Open roll-to-roll chemical vapor deposition system and thin film preparation method

Abstract

The present application provides an open roll-to-roll chemical vapor deposition system, comprising a reaction device, a reaction gas device, at least four exhaust devices, at least two protective gas devices, at least one left slit flange, at least one right slit flange, an unwinding device, and a rewinding device. The reaction device comprises a reaction chamber, the reaction gas device, at least four exhaust devices, and at least two protective gas devices are all connected to the reaction chamber, the left slit flange is arranged on the left side of the reaction chamber, and the right slit flange is arranged on the right side of the reaction chamber. The open roll-to-roll chemical vapor deposition system of the present application has a pressure in the reaction chamber of less than 1000 Pa, which can realize the replacement of the coil without opening the reaction chamber, and can monitor the product online or offline in real time.

Description

Technical Field

[0001] The present application relates to a thin film preparation device and a thin film preparation method, and more specifically to an open roll-to-roll chemical vapor deposition system and a thin film preparation method. Background Art

[0002] Traditional graphene film chemical vapor deposition equipment, which we often call a tubular furnace, generally uses a quartz tube as the reaction chamber. The copper foil to be grown is placed in the quartz tube. It is a static growth method with low production capacity and is not suitable for mass production.

[0003] There are also some chemical vapor deposition roll-to-roll equipment, in which the copper foil to be grown is placed outside the quartz tube, and dynamic growth is achieved as the copper foil is wound and unwound. However, the winding and unwinding chamber and the quartz tube reaction chamber are in the same vacuum environment. When the roll is to be changed, the vacuum needs to be released and the process needs to be stopped, which is still not conducive to mass production.

[0004] The existing chemical vapor deposition roll-to-roll equipment all places the roll-to-roll conveyor mechanism inside a low-pressure environment, completely isolated from the outside air. It is inconvenient to replace the roll material, and the air pressure in the chamber needs to be adjusted to atmospheric pressure before it can be replaced. After replacement, the gas needs to be pumped back to low pressure before the process can be restarted, affecting production efficiency and process stability. In addition, the roll material is in a closed environment in the low-pressure chamber, and the quality of the growing film layer cannot be monitored in real time, and unqualified products cannot be discovered in time, which is not conducive to improving the quality of the film. Summary of the Invention

[0005] The main purpose of the present application is to overcome at least one of the defects of the above-mentioned prior art and to provide an open roll-to-roll chemical vapor deposition system that can replace the roll material without adjusting the pressure of the reaction chamber and can monitor the quality of the growing film in real time.

[0006] To achieve the above objectives, this application adopts the following technical solutions:

[0007] According to one aspect of the present application, an open roll-to-roll chemical vapor deposition system is provided, comprising a reaction apparatus, a reaction gas apparatus, at least four exhaust devices, at least two shielding gas apparatuses, at least one left slit flange, at least one right slit flange, an unwinding apparatus, and a rewinding apparatus. The reaction apparatus comprises a reaction chamber, at least one first flange, and at least one second flange. The at least one first flange is connected to the left end of the reaction chamber and is connected to a pipeline communicating with the reaction chamber. The at least one second flange is connected to the right end of the reaction chamber and is connected to a pipeline communicating with the reaction chamber. The reaction gas apparatus is in communication with the reaction chamber for introducing reaction gas into the reaction chamber. Two of the exhaust devices are located on the left side of the reaction chamber and are in communication with the reaction chamber, while the other two are located on the right side of the reaction chamber and are in communication with the reaction chamber. At least two shielding gas apparatuses are located on either side of the reaction chamber and are both in communication with the reaction chamber. The left slit flange is located to the left of the first flange, and the right slit flange is located to the right of the second flange. The unwinding device is arranged on the left side of the left slit flange, and the winding device is arranged on the right side of the right slit flange.

[0008] According to one embodiment of the present application, the reaction gas device includes a first reaction gas pipeline, a second reaction gas pipeline, a third reaction gas pipeline and a main reaction gas pipeline. The main reaction gas pipeline is connected to the reaction gas inlet of the reaction chamber, and the first reaction gas pipeline, the second reaction gas pipeline, and the third reaction gas pipeline are all connected to the main reaction gas pipeline.

[0009] According to one embodiment of the present application, a gas homogenizing tank is provided on the main reaction gas pipeline, and the gas homogenizing tank is used to homogenize the reaction gases entering the main reaction gas pipeline from the first reaction gas pipeline, the second reaction gas pipeline, and the third reaction gas pipeline.

[0010] According to one embodiment of the present application, the flange includes a first flange and a second flange, the first flange is arranged at the left end of the reaction chamber, and the second flange is arranged at the right end of the reaction chamber, and the gas extraction device includes a first gas extraction sub-device and a second gas extraction sub-device, the first gas extraction sub-device is arranged on the first flange and communicates with the reaction chamber through the first flange, and the second gas extraction sub-device is arranged on the second flange and communicates with the reaction chamber through the second flange.

[0011] According to one embodiment of the present application, the open roll-to-roll chemical vapor deposition system also includes a third flange, a fourth flange, a fifth flange and a sixth flange, the third flange is adjacent to the right side of the left slit flange, the fourth flange is adjacent to the left side of the right slit flange, the fifth flange is arranged between the first flange and the third flange, and the sixth flange is arranged between the second flange and the fourth flange.

[0012] According to one embodiment of the present application, a first transfer chamber is sequentially provided between the first flange, the fifth flange, the third flange and the left slit flange, and a second transfer chamber is sequentially provided between the second flange, the sixth flange, the fourth flange and the right slit flange, and the first transfer chamber and the second transfer chamber are connected to the reaction chamber.

[0013] According to one embodiment of the present application, the exhaust device also includes a third exhaust sub-device and a fourth exhaust sub-device. The third exhaust sub-device is arranged on the third flange and is connected to the first transfer chamber through the third flange. The fourth exhaust sub-device is arranged on the fourth flange and is connected to the second transfer chamber through the fourth flange.

[0014] According to one embodiment of the present application, the exhaust device includes an exhaust pipe, and a vacuum gauge, a valve, a gas monitor and a vacuum pump are provided on the exhaust pipe along the direction of gas discharge.

[0015] According to one embodiment of the present application, the gas monitors on the first and second gas pumping sub-devices are both oxygen monitors, and the gas monitors on the third and fourth gas pumping sub-devices are both reaction gas monitors.

[0016] According to one embodiment of the present application, the protective gas device includes a left protective gas device and a right protective gas device. The left protective gas device is arranged on the fifth flange and is connected to the first transfer chamber through the fifth flange. The right protective gas device is arranged on the sixth flange and is connected to the second transfer chamber through the sixth flange.

[0017] According to one embodiment of the present application, both the reaction gas device and the protective gas device are provided with a gas flow controller.

[0018] According to another aspect of the present application, a thin film preparation method is provided, using the above-mentioned open roll-to-roll chemical vapor deposition system, comprising the following steps:

[0019] Step 1: The substrate is mounted on the unwinding shaft of the unwinding device, and then the substrate is passed through the left slit flange, the flange at one end of the reaction chamber, the reaction chamber, the flange at the other end of the reaction chamber, and the right slit flange in sequence to the rewinding shaft of the rewinding device;

[0020] Step 2: Turn on the vacuum device to pump air and set the vacuum degree to 1Pa;

[0021] Step 3: When the vacuum degree is below 1Pa, turn on the protective gas device, set the pressure to below 1000Pa, turn on the heater for heating, and set the heating temperature set value;

[0022] Step 4: When the pressure and temperature reach the set value and stabilize and maintain, turn on the reaction gas device, and then turn on the unwinding device and the winding device.

[0023] As can be seen from the above technical solution, the advantages and positive effects of the open roll-to-roll chemical vapor deposition system proposed in this application are:

[0024] The open roll-to-roll chemical vapor deposition system proposed in this application adopts four exhaust devices and two protective gas devices, which can effectively avoid the contact between the reaction gas and the air, and can reduce the pressure in the reaction chamber to below 1000Pa. The left slit flange and the right slit flange are used to further limit the amount of air entering the reaction chamber, isolating the reaction chamber from the air. The reeling and unreeling device is arranged on the outside of the slit flange. When in use, the substrate is arranged on the unreeling shaft of the reeling device. The substrate passes through the left slit flange, the first flange at one end of the reaction chamber, the reaction chamber, the second flange at the other end of the reaction chamber and the right slit flange in sequence to reach the reeling shaft of the reeling device. In this way, when replacing the coil, there is no need to adjust the low pressure in the reaction environment, and the replacement can be completed quickly without stopping the operation, realizing continuous operation in the true sense, providing production efficiency and production stability. The reeling and unreeling device is not in the same air pressure environment as the reaction chamber, and can also monitor the film in real time to improve the quality of the film. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The above and other features and advantages of the present application will become more apparent by describing in detail example embodiments thereof with reference to the accompanying drawings.

[0026] Figure 1 It is a schematic structural diagram of the open roll-to-roll chemical vapor deposition system of the present application.

[0027] The description of the accompanying drawings is as follows:

[0028] 10-Open roll-to-roll chemical vapor deposition system;

[0029] 11- unwinding device;

[0030] 12-rewinding device;

[0031] 13-substrate;

[0032] 100-reaction device;

[0033] 101-reaction chamber;

[0034] 102-heater;

[0035] 103-first flange;

[0036] 104- second flange;

[0037] 105 - reaction gas inlet; 200 - reaction gas device; 201 - first reaction gas pipeline;

[0038] 202-second reaction gas pipeline;

[0039] 203-third reaction gas pipeline;

[0040] 204-main reaction gas pipeline;

[0041] 205-gas tank;

[0042] 300-exhaust device;

[0043] 301-first air pumping sub-device;

[0044] 302-second air pumping sub-device;

[0045] 303-third air pumping sub-device;

[0046] 304-fourth air pumping sub-device;

[0047] 311-exhaust pipe;

[0048] 312-Vacuum gauge;

[0049] 313-valve;

[0050] 314-gas monitor; 315-vacuum pump;

[0051] 401-shielding gas left device;

[0052] 402-shielding gas right device;

[0053] 501-left slit flange; 502-right slit flange; 601-third flange;

[0054] 602-fourth flange;

[0055] 603-fifth flange;

[0056] 604-sixth flange;

[0057] 701-first transfer chamber; 702-second transfer chamber;

[0058] MFC - Gas Flow Controller. DETAILED DESCRIPTION

[0059] Typical embodiments that embody the features and advantages of the present application will be described in detail in the following description. It should be understood that the present application can have various variations in different embodiments without departing from the scope of the present application, and the description and drawings therein are essentially for illustrative purposes and are not intended to limit the present application.

[0060] In the following description of different exemplary embodiments of the present application, reference is made to the accompanying drawings, which form a part of the present application and in which different exemplary structures, systems and steps that can implement various aspects of the present application are shown by way of example. It should be understood that other specific schemes of components, structures, exemplary devices, systems and steps can be used, and structural and functional modifications can be made without departing from the scope of the present application. Moreover, although the terms "upper", "middle", "inner", etc. may be used in this specification to describe different exemplary features and elements of the present application, these terms are used herein for convenience only, for example, according to the direction of the examples described in the accompanying drawings. Nothing in this specification should be construed as requiring a specific three-dimensional orientation of the structure to fall within the scope of the present application.

[0061] In order to make the above-mentioned objects, features and advantages of the present application clear and easy to understand, the specific embodiments of the present application are described in detail below with reference to the accompanying drawings.

[0062] like Figure 1As shown, the open roll-to-roll chemical vapor deposition system 10 of the present application includes a reaction device 100, a reaction gas device 200, at least four exhaust devices 300, at least two protective gas devices (401, 402), at least one left slit flange 501, at least one right slit flange 502, an unwinding device 11, and a rewinding device 12. The reaction device 100 includes a reaction chamber 101, at least one first flange 103, and at least one second flange 104. The at least one first flange 103 is connected to the left end of the reaction chamber 101 and is connected to a pipeline communicating with the reaction chamber 101. The at least one second flange 104 is connected to the right end of the reaction chamber 101 and is connected to a pipeline communicating with the reaction chamber 101. The reaction gas device 200 is in communication with the reaction chamber 101 and is used to introduce reaction gas into the reaction chamber 101. At least four exhaust devices 200, two of which (301, 303) are disposed on the left side of the reaction chamber 101 and communicate with the reaction chamber 101; the other two exhaust devices (302, 304) are disposed on the right side of the reaction chamber 101 and communicate with the reaction chamber 101. At least two protective gas devices (401, 402) are disposed on both sides of the reaction chamber 101 and communicate with the reaction chamber 101. At least one left slit flange 501 and at least one right slit flange 502 are disposed, wherein the left slit flange 501 is disposed on the left side of the first flange 103 and the right slit flange 502 is disposed on the right side of the second flange 104. The unwinding device 11 is disposed on the left side of the left slit flange 501, and the winding device 12 is disposed on the right side of the right slit flange 502.

[0063] The open roll-to-roll chemical vapor deposition system of the present application adopts four exhaust devices and two protective gas devices, which can effectively avoid the contact between the reaction gas and the air, and can reduce the pressure in the reaction chamber to below 1000Pa. The left slit flange and the right slit flange are adopted to further limit the amount of air entering the reaction chamber, isolating the reaction chamber from the air. The reeling and unreeling device is arranged on the outside of the slit flange. When in use, the substrate is arranged on the unreeling shaft of the reeling device, and the substrate passes through the left slit flange, the first flange at one end of the reaction chamber, the reaction chamber, the second flange at the other end of the reaction chamber and the right slit flange to reach the reeling shaft of the reeling device. In this way, when the coil is replaced, there is no need to adjust the low pressure in the reaction environment, and the replacement can be completed quickly without stopping the operation, realizing continuous operation in the true sense, providing production efficiency and production stability. The reeling and unreeling device is not in the same air pressure environment as the reaction chamber, and can also monitor the film in real time.

[0064] It should be noted that a heater 102 is disposed on the outer wall of the reaction chamber 101. The reaction chamber can be formed of a quartz tube, and its length can be designed according to actual needs, generally ranging from 0.5m to 2m. Other hollow structures are also possible. A reaction gas inlet 105 is also disposed on the outer wall of the reaction chamber, through which the reaction gas from the reaction gas device enters the reaction chamber 101.

[0065] In this embodiment, the reaction gas apparatus 200 includes a first reaction gas pipeline 201, a second reaction gas pipeline 202, a third reaction gas pipeline 203, and a main reaction gas pipeline 204. The main reaction gas pipeline 204 is in communication with the reaction chamber 101, and the first reaction gas pipeline 201, the second reaction gas pipeline 202, and the third reaction gas pipeline 203 are all in communication with the main reaction gas pipeline 204. Mixing multiple reaction gases through the main reaction gas pipeline before entering the reaction chamber ensures that the reaction gases entering the reaction chamber are already mixed, compared to mixing multiple reaction gases separately before entering the reaction chamber. This improves the efficiency of the entire preparation process and enhances the quality of thin film preparation.

[0066] It should be noted that the first reaction gas line 201, the second reaction gas line 202, the third reaction gas line 203, and the main reaction gas line 204 can all be quartz tubes. The diameter of the quartz tube of the main reaction gas line 204 is 1 / 10 to 1 / 2 of the diameter of the quartz tube forming the reaction chamber 101. Taking graphene growth as an example, the reaction gases are generally methane, hydrogen, and argon. The apparatus of the present application is not limited to graphene growth and can also be used to grow other materials.

[0067] In this embodiment, a gas homogenizing tank 205 is provided on the main reaction gas line 204. The gas homogenizing tank 205 is used to homogenize the reaction gases entering the main reaction gas line 204 from the first reaction gas line 201, the second reaction gas line 202, and the third reaction gas line 203. The provision of the gas homogenizing tank allows the reaction gases to be thoroughly mixed before entering the reaction chamber, which helps ensure the quality of the film and the uniformity and stability of the reaction.

[0068] In this embodiment, the gas extraction device 300 includes a first gas extraction sub-device 301 and a second gas extraction sub-device 302. The first gas extraction sub-device 301 is disposed on the first flange 103 and communicates with the reaction chamber 101 through the first flange 103. The second gas extraction sub-device 302 is disposed on the second flange 104 and communicates with the reaction chamber 101 through the second flange 104. Using flanges to connect the gas extraction sub-devices can simplify the overall structure and enable the gas extraction device to promptly extract air from the reaction chamber, quickly achieving the required vacuum level within the reaction chamber.

[0069] In this embodiment, the open roll-to-roll chemical vapor deposition system 10 further includes a third flange 601, a fourth flange 602, a fifth flange 603, and a sixth flange 604. The third flange 601 is disposed adjacent to the right side of the left slit flange 501, the fourth flange 602 is disposed adjacent to the left side of the right slit flange 502, the fifth flange 603 is disposed between the first flange 103 and the third flange 601, and the sixth flange 604 is disposed between the second flange 104 and the fourth flange 602. The provision of multiple flanges enables the gas devices required in the deposition system to be connected to the reaction chamber through the flanges. The provision of multiple flanges also increases the distance between the reaction chamber and the outside world, thereby helping to prevent the reaction chamber from being affected by the outside world.

[0070] In this embodiment, first transfer chambers 701 are sequentially disposed between the first flange 103, the fifth flange 603, the third flange 601, and the left slit flange 501. Second transfer chambers 702 are sequentially disposed between the second flange 104, the sixth flange 604, the fourth flange 602, and the right slit flange 502. The first transfer chamber 701 and the second transfer chamber 702 are in communication with the reaction chamber 101. Sequentially disposing the first and second transfer chambers between the multiple flanges allows the reaction chamber to communicate with the multiple flanges, allowing gases required by the reaction chamber to be communicated with the reaction chamber via the transfer chambers. This also increases the distance between the reaction chamber and the outside world, helping to protect the reaction chamber from external influences and improving the stability of the entire system during use.

[0071] In this embodiment, the gas extraction device 300 further includes a third gas extraction sub-device 303 and a fourth gas extraction sub-device 304. The third gas extraction sub-device 303 is disposed on the third flange 601 and communicates with the first transfer chamber 701 via the third flange 601. The fourth gas extraction sub-device 304 is disposed on the fourth flange 602 and communicates with the second transfer chamber 702 via the fourth flange 602. The provision of the third and fourth gas extraction sub-devices can reduce the pressure of the reaction chamber to below 1000 Pa and further effectively isolate the reaction gases from contact with air during the reaction process.

[0072] In this embodiment, the gas extraction device 300 includes a gas extraction pipe 311. Along the gas exhaust direction, the gas extraction pipe 300 is equipped with a vacuum gauge 312, a valve 313, a gas monitor 314, and a vacuum pump 315. The pressure of the gas extraction device can be individually adjusted via valve 313, typically maintaining the pressure of each sub-device of the gas extraction device at the same level. The presence of the gas monitor effectively protects the safety of the entire device.

[0073] In this embodiment, the gas monitors 314 on the first and second air extraction sub-assemblies 301, 302 are both oxygen monitors, and the gas monitors 314 on the third and fourth air extraction sub-assemblies 303, 304 are both reactive gas monitors. When the monitored oxygen or reactive gas content exceeds a standard set value, the gas monitors send a signal to automatically shut off the gas supply to the reactive gas device, thereby protecting the entire system.

[0074] In this embodiment, the protective gas system includes a left protective gas system and a right protective gas system. The left protective gas system is mounted on the fifth flange and communicates with the first transfer chamber via the fifth flange. The right protective gas system is mounted on the sixth flange and communicates with the second transfer chamber via the sixth flange. The configuration of the protective gas system allows the vacuum system to evacuate the reaction chamber, then introduce protective gas throughout the reaction chamber before film production begins, ensuring film quality.

[0075] In this embodiment, both the reaction gas device and the protective gas device are provided with gas flow controllers. By providing the gas flow controllers, the flow rates of the reaction gas and the protective gas are controlled, thereby ensuring the stability of the entire preparation process and facilitating the quality of the film.

[0076] It should be noted that all of the above gases can be transported using quartz tubes, and the wall thickness of the quartz tubes is generally 3-5mm. The heater is mainly used to heat the gas in the quartz tube reactor, causing it to decompose at high temperature and undergo a chemical reaction. Taking the preparation of graphene from methane as an example, the heating temperature is 1000°C, and a resistance wire heating method is used. When the carbon source for preparing graphene is a liquid carbon source, such as ethanol, the heating temperature can be below 800°C, and infrared heating can be used. The heater can be designed as a single temperature zone or a multi-temperature zone structure, and the multi-temperature zone method can achieve temperature gradient control.

[0077] The first and second transfer chambers can be designed with the same diameter as the reaction chamber or flattened. They can be made of quartz, stainless steel, or other materials. The shielding gas is typically nitrogen, argon, or other inert gases. The unwinding and rewinding devices are designed with speed control, tension control, and a correction system.

[0078] It should be noted that the open roll-to-roll chemical vapor deposition systems shown in the drawings and described in this specification are only a few examples of the many types of open roll-to-roll chemical vapor deposition systems that can employ the principles of the present application. It should be clearly understood that the principles of the present application are in no way limited to any details of the open roll-to-roll chemical vapor deposition systems shown in the drawings or described in this specification, or to any components of the open roll-to-roll chemical vapor deposition systems.

[0079] The above is a detailed description of several exemplary embodiments of the open roll-to-roll chemical vapor deposition system proposed in this application. The following is an exemplary description of the method for preparing the thin film proposed in this application.

[0080] Combined with attachment Figure 1 The thin film preparation method proposed in this application uses the above-mentioned open roll-to-roll chemical vapor deposition system and includes the following steps:

[0081] Step 1: The substrate is mounted on the unwinding shaft of the unwinding device. The substrate is then passed through the left slit flange, the flange at one end of the reaction chamber, the reaction chamber, the flange at the other end of the reaction chamber, and the right slit flange to the rewinding shaft of the rewinding device.

[0082] Step 2: Turn on the vacuum device to pump air and set the vacuum degree to 1Pa;

[0083] Step 3: When the vacuum degree is below 1Pa, turn on the protective gas device, set the pressure setting value to below 1000Pa, turn on the heater for heating, and set the heating temperature setting value;

[0084] Step 4: When the pressure and temperature reach the set value and stabilize and maintain, turn on the reaction gas device, and then turn on the unwinding device and the winding device.

[0085] It should be noted that the oxygen monitor on the exhaust device must be shielded when the exhaust device is activated. Throughout the entire preparation process, the shielding gas pressure is below 1000 Pa. By setting and maintaining the shielding gas pressure, a low-pressure environment is maintained throughout the entire device during film preparation. The oxygen monitor is activated after the shielding gas device is activated.

[0086] When the substrate at the unwinding end is used up, the transmission of the rewinding end can be stopped, and the other parts remain unchanged. At this time, the used reel is removed and replaced with a new substrate roll. The new and old substrates can be connected together using a quick welding method, and then the transmission is started to continue the preparation of graphene.

[0087] The substrate can typically be copper foil or other metal foils, or fiber fabrics. Its thickness is typically 50-100 μm. The thin film preparation method of this application enables the continuous production of single or multilayer graphene on a substrate surface. Replacing the substrate reel does not require opening the reaction chamber or shutting down the process, allowing for rapid replacement, achieving truly continuous operation.

[0088] To further understand the content of this application, the present application is now described in detail in conjunction with specific examples. It should be noted that due to limited space, only some examples are listed below, and the various parameters in the preparation method are not limited to the following specific examples.

[0089] Example 1

[0090] The copper foil is mounted on the unwinding shaft of the unwinding device. The copper foil is then passed through the left slit flange, the flange at one end of the reaction chamber, the reaction chamber, the flange at the other end of the reaction chamber, and the right slit flange, before being transferred to the rewinding shaft of the rewinding device. The vacuum system is activated to evacuate the copper foil to a vacuum level of 1 Pa, while shielding the oxygen detector. Once the vacuum level drops below 1 Pa, the shielding gas system is activated with nitrogen and the pressure set to 1000 Pa. The oxygen detector is activated, and the heater is activated to heat the foil at 1000°C. Once the pressure reaches 1000 Pa and the temperature stabilizes at 1000°C, the reaction gas system is activated with methane, hydrogen, and helium, and the unwinding and rewinding devices are operated. When the copper foil at the unwinding end is exhausted, the rewinding end can be stopped, while other procedures remain unchanged. The exhausted reel is then removed and replaced with a new copper foil roll. The new and old copper foils can be connected using a quick soldering method. After this, the rewinding process is resumed, and graphene production can continue.

[0091] Example 2

[0092] The aluminum foil is mounted on the unwinding shaft of the unwinding device. The foil is then passed through the left slit flange, the flange at one end of the reaction chamber, the reaction chamber, the flange at the other end of the reaction chamber, and the right slit flange, before being transferred to the rewinding shaft of the rewinding device. The vacuum system is activated to evacuate the foil, setting the vacuum to 1 Pa (1 Pa), while shielding the oxygen monitor. Once the vacuum is below 1 Pa, the shielding gas system is activated with argon, and the pressure setpoint is set to 900 Pa (900 Pa). The oxygen monitor is activated, and the heater is activated to heat the foil at 900°C (900°C). Once the pressure reaches 900 Pa and the temperature stabilizes at 900°C, the reaction gas system is activated with ethane, hydrogen, and argon, and the unwinding and rewinding devices are operated. When the unwinding end of the foil is exhausted, the rewinding end can be stopped, while other procedures remain unchanged. The exhausted reel is then removed and replaced with a new reel of aluminum foil. The new and old foils can be joined using a quick weld method. The conveyor system is then resumed, and graphene production can continue.

[0093] Example 3

[0094] Install the quartz fiber substrate on the unwinding shaft of the unwinding device, and then pass the quartz fiber substrate through the left slit flange, the flange at one end of the reaction chamber, the reaction chamber, the flange at the other end of the reaction chamber and the right slit flange to the rewinding shaft of the rewinding device. Turn on the exhaust device to evacuate the air, set the vacuum degree to 0.9Pa, and shield the oxygen monitor at the same time. When the vacuum degree is below 0.9Pa, turn on the protective gas device, the protective gas is nitrogen, set the pressure setting value to 850Pa, turn on the oxygen detector, turn on the heater for heating, and set the heating temperature to 800℃. When the pressure reaches 850Pa and the temperature reaches 800℃ and stabilizes, turn on the reaction gas device, the reaction gases are methane, hydrogen and helium, and then turn on the unwinding device and rewinding device to operate. When the quartz fiber substrate at the unwinding end is used up, the transmission of the rewinding end can be stopped, and the other parts remain unchanged. At this time, the used reel is removed and replaced with a new quartz fiber substrate roll. The old and new quartz fiber substrates can be connected together using a quick bonding method, and then the transmission is started to continue the preparation of graphene.

[0095] Example 4

[0096] Install the alumina fiber substrate on the unwinding shaft of the unwinding device, and then pass the alumina fiber substrate through the left slit flange, the flange at one end of the reaction chamber, the reaction chamber, the flange at the other end of the reaction chamber, and the right slit flange to the rewinding shaft of the rewinding device. Turn on the exhaust device to evacuate the air, set the vacuum degree to 0.8Pa, and shield the oxygen monitor at the same time. When the vacuum degree is below 0.8Pa, turn on the protective gas device, the protective gas is argon, set the pressure setting value to 850Pa, turn on the oxygen detector, turn on the heater for heating, and set the heating temperature to 800℃. When the pressure reaches 850Pa and the temperature reaches 800℃ and stabilizes, turn on the reaction gas device, the reaction gases are methane, hydrogen and argon, and then turn on the unwinding device and rewinding device for operation. When the alumina fiber substrate at the unwinding end is used up, the transmission of the rewinding end can be stopped, and the other conditions remain unchanged. At this time, the used reel is removed and replaced with a new alumina fiber substrate roll. The old and new alumina fiber substrates can be connected together using a quick bonding method, and then the transmission is started to continue the preparation of graphene.

[0097] Through the above-mentioned open roll-to-roll chemical vapor deposition system and film preparation method of the present application, it can be derived that the open roll-to-roll chemical vapor deposition system of the present application adopts four exhaust devices and two protective gas devices, which can effectively avoid the contact between the reaction gas and the air, and can reduce the pressure in the reaction chamber to below 1000Pa. The left slit flange and the right slit flange are adopted to further limit the amount of air entering the reaction chamber, isolating the reaction chamber from the air. The reeling and unreeling device is arranged on the outside of the slit flange. When in use, the substrate is arranged on the unreeling shaft of the reeling device, and the substrate passes through the left slit flange, the first flange at one end of the reaction chamber, the reaction chamber, the second flange at the other end of the reaction chamber and the right slit flange in sequence to reach the reeling shaft of the reeling device. In this way, when the coil is replaced, there is no need to adjust the low pressure in the reaction environment, and the replacement can be completed quickly without stopping the operation, realizing a truly continuous operation, providing production efficiency and production stability. The reeling and unreeling device is not in the same air pressure environment as the reaction chamber, and can also monitor the film in real time to improve the quality of the film.

[0098] In summary, the open roll-to-roll chemical vapor deposition system proposed in this application includes a reaction device, a reaction gas device, at least four exhaust devices, at least two protective gas devices, at least one left slit flange, at least one right slit flange, an unwinding device, and a rewinding device. The reaction device includes a reaction chamber, at least one first flange, and at least one second flange; the at least one first flange is connected to the left end of the reaction chamber and is connected to a pipeline communicating with the reaction chamber; the at least one second flange is connected to the right end of the reaction chamber and is connected to a pipeline communicating with the reaction chamber. The reaction gas device is connected to the reaction chamber and is used to introduce reaction gas into the reaction chamber. Two of the exhaust devices are arranged on the left side of the reaction chamber and are connected to the reaction chamber, and the other two are arranged on the right side of the reaction chamber and are connected to the reaction chamber. At least two protective gas devices are respectively arranged on both sides of the reaction chamber and are both connected to the reaction chamber. The left slit flange is arranged on the left side of the first flange, and the right slit flange is arranged on the right side of the second flange. The unwinding device is arranged on the left side of the left slit flange, and the rewinding device is arranged on the right side of the right slit flange.

[0099] The open roll-to-roll chemical vapor deposition system of the present application can effectively avoid the contact between the reaction gas and the air, and can reduce the pressure in the reaction chamber to below 1000Pa. It can also further limit the amount of air entering the reaction chamber, isolating the reaction chamber from the air. The reeling and unreeling device is arranged on the outside of the slit flange, so that when the coil is replaced, there is no need to adjust the low pressure in the reaction environment, and the replacement can be completed quickly without stopping the operation, thereby improving production efficiency and production stability. The reeling and unreeling device is not in the same air pressure environment as the reaction chamber, and can also monitor the film in real time.

[0100] The method for preparing a thin film proposed in this application adopts the above-mentioned open roll-to-roll chemical vapor deposition system, installs the substrate on the unwinding shaft of the unwinding device, and then passes the substrate through the left slit flange, the flange at one end of the reaction chamber, the reaction chamber, the flange at the other end of the reaction chamber and the right slit flange to the rewinding shaft of the rewinding device. Turn on the exhaust device to evacuate the air and set the vacuum degree to 1Pa. When the vacuum degree is below 1Pa, turn on the protective gas device, set the pressure setting value to below 1000Pa, turn on the heater for heating, and set the heating temperature setting value. When the pressure and temperature reach the set value and stabilize and maintain, turn on the reaction gas device, and then turn on the unwinding device and rewinding device for operation. Since this method adopts an open roll-to-roll chemical vapor deposition system to prepare the thin film, it can effectively reduce the amount of air entering during the preparation process and improve the quality of the film. It can also achieve the change of the coil without opening the reaction chamber, which improves production efficiency and reduces costs. The product can also be monitored online or offline, which is conducive to real-time control of product quality.

[0101] The above describes and / or illustrates in detail exemplary embodiments of the open roll-to-roll chemical vapor deposition system and thin film preparation method proposed in the present application. However, the embodiments of the present application are not limited to the specific embodiments described herein. On the contrary, the components and / or steps of each embodiment can be used independently and separately from the other components and / or steps described herein. Each component and / or each step of an embodiment can also be used in combination with other components and / or steps of other embodiments. When introducing the elements / components / etc. described and / or illustrated herein, the terms "one", "first", "second" and "above" are used to indicate the presence of one or more elements / components / etc. The terms "comprising", "including" and "having" are used to indicate an open-ended inclusive meaning and mean that in addition to the listed elements / components / etc., additional elements / components / etc. may be present.

[0102] The embodiments of the present application are not limited to the specific embodiments described herein. On the contrary, the components of each embodiment can be used independently and separately from the other components described herein. Each component of an embodiment can also be used in combination with other components of other embodiments. In the description of this specification, the description of the terms "one embodiment", "some embodiments", "other embodiments" and the like means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the embodiment. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0103] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. An open roll-to-roll chemical vapor deposition system, characterized by: include: A reaction device, comprising a reaction chamber, at least one first flange, and at least one second flange; the at least one first flange is connected to a left end of the reaction chamber and is connected to a pipeline communicating with the reaction chamber; the at least one second flange is connected to a right end of the reaction chamber and is connected to a pipeline communicating with the reaction chamber; a reaction gas device, connected to the reaction chamber, for introducing reaction gas into the reaction chamber; at least four gas extraction devices, two of which are disposed on the left side of the reaction chamber and communicate with the reaction chamber, and the other two are disposed on the right side of the reaction chamber and communicate with the reaction chamber; At least two protective gas devices, respectively disposed on both sides of the reaction chamber and both in communication with the reaction chamber; at least one left slit flange and at least one right slit flange, wherein the left slit flange is disposed on the left side of the first flange and the right slit flange is disposed on the right side of the second flange; an unwinding device and a rewinding device, wherein the unwinding device is arranged on the left side of the left slit flange, and the rewinding device is arranged on the right side of the right slit flange; The pressure in the reaction chamber is below 1000 Pa.

2. The open roll-to-roll chemical vapor deposition system according to claim 1, wherein: The reaction gas device includes a first reaction gas pipeline, a second reaction gas pipeline, a third reaction gas pipeline and a main reaction gas pipeline. The main reaction gas pipeline is connected to the reaction chamber, and the first reaction gas pipeline, the second reaction gas pipeline and the third reaction gas pipeline are all connected to the main reaction gas pipeline.

3. The open roll-to-roll chemical vapor deposition system according to claim 2, wherein: The main reaction gas pipeline is provided with a gas homogenizing tank, which is used to homogenize the reaction gases entering the main reaction gas pipeline from the first reaction gas pipeline, the second reaction gas pipeline, and the third reaction gas pipeline.

4. The open roll-to-roll chemical vapor deposition system according to claim 1, wherein: The gas extraction device includes a first gas extraction sub-device and a second gas extraction sub-device. The first gas extraction sub-device is arranged on the first flange and communicates with the reaction chamber through the first flange. The second gas extraction sub-device is arranged on the second flange and communicates with the reaction chamber through the second flange.

5. The open roll-to-roll chemical vapor deposition system according to claim 4, wherein: The open roll-to-roll chemical vapor deposition system also includes a third flange, a fourth flange, a fifth flange and a sixth flange, the third flange being adjacent to the right side of the left slit flange, the fourth flange being adjacent to the left side of the right slit flange, the fifth flange being arranged between the first flange and the third flange, and the sixth flange being arranged between the second flange and the fourth flange.

6. The open roll-to-roll chemical vapor deposition system according to claim 5, wherein: A first transfer chamber is sequentially provided between the first flange, the fifth flange, the third flange and the left slit flange, and a second transfer chamber is sequentially provided between the second flange, the sixth flange, the fourth flange and the right slit flange. The first transfer chamber and the second transfer chamber are communicated with the reaction chamber.

7. The open roll-to-roll chemical vapor deposition system according to claim 6, wherein: The exhaust device also includes a third exhaust sub-device and a fourth exhaust sub-device. The third exhaust sub-device is arranged on the third flange and is connected to the first transfer chamber through the third flange. The fourth exhaust sub-device is arranged on the fourth flange and is connected to the second transfer chamber through the fourth flange.

8. The open roll-to-roll chemical vapor deposition system according to claim 7, wherein: The gas extraction device includes a gas extraction pipe, and a vacuum gauge, a valve, a gas monitor and a vacuum pump are arranged on the gas extraction pipe along the direction of gas discharge.

9. The open roll-to-roll chemical vapor deposition system according to claim 8, wherein: The gas monitors on the first gas pumping sub-assembly and the second gas pumping sub-assembly are both oxygen monitors, and the gas monitors on the third gas pumping sub-assembly and the fourth gas pumping sub-assembly are both reaction gas monitors.

10. The open roll-to-roll chemical vapor deposition system according to claim 6, wherein: The protective gas device includes a left protective gas device and a right protective gas device. The left protective gas device is arranged on the fifth flange and communicates with the first transfer chamber through the fifth flange. The right protective gas device is arranged on the sixth flange and communicates with the second transfer chamber through the sixth flange.

11. The open roll-to-roll chemical vapor deposition system according to any one of claims 1 to 10, wherein: The reaction gas device and the protective gas device are both provided with a gas flow controller.

12. A method for preparing a thin film, using the open roll-to-roll chemical vapor deposition system according to any one of claims 1 to 10, comprising the following steps: Step 1: The substrate is mounted on the unwinding shaft of the unwinding device, and then the substrate is sequentially passed through the left slit flange, the first flange at one end of the reaction chamber, the reaction chamber, the second flange at the other end of the reaction chamber, and the right slit flange to the rewinding shaft of the rewinding device; Step 2: Turn on the vacuum device to pump air and set the vacuum degree to 1Pa; Step 3: When the vacuum degree is below 1Pa, turn on the protective gas device, set the pressure setting value to below 1000Pa, turn on the heater for heating, and set the heating temperature setting value; Step 4: When the pressure and temperature reach the set value and stabilize and maintain, turn on the reaction gas device, and then turn on the unwinding device and the winding device.

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