apparatus of the present invention;

[0032] Figure 2 This is a schematic diagram of the reaction chamber structure in this invention;

[0033] Figure 3 This is a schematic diagram of the end cap and bottom groove structure in this invention;

[0034] Figure 4 This is a schematic diagram of the storage bottle structure for storing the first precursor source according to the present invention.

[0035] Figure 5 This is a photocatalytic activity diagram of anatase TiO2 (A-TiO2) with deposited SiO2 prepared in Example 1 of the present invention;

[0036] Figure 6 The photocatalytic activity diagram of rutile TiO2 (R-TiO2) with SiO2 deposited prepared in Example 2 of this invention is shown.

[0037] Explanation of reference numerals in the attached figures:

[0038] 110 - Reaction chamber, 111 - Reaction cylinder, 112 - End cap, 113 - Groove;

[0039] 120 - Heating mechanism, 121 - Electric heating plate, 122 - Temperature controller;

[0040] 130 - Vibration mechanism, 131 - Vibration motor, 132 - Vibration controller;

[0041] 210-First interface, 220-Second interface, 230-First valve, 240-Second valve, 250-Cylinder, 260-Air hole;

[0042] 310 - Third interface, 320 - Fourth interface, 330 - Third valve, 340 - Fourth interface. Detailed Implementation

[0043] The following description, in conjunction with embodiments, illustrates a vibratory vapor deposition apparatus and a vapor deposition method according to the present invention.

[0044] However, the invention may be exemplified in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided so that the invention will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

[0045] Based on the inventor's preliminary research and investigation of vapor deposition equipment, the inventor previously applied for a patent with the patent number CN111218669B and the patent title: "A Rotary Drum Reactor for Pulsed Chemical Vapor Deposition Coating and Its Application." This technology uses a rotary drum reactor to promote the dispersion of TiO2 particles during the vapor deposition process and increase the throughput. However, it is not easy to achieve uniform heating of the reaction chamber under rotating conditions, and it is also necessary to heat the source bottle storing the precursor to provide precursor gas, making the sample introduction method relatively complicated; in addition, there is also the problem that the dispersion of the matrix during the vapor deposition process is not very high.

[0046] Therefore, there is an urgent need for a vapor deposition device that can promote higher dispersibility and uniform heating of the substrate during the coating process.

[0047] An embodiment of the first aspect of the present invention provides a vibratory vapor deposition apparatus. According to... Figures 1-4 As shown, the vibratory vapor deposition apparatus in the embodiments of the present invention includes a reaction unit, a sample introduction unit, and a gas extraction unit; specifically, the reaction unit includes a reaction chamber 110, a heating mechanism 120, and a vibration mechanism 130, wherein the heating mechanism 120 heats the reaction chamber 110, and the vibration mechanism 130 provides vertical vibration to the reaction chamber; preferably, according to Figure 1 As illustrated, in this embodiment, the reaction chamber 110, heating mechanism 120, and vibration mechanism 130 are arranged sequentially from top to bottom, with the heating mechanism 120 in contact with the reaction chamber 110 and the vibration mechanism 130 in contact with the heating mechanism 120. In this embodiment, the vibration generated by the vibration mechanism 130 is transmitted to the reaction chamber 110 via the heating mechanism 120.

[0048] In this embodiment, the vertical vibration generated by the vibration mechanism 130 facilitates the formation of a well-dispersed substrate in the reaction chamber. Compared with the prior art, which disperses the substrate during the vapor deposition process by rotation, the vertical vibration of the vibration mechanism 130 increases the dispersion of the substrate during the vapor deposition process, which is conducive to sufficient contact between the substrate and the vapor reactants (such as the first precursor source and the second precursor source), thereby reducing the amount of vapor reactants used; at the same time, it improves the uniformity of the substrate coating.

[0049] Furthermore, in practice, the connection relationship between the reaction chamber 110, the heating mechanism 120, and the vibration mechanism 130 in this invention is not limited to... Figure 1 As shown, any connection that satisfies the requirement that the heating mechanism 120 can heat the reaction chamber and the vibration mechanism 130 can transmit vertical vibration to the reaction chamber 110 is acceptable. No further examples will be given in this application.

[0050] according to Figures 1-3 As illustrated, the sample introduction unit in this embodiment includes a first interface 210, a second interface 220, a first valve 230, a second valve 240, a cylinder 250, and vents 260. Specifically, the first interface 210 and the second interface 220 are located on the reaction chamber 110. The first precursor source and the second precursor source are connected to the first interface and the second interface respectively through the first valve 230 and the second valve 240. The cylinder 250 is disposed inside the reaction chamber 110 and located below the first interface. The cylinder 250 is used to hold the first precursor source. The vents 260 are disposed on the side wall of the cylinder 250, and there are multiple vents 260, which facilitates the vaporized first precursor source to escape from the cylinder.

[0051] In this example, the first precursor source is a liquid, such as SiCl4. By placing the first precursor in a cylinder, it gradually vaporizes into a gas as the reaction chamber is heated by the heating mechanism 120. The resulting gas enters the reaction chamber through the vent 260 and reacts with the matrix. Therefore, this embodiment achieves vaporization of the first precursor while controlling the reaction temperature, enabling rapid introduction of the first precursor source. This simplifies the precursor feeding method and improves safety; it also avoids the inconvenience of heating the first precursor source before introducing it into the reaction chamber, as required in existing technologies.

[0052] Furthermore, in this embodiment, to facilitate the addition of the first precursor into the reaction vessel, a storage tank used to store the first precursor source is actually used, such as... Figure 4 As shown, the bottle opening and the first interface are sealed with nuts and rubber gaskets.

[0053] according to Figures 1-3 As shown, the vacuum pumping unit in this embodiment includes a third interface 310, a fourth interface 320, and a third valve 330. Specifically, the third interface 310 and the fourth interface 320 are located on the reaction chamber 110. The vacuum pump is connected to the third interface 310 through the third valve 330 (the vacuum pump is not shown in the figure), and the pressure detector is connected to the fourth interface 320.

[0054] In this embodiment, the vacuum pump is connected to the third interface 310 through the third valve 330 to extract the gas from the reaction chamber.

[0055] To facilitate the addition of the matrix into reaction chamber 110, such as Figure 1 In this embodiment, the reaction chamber 110 includes a reaction cylinder 111, an end cap 112, and a groove 113. Specifically, the end cap 112 is located on top of the reaction cylinder 111 and is connected to the reaction cylinder via a flange. In this example, a rubber gasket is used to seal between the upper and lower flanges, and 12 bolts are used to tightly connect the upper and lower flanges. The groove (113) is located on the bottom wall of the reaction cylinder, and there are multiple grooves distributed in concentric circles. In addition, the first interface, the second interface, the third interface, and the fourth interface are all located on the end cap. One end of the cylinder is connected to the end cap, and the other end extends toward the bottom of the reaction cylinder. In this embodiment, the cylinder is fixedly connected to the bottom wall of the end cap.

[0056] In addition, the reaction cylinder 111 in this example has a smooth inner wall, and the end cap, reaction cylinder and cylinder in this embodiment are all made of titanium to avoid corrosion problems caused by the reaction.

[0057] like Figure 1As shown, the heating mechanism 120 in this embodiment includes an electric heating plate 121 and a temperature controller 122; specifically, the electric heating plate 121 is located at the bottom of the reaction cylinder 111 and is in contact with the outer bottom wall of the reaction cylinder, and the temperature controller 122 is connected to the electric heating plate 121.

[0058] The vibration mechanism 130 includes a vibration motor 131 and a vibration controller 132. Specifically, the vibration motor 131 is located at the bottom of the electric heating plate 121 and in contact with the electric heating plate 121, while the vibration controller 132 is located on the side wall of the vibration motor 131. In this example, the vibration motor 131 is selected to provide vertical vibration to the reaction cylinder with an amplitude of 2~60mm and a frequency of 30~300 times / min.

[0059] A second aspect of the present invention provides a vapor deposition method based on the vibratory vapor deposition apparatus of the first aspect embodiment, the vapor deposition method comprising the following steps:

[0060] Step 1: Place the substrate in the reaction chamber and heat and vibrate the reaction chamber; specifically, the temperature controller starts the electric heating plate to heat the reaction chamber, and the vibration controller starts the vibration motor to vibrate the reaction chamber; during the vibration process, the substrate is in a state of motion and dispersion due to the vibration.

[0061] Step 2: The first precursor source and the second precursor source are simultaneously or sequentially transported directly into the reaction chamber. The heat of the reaction chamber is used to vaporize the first precursor source, causing a reaction between the first and second precursor sources and / or between the first precursor source and the substrate, ultimately depositing a film material on the substrate surface.

[0062] After the reactions in steps 3 and 2 are completed, the vacuum pump is connected to the reaction chamber to remove excess gas and reaction byproducts from the reaction chamber; the final modified material is obtained by depositing one or more film layers on the substrate.

[0063] The first precursor source is chloride, and the second precursor source is humid air.

[0064] Furthermore, in this embodiment, when the first precursor source and the second precursor source are simultaneously delivered to the reaction chamber, the specific operation is as follows: the first valve 230 and the second valve 240 are opened simultaneously, the first precursor source and the first interface 210 are connected through the first valve 230, thereby directly delivering the first precursor source into the cylinder; the second precursor source and the second interface 220 are connected through the second valve 240, thereby directly delivering the second precursor source into the reaction cylinder.

[0065] When the first precursor source and the second precursor source are successively introduced into the reaction chamber, the specific operation is as follows: Step C1: After completing the above step 1, the first precursor source is transported to the cylinder through the first valve, and the heat in the reaction cylinder is used to promote the vaporization of the first precursor source and react with the matrix.

[0066] After the reactions in steps C2 and C1 are completed, the vacuum pump is connected to the third port through the third valve, and then the gas in the reaction chamber is extracted and the reaction chamber is evacuated.

[0067] After steps C3 and C2 are completed, the second precursor and the second interface are connected through the second valve, and the second precursor source is introduced into the reaction chamber for reaction. After the reaction is completed, a film layer is formed on the substrate.

[0068] In this embodiment, the above-mentioned vibratory vapor deposition apparatus is used for vapor deposition. The vertical vibration in the apparatus can disturb the substrate, thereby allowing for more thorough contact with the gaseous reactants and enabling large-volume vapor deposition.

[0069] In some embodiments, the matrix in step 1 is TiO2, the chloride is SiCl4, and the amount of SiCl4 added per 100g TiO2 is greater than 9 × 10⁻⁶ g. -3 mol; in practice, it is usually the case that an excess of chloride is added.

[0070] In addition, in some embodiments, the reaction temperature is 60~240°C and the reaction time is 5~80 min.

[0071] In addition, in some embodiments, the vibration conditions are: amplitude of 2~60 mm and frequency of 30~300 times / min.

[0072] In addition, the relative humidity of the humid air in this embodiment is 40% to 60%; preferably, the relative humidity of the humid air is 60%.

[0073] Example

[0074] Example 1

[0075] Vapor deposition is performed using the vibratory vapor deposition apparatus described above, and the vapor deposition process includes the following steps:

[0076] Step 1: Take 100g of anatase TiO2 (A-TiO2) pigment into the reaction vessel, cover it with the end cap and tighten the bolts on the flange; set the heating temperature to 100°C using the temperature controller, and then start the electric heating plate to heat the reaction vessel; set the vibration frequency of the vibration motor to 120 times / min and the amplitude to 40 mm using the vibration controller.

[0077] Step 2: Start the first valve to connect the SiCl4 liquid storage tank and the first interface, and input 20mL of SiCl4 liquid into the cylinder. Use the heat in the reaction cylinder to cause the SiCl4 liquid to vaporize and allow the SiCl4 gas to react with TiO2 for 60min.

[0078] Step 3: Open the third valve and evacuate the reaction chamber for 20 minutes.

[0079] Step 4: Open the second valve and introduce humid air into the reaction chamber through the second port, allowing H2O in the air to participate in the reaction for 30 minutes. After the reaction is completed, turn off the vibration motor and the electric heating plate to obtain anatase TiO2 with a SiO2 film deposited on the surface, namely A-TiO2 / SiO2; wherein the relative humidity of the humid air is 60%.

[0080] The photocatalytic degradation performance of A-TiO2 and the A-TiO2 / SiO2 prepared in this example on Rhodamine B dye was tested, and the photocatalytic degradation of Rhodamine B dye by A-TiO2 was used as a control group. The test results are detailed in [link to test results]. Figure 5 As shown.

[0081] from Figure 5 It can be seen that the degradation and removal rates of Rhodamine B by A-TiO2 and A-TiO2 / SiO2 were 94.3% and 27.5%, respectively, indicating that the film layer significantly weakened the photocatalytic activity of TiO2.

[0082] Example 2

[0083] Vapor deposition is performed using the vibratory vapor deposition apparatus described above, and the vapor deposition process includes the following steps:

[0084] Step 1: Take 100g of rutile TiO2 (R-TiO2) pigment into the reaction vessel, cover it with the end cap and tighten the bolts on the flange; set the heating temperature to 100°C using the temperature controller, and then start the electric heating plate to heat the reaction vessel; set the vibration frequency of the vibration motor to 120 times / min and the amplitude to 40 mm using the vibration controller.

[0085] Step 2: Start the first valve to connect the SiCl4 liquid storage tank and the first interface, and input 20mL of SiCl4 liquid into the cylinder. Use the heat in the reaction cylinder to cause the SiCl4 liquid to vaporize and allow the SiCl4 gas to react with TiO2 for 60min.

[0086] Step 3: Open the third valve and evacuate the reaction chamber for 20 minutes.

[0087] Step 4: Open the second valve and introduce humid air into the reaction chamber through the second port, allowing H2O in the air to participate in the reaction for 30 minutes. After the reaction is completed, a layer of SiO2 film will be coated on the surface of the rutile TiO2. The relative humidity of the humid air is 60%.

[0088] Step 5: After step 4 is completed, repeat steps 2-4 above to deposit a second SiO2 film on rutile TiO2; after the reaction is completed, turn off the vibration motor and the electric heating plate to obtain a sample of a SiO2 film sample coated with two layers of rutile TiO2.

[0089] Samples located at the surface and bottom of the reaction vessel after reaction in this example were tested and labeled as R-TiO2 / SiO2-top and R-TiO2 / SiO2-bottom, respectively.

[0090] The photocatalytic degradation performance of R-TiO2, as well as the R-TiO2 / SiO2-top and R-TiO2 / SiO2-bottom prepared in this example, on Rhodamine B dye was tested, with the photocatalytic degradation of R-TiO2 on Rhodamine B dye used as a control group. The test results are as follows: Figure 6 As shown.

[0091] from Figure 6 As can be seen, the degradation removal rates of R-TiO2, R-TiO2 / SiO2-top and R-TiO2 / SiO2-bottom for Rhodamine B were 14.3%, 4.6% and 5.1%, respectively, indicating that the film layer weakened the photocatalytic activity of TiO2, and the activity of the surface and bottom particles was similar.

[0092] Example 3

[0093] Vapor deposition is performed using the vibratory vapor deposition apparatus described above, and the vapor deposition process includes the following steps:

[0094] Step 1: Take 3 kg of rutile TiO2 pigment into the reaction chamber, set the heating temperature to 120°C using the temperature controller, and then start the electric heating plate to heat the reaction chamber; set the vibration frequency of the vibration motor to 50 times / min and the amplitude to 20 mm using the vibration controller.

[0095] Step 2: Start the first valve and input 20 mL of SnCl4 liquid. Use the heat in the reaction chamber to vaporize the SnCl4 liquid and let the SnCl4 gas react with TiO2 for 120 min.

[0096] Step 3: Purge the reaction chamber with N2 gas at a rate of 2 L / min for 30 min.

[0097] Step 4: Open the second valve, and 2L / min of N2 will be introduced into the reaction chamber through the washing bottle to carry gaseous water. H2O will participate in the reaction for 40 min. After the reaction is completed, a SnO2 film will be coated on the surface of rutile TiO2.

[0098] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for performing vapor deposition using a vibrating vapor deposition apparatus, characterized in that, Includes the following steps: Step 1: Place the substrate in the reaction chamber and heat and vibrate the reaction chamber; Step 2: The first precursor source and the second precursor source are simultaneously or sequentially transported directly into the reaction chamber. The heat of the reaction chamber is used to vaporize the first precursor source, causing a reaction between the first and second precursor sources or between the first precursor source and the substrate, and finally depositing a film material on the substrate surface. After the reactions in steps 3 and 2 are completed, connect the vacuum pump to the reaction chamber to remove excess gas and reaction byproducts from the reaction chamber to obtain the product. The first precursor source is chloride, and the second precursor source is humid air. The vibratory vapor deposition apparatus includes: The reaction unit includes a reaction chamber (110), a heating mechanism (120) for heating the reaction chamber (110), and a vibration mechanism (130) for providing vertical vibration to the reaction chamber. The sample injection unit includes a first interface (210) and a second interface (220) located on the reaction chamber (110), a first precursor source and a second precursor source respectively connected to the first interface and the second interface via a first valve (230) and a second valve (240), and a cylinder (250) disposed in the reaction chamber (110) and located below the first interface, the cylinder being used to hold the first precursor source and having vent holes (260) on it. The vacuum pump unit includes a third port (310) and a fourth port (320) located on the reaction chamber (110), a vacuum pump connected to the third port (310) via a third valve (330), and a pressure detector connected to the fourth port (320). The reaction chamber (110) includes a reaction cylinder (111), an end cap (112) located at the top of the reaction cylinder (111) and connected to the reaction cylinder via a flange, and a groove (113) located on the bottom wall of the reaction cylinder. There are multiple grooves and they are distributed in concentric circles. The first interface, the second interface, the third interface and the fourth interface are all located on the end cap. One end of the cylinder is connected to the end cap and the other end extends toward the bottom of the reaction cylinder.

2. The vapor deposition method according to claim 1, characterized in that, The heating mechanism (120) includes an electric heating plate (121) located at the bottom of the reaction cylinder (111) and a temperature controller (122) connected to the electric heating plate (121).

3. The vapor deposition method according to claim 2, characterized in that, The vibration mechanism (130) includes a vibration motor (131) located at the bottom of the electric heating plate (121) and a vibration controller (132) located on the side wall of the vibration motor (131).

4. The vapor deposition method according to claim 1, characterized in that, The substrate mentioned in step 1 is TiO2, and the amount of chloride added per 100 g TiO2 is greater than 9 × 10⁻⁶ g. -3 mol, wherein the chloride is any one of SiCl4, SnCl4, AlCl3 and SiCl4.

5. The vapor deposition method according to claim 1, characterized in that, The reaction temperature is 60~240°C, and the reaction time is 5~80 min.

6. The vapor deposition method according to claim 1, characterized in that, The vibration conditions are: amplitude of 2~60mm and frequency of 30~300 times / min.

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