CN109295424B - High-conductivity parallel-arranged carbon nanotube spinning continuous production equipment and manufacturing method - Google Patents
High-conductivity parallel-arranged carbon nanotube spinning continuous production equipment and manufacturing method Download PDFInfo
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
Abstract
The invention relates to high-conductivity in-line carbon nanotube spinning continuous production equipment and a manufacturing method thereof. The invention uses the manipulator to convey the silicon chip, and the catalyst preparation, the preparation of the in-line carbon nanotube array and the drawing film spinning winding are connected in series to realize continuous production, the reaction chamber adopts a full vacuum plane structure and local heating, and the airflow direction, the gas concentration gradient and the temperature gradient are consistent with the growth direction of the in-line carbon nanotube array, thereby being beneficial to improving the growth quality of the array and enlarging the process window. The chamber material for the reaction growth of the carbon tube does not use a quartz tube, adopts a metal material, is easy to process, and the diameter of the chamber is easy to be enlarged.
Description
Technical Field
The invention relates to the technical field of nano material manufacturing equipment, in particular to high-conductivity in-line carbon nano tube spinning continuous production equipment and a manufacturing method.
Background
Since 1991 Japanese scientists discovered carbon nanotubes, their unique nanostructures, excellent electrical, mechanical and optical properties, have attracted extensive attention in the fields of flexible optoelectronic devices, energy storage devices, sensors, etc. The raw materials for producing the carbon nano tube are hydrocarbon gas such as methane, ethylene, acetylene and the like, are not limited by rare mineral resources, and the production process does not damage the environment. The preparation method mainly comprises an arc discharge method, a laser evaporation method and a Chemical Vapor Deposition (CVD) method. The carbon nano-tube prepared by different methods and process conditions is divided into single-wall type and multi-wall type, and is of metal type and semiconductor type, and has diverse characteristics. In 1996, it was reported that CVD was used to grow a unique array of carbon nanotubes in which the carbon nanotubes are aligned perpendicular to a planar substrate [ Science,1996,274(5293):1701-1703 ]. Subsequently, scientists have synthesized the super-ordered carbon nanotube array by controlling the growth rate of the carbon nanotubes [ Nature,2002,419(6909):801 ]. The super-ordered carbon nanotube array is characterized in that: high nucleation density, fast growth rate, narrow diameter distribution and higher order of parallel arrangement. Strong van der waals forces exist between the carbon nanotubes. When a bundle of carbon nanotubes is pulled out from the carbon nanotube array in the super-ordered arrangement, the carbon nanotubes can self-organize to form a continuous long line.
International patents WO2008/060665a2, US6350488B1, US6808746B1, US6863942B2, US7160531B1, US7854991B2, US8617650B2, etc. disclose the growth of a super-ordered carbon nanotube array using CVD methods using metal nanoparticle catalysis. International patents EP2397441a1, EP 2716600 a1, US7504078B1, US8709374B2 and the like disclose devices for growing aligned carbon nanotube films using metal catalysts and CVD methods followed by metal nanoparticle catalysis.
Although the steps of research and industrialization are increased for the preparation of the super-ordered carbon nano-tube in the world, with the deepening of the research, the new material technology is continuously perfected and matured and gradually goes to industrialized application. However, the CVD reaction process involves complicated gas phase chemical reaction and solid phase reaction, and how to precisely control the growth of the carbon nanotubes is still one of the problems to be solved. In addition, the highest conductivity of the conventional super-parallel-type conductive material is 105S/m, but as the conductive material of devices such as photoelectricity, energy storage and the like, the electrical property of the device needs to be further improved, and the existing method for manufacturing the super-ordered carbon nanotube array mainly comprises the steps of preparing a catalyst on a substrate and then placing the substrate into a tubular CVD (chemical vapor deposition) chamber (usually a quartz tube) for growth.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to overcome the defects in the prior art, the invention provides high-conductivity in-line carbon nanotube spinning continuous production equipment and a manufacturing method thereof, so as to overcome the technical problems that the existing in-line carbon nanotube film production process is not easy to control, has low conductivity, is not beneficial to continuous production and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows: a high-conductivity in-line carbon nanotube spinning continuous production device comprises a sample injection system, a metal catalytic film preparation system, a carbon nanotube growth system and a drawn film coated spinning winding system which are sequentially arranged, wherein a nanostructure transition system is arranged between the metal catalytic film preparation system and the carbon nanotube growth system, and a transfer transition system is arranged between the carbon nanotube growth system and the drawn film coated spinning winding system.
A sample introduction system: the device comprises a vacuum cavity, wherein a sample support with clamping grooves at two sides for clamping a silicon wafer is arranged in the vacuum cavity, and a first mechanical arm capable of transmitting the sample support with the silicon wafer to a subsequent system is arranged above the sample support.
Metal catalytic membrane preparation system: the vacuum chamber is internally provided with a substrate frame for placing a silicon wafer, an electron beam evaporation source is arranged below the substrate frame, and a substrate heater is arranged above the substrate frame. A baffle plate for preventing impurities from being deposited on the surface of the silicon wafer is arranged between the electron beam evaporation source and the substrate frame, and condensate pipes for cooling the wall of the vacuum chamber are wound around the vacuum chamber.
Carbon nanotube growth system: the device comprises a vacuum growth cavity and a substrate frame arranged in the growth cavity, wherein a double-layer air hole air homogenizing device is arranged above the substrate frame, a heating device is arranged below the substrate frame, the top of the growth cavity is connected with an air mixing cavity for introducing four paths of air for mixing, and the air mixing cavity is connected with four paths of air inlet systems for introducing four types of air.
Drawing a film, coating a film, spinning and winding the system: the device comprises a vacuum cavity, wherein a substrate frame, a spinning device and a winding device are arranged in the vacuum cavity, a nanoparticle deposition system is arranged above the substrate frame, a blade manipulator for pulling a carbon film from a carbon nanotube array on a silicon wafer is arranged at the discharge end of the substrate frame, a roller for guiding the carbon film to move is arranged between the blade manipulator and the spinning device, and yarns twisted by the spinning device are wound by the winding device in a rotating manner.
Nanostructure transition system: including the vacuum transition chamber, be equipped with the second manipulator that transfers the sample support between vacuum chamber and growth cavity in the vacuum transition chamber.
Transferring a transition system: the device comprises a vacuum transition chamber, wherein a third mechanical hand for transferring a sample support between a growth cavity and a vacuum cavity is arranged in the vacuum transition chamber.
Particularly, the vacuum cavity, the vacuum transition cavity, the growth cavity and the bottom of the vacuum transition chamber are all connected with a mechanical pump for pumping vacuum; the vacuum chamber and the bottom of the vacuum chamber are connected with a vacuum system for realizing high vacuum or low vacuum in the vacuum chamber and the vacuum chamber, so that the silicon wafer sample can be ensured to penetrate through the chambers in all vacuum states for transmission, the whole operation process is completed in a vacuum environment, and the carbon nano tube is ensured not to be polluted by the outside.
Furthermore, the two sides of the vacuum cavity, the vacuum transition cavity, the growth cavity and the vacuum transition chamber are respectively communicated through transition cabin doors capable of controlling opening and closing.
In order to improve the operation efficiency, the vacuum cavity is internally provided with a multi-layer frame for placing the sample support, and the multi-layer frame is internally provided with a lifting device for lifting the sample support up and down.
The manufacturing method for spinning and producing the high-conductivity aligned carbon nano tube by using the continuous production equipment comprises the following steps:
a. transferring the silicon wafer into a vacuum chamber of a metal catalytic film preparation system from a vacuum chamber of a sample injection system;
b. depositing a metal catalytic film: evaporating Fe or Ni material onto a silicon wafer deposited with silicon oxide with the thickness of 1 micron by using an electron beam evaporation source, wherein the thickness of Fe or Ni is 5-10 nm, and starting a substrate heater in the deposition process;
c. rapidly transferring the silicon wafer deposited with the metal catalytic film to a nano-structure transition system to form nano-particles on the silicon wafer;
d. growing a carbon nano tube array; opening the heating device, raising the temperature of the substrate frame to 700-800 ℃, enabling four paths of mixed gas in the gas mixing cavity to enter the double-layer gas hole homogenizing device to reach a silicon wafer sample on the substrate frame, and promoting the vertical growth of the carbon nano tube by utilizing the fact that the gas flow direction and the temperature gradient direction are perpendicular to the silicon wafer;
e. transferring the carbon nanotube array into a vacuum transition chamber of a transfer transition system;
f. film drawing, nanoparticle deposition, spinning and winding; the blade manipulator horizontally moves to the edge of the carbon nano tube array and lightly presses the carbon nano tube along the vertical direction to pull out carbon filaments, then a nano particle deposition system starts to evaporate metal nano particles or oxide nano particles to deposit on a carbon nano tube film, the carbon nano tube film moves while the nano particles are evaporated, a rotating motor of a spinning device starts to rotate, the carbon nano tube is twisted and spun, and the spinning is rotated and wound by a winding device while the spinning is carried out.
The invention has the beneficial effects that: the invention uses a manipulator to convey the silicon chip, and the catalyst preparation, the preparation of the in-line carbon nanotube array and the drawing film spinning winding are connected in series, thereby realizing the continuous production. The chamber for reacting and growing the in-line carbon nano tubes adopts a planar structure and local heating, and the airflow direction, the gas concentration gradient and the temperature gradient are consistent with the growth direction of the in-line carbon nano tube array, thereby being beneficial to improving the growth quality of the array and expanding the process window. The chamber material for the reaction growth of the carbon tube does not use a quartz tube, adopts a metal material, is easy to process, and the diameter of the chamber is easy to be enlarged. In addition, the carbon tube is modified by the nano particles, so that the conductivity is improved.
Drawings
The invention is further illustrated with reference to the following figures and examples.
Fig. 1 is a schematic structural view of the present invention.
Fig. 2 is a schematic view illustrating a process of transferring a silicon wafer by the first robot according to the present invention.
In the figure: 100. sample introduction system 101, multi-layer rack 102, silicon wafer 103, first manipulator 104, sample holder 105, vacuum chamber 106, mechanical pump 107 and transition door
200. Metal catalytic film preparation system 201, vacuum chamber 202, vacuum system 204, electron beam evaporation source 205, substrate holder 206, substrate heater 207 and baffle plate
300. Nanostructure transition system 301, vacuum transition chamber 303, second manipulator
400. Carbon nano tube growth system 401, growth cavity 403, double-layer air hole gas uniformizing device 404, heating device 405, four-way air inlet system 406 and gas mixing cavity
500. Transfer transition system 501, vacuum transition chamber 503, third manipulator
600. Film-drawing coating spinning winding system 601, vacuum chamber 604, blade manipulator 605, roller 606, nanoparticle deposition system 607, spinning device 608 and winding device
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic views illustrating only the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
As shown in fig. 1 and 2, the high-conductivity in-line carbon nanotube spinning continuous production equipment comprises a sample injection system 100, a metal catalytic film preparation system 200, a nanostructure transition system 300, a carbon nanotube growth system 400, a transfer transition system 500 and a drawn film coating spinning winding system 600 which are sequentially arranged and hermetically connected with one another.
The sample introduction system 100: the device comprises a square vacuum cavity 105 made of stainless steel, wherein the bottom of the vacuum cavity 105 is connected with a mechanical pump 106 for vacuum pumping, the mechanical pump is used for maintaining the vacuum degree of the vacuum cavity 105, a cleaned square silicon wafer 102 is placed on a multi-layer frame 101 capable of moving up and down, a lifting device for lifting a sample support 104 up and down is arranged in the multi-layer frame 101, a first mechanical arm 103 capable of rotating and moving horizontally is arranged, and the sample support 104 with clamping grooves on two sides is used for clamping the silicon wafer 102. The transition port 107 (using a pneumatic gate valve, the same applies hereinafter) located on the right side of the vacuum chamber 105 is connected to the metal catalyst film preparation system 200, and the transition port 107 located on the left side of the vacuum chamber 105 is used for replacing objects inside the vacuum chamber 105. The electric control system is provided for controlling the vacuum chamber 105, the mechanical pump 106, and the first robot 103, including controlling the chamber pressure of the vacuum chamber 105, the transfer operation of the silicon wafer 102, and the like.
Metal catalytic thin film preparation system 200: the device comprises a square vacuum chamber 201 made of 316L stainless steel, wherein a substrate frame 205 for placing a silicon wafer 102 is arranged in the vacuum chamber 201, an electron beam evaporation 204 is arranged below the substrate frame 205, the electron acceleration voltage of the electron beam evaporation source 204 is 5-10 kilovolts, the electron current is 100-600 mA, the power of an electron gun is 0-6 KW and can be continuously adjusted, an electron beam spot is focused on the evaporation source and can perform scanning motion, the scanning frequency and amplitude are adjustable, the surface of the silicon wafer 102 is cleaned by an ion bombardment mode (adopting an alternating current high-voltage power supply), and the adhesive force between a film layer and the surface of the silicon wafer 102 is increased; a substrate heater 206 is arranged above the substrate holder 205, a baffle plate 207 for preventing impurities from being deposited on the surface of the silicon wafer 102 is arranged between the electron beam evaporation source 204 and the substrate holder 205, the baffle plate 207 is driven by compressed air, and when an evaporation material in the crucible is preheated, the baffle plate 207 can shield the upper part of the electron beam evaporation source 204 to prevent the impurities in the material from being deposited on the surface of the silicon wafer 102; the baffle 207 may also be used to control the film thickness when the film thickness meets the desired thickness requirement. The bottom of the vacuum chamber 201 is connected with a vacuum system 202, the high vacuum system of the vacuum system 202 comprises a molecular pump, a molecular pump valve, a transition pipeline and the like, and the low vacuum system comprises a pipeline valve, a low vacuum pipeline, a mechanical air pump, an air release valve and the like. Condensed water pipes for cooling the wall of the vacuum chamber 201 are wound around the vacuum chamber 201, so that the purpose of cooling the crucible filled with evaporated materials can be achieved; in order to make the film layer uniform, the substrate holder 205 can rotate, the rotation of the substrate holder 205 is driven by a variable speed motor, and the rotation speed is continuously adjustable and is 3-30 RPM. Heating temperature range of the silicon wafer 102: room temperature to 800 ℃. The electric control system respectively controls the vacuum chamber 201, the electron beam evaporation source 204, the vacuum system 202 and the like, and comprises growth pressure, power, heating temperature and the like;
nanostructure transition system 300: the device comprises a square vacuum transition cavity 301 (made of 316L stainless steel), wherein a second mechanical arm 303 for transferring a sample holder between a vacuum cavity 201 and a carbon nano tube growth system 400 is arranged in the vacuum transition cavity 301, the second mechanical arm 303 can rotate and horizontally move, and the bottom of the vacuum transition cavity 301 is connected with a mechanical pump 106 for pumping vacuum; the transition cabin door 107 on the right side of the vacuum transition cavity 301 is communicated with the carbon nano tube growth system 400, and the transition cabin door 107 on the left side of the vacuum transition cavity is communicated with the metal catalytic film preparation system 200. The equipped electric control system respectively controls the vacuum transition cavity 301, the mechanical pump 106, the second mechanical arm 303 and the like, including cavity pressure, sample transmission and the like;
carbon nanotube growth system 400: comprises a square growth cavity 401 (made of 316L stainless steel), a substrate frame 205, a double-layer air hole uniform gas device 403, a heating device 404 (capable of heating a silicon wafer to 700-. The left side and the right side of the growth cavity 401 are respectively communicated with the nanostructure transition system 300 and the transfer transition system 500 through the transition cabin door 107 for transferring the silicon wafer 102 sample, and the three main cavities of the metal catalytic film preparation system 200, the carbon nanotube growth system 400 and the film drawing, coating, spinning and winding system 600 are not interfered with each other.
The bottom of the growth cavity 401 is connected with a mechanical pump 106 for pumping vacuum, the front of the growth cavity 401 is provided with an observation window for observing the growth condition of the carbon nano tube, and the corresponding surface of the observation window is provided with an extraction opening for maintaining the vacuum state of the growth cavity 401.
The gas mixing cavity 406 is located above the growth cavity 401, and the four-way gas inlet system 405 is connected with the gas mixing cavity 406 to provide growth gases, including carbon source gas, inert gas, hydrogen gas and reducing gas, for the growth cavity 401. The gas enters a mixing cavity 406 through a valve and a mass flow meter (the flow can be adjusted by 0-100 sccm) to be mixed, and then enters a growth cavity 401 to grow the carbon nano tube through a chemical reaction. The four-way air intake system 405 is mainly used for controlling the flow of growth gas, and mainly comprises a mass flow meter, a one-way valve, a pneumatic stop valve and a pipeline. The gas source supplied by the gas cylinder enters the growth cavity 401 through the pressure reducer, the mass flow meter, the check valve and the pneumatic stop valve. All parts of the four-way air inlet system 405 are connected through stainless steel pipelines, and air channel control signals of the four-way air inlet system 405 are provided by an electric control system (PLC).
The double-layer air hole air evening device 403 is positioned at the upper part in the growth cavity 401 and is arranged between the air mixing cavity 406 and the substrate frame 205 which is arranged in parallel, so that the uniformity of the vacuum degree and the air flow direction in the growth cavity 401 is ensured, and the growth uniformity of the carbon film is improved; a heating device 404 is positioned below the substrate holder 205 for locally heating the silicon wafer 102.
The electric control system respectively controls the growth cavity 401, the four-way air inlet system 405, the mechanical pump 106 and the heating device 404; the electric control system mainly controls the four-way air intake system 405 according to the opening and closing time of the valve, the air flow and the like; the control of the mechanical pump 106 by the electronic control system is mainly the start and stop time of the mechanical pump 106. Wherein the mechanical pump 106 primarily provides vacuum to the growth chamber 401.
Transfer transition system 500: the device comprises a square vacuum transition chamber 501 (made of 316L stainless steel), a mechanical pump 106 is connected to the bottom of the vacuum transition chamber 501, a third mechanical arm 503 capable of rotating and moving horizontally is installed on the vacuum transition chamber 501, and the two sides of the vacuum transition chamber 501 are communicated with a carbon nanotube growth system 400 and a film drawing, coating, spinning and winding system 600 through transition doors 107. The electric control system respectively controls the vacuum transition chamber 501, the mechanical pump 106 and the third mechanical arm 503, including chamber pressure, sample transmission and the like;
a film drawing, coating, spinning and winding system 600: the device comprises a vacuum cavity 601 (made of 316L stainless steel), a substrate rack 205, a spinning device 607 and a winding device 608 are arranged in the vacuum cavity 601, a nanoparticle deposition system 606 is arranged above the substrate rack 205, a blade manipulator 604 for pulling a carbon film from a carbon nanotube array on a silicon wafer 102 is arranged at the discharge end of the substrate rack 205, a roller 605 for guiding the carbon film to move is arranged between the blade manipulator 604 and the spinning device 607, and yarns twisted by the spinning device 607 are wound by the winding device 608 in a rotating manner.
The vacuum system 202 which is the same as that used by the metal catalytic thin film preparation system 200 is connected to the bottom of the vacuum cavity 601, the vacuum system 202 is composed of a high vacuum system and a low vacuum system, the high vacuum system comprises a molecular pump, a molecular pump valve, a transition pipeline and the like, and the low vacuum system is composed of a pipeline valve, a low vacuum pipeline, a mechanical air pump, a deflation valve and the like.
The nanoparticle deposition system 606 has an electron beam acceleration voltage of 5-10 kV, an electron current of 100-600 mA, and an electron gun power of 0-6 KW which is continuously adjustable. The electron beam spot is focused on the evaporation source, can do scanning movement, and the scanning frequency and the amplitude can be adjusted.
The manufacturing method for spinning and producing the high-conductivity aligned carbon nano tube by using the continuous production equipment comprises the following steps:
a. transferring the silicon wafer 102 from the vacuum chamber 105 of the sample injection system 100 into the vacuum chamber 201 of the metal catalytic film preparation system 200:
the vacuum chamber 105 is evacuated to a pressure of 1Pa or less by the mechanical pump 106, the first robot 103 is horizontally inserted into the chuck slot of the lowermost sample holder 104 of the multi-stage rack 101, the sample holder 104 is then pulled out of the multi-stage rack 101, the multi-stage rack 101 is moved downward one frame, the first robot 103 is horizontally inserted into the multi-stage rack 101 again, the silicon wafer 102 is inserted into the chuck slot of the upper sample holder 104, the first robot 103 is horizontally moved out of the multi-stage rack 101, and then the first robot 103 is horizontally rotated by 180 degrees. The transition door 107 connected to the metal catalytic film preparation system 200 is opened, and the silicon wafer 102 sample is introduced into the vacuum chamber 201 of the metal catalytic film preparation system 200. At this time, the vacuum chamber 201 is also communicated with the vacuum system 202, and the air pressure is below 1 Pa. The first robot 103 is flipped upside down to place the silicon wafer 102 with the sample holder 104 in the vacuum chamber 201 on the substrate holder 205, and then the first robot 103 returns from the pod door 107 to the vacuum chamber 105 to close the pod door 107.
b. Depositing a metal catalytic film:
the valve between the vacuum chamber 201 and the molecular pump is opened to pump the pressure in the vacuum chamber 201 to 10-3Pa or less. And evaporating Fe or Ni material onto the silicon wafer 102 deposited with silicon oxide with the thickness of about one micron by using an electron beam evaporation method, wherein the thickness of the Fe or Ni is 5-10 nm. And starting the substrate heater 206 in the deposition process, and controlling the heating temperature to be 600-800 ℃. After deposition is complete, the substrate heater 206 is turned off and the valves between the vacuum chamber 201 and the molecular pumps are closed.
c. The silicon wafer 102 substrate deposited with the metal catalytic film is rapidly transferred into a vacuum transition cavity 301 of a nanostructure transition system 300 to form nanoparticles:
opening a transition cabin door 107 on the left side of a vacuum transition cavity 301, horizontally moving the second mechanical arm 303 in the vacuum transition cavity 301 to the position of a substrate frame 205 in a vacuum cavity 201, inserting the transition cabin door 107 into clamping grooves on two sides of a sample holder 104, horizontally moving the sample holder 104 with a silicon wafer 102 out of the substrate frame 205, sending the sample into the vacuum transition cavity 301, closing the transition cabin door 107, horizontally rotating the second mechanical arm 303 by 180 degrees, and constantly connecting the vacuum transition cavity 301 with a mechanical pump 106 to keep the air pressure of the vacuum transition cavity 301 below 1 Pa. As the silicon wafer 102 deposited with the metal Fe layer is rapidly moved from the high temperature area to the vacuum transition cavity 301 at room temperature, the difference between the thermal expansion coefficient of iron (11.8 ppm/DEG C) and the thermal expansion coefficient of the silicon wafer 102 (2.5 ppm/DEG C) is large, so that the Fe film forms nano-particles on the silicon wafer 102, which is beneficial to the subsequent nucleation growth of the carbon nano-tube.
d. Growing the carbon nanotube array:
and opening a transition cabin door 107 at the right side of the vacuum transition cavity 301, horizontally moving the second mechanical arm 303 to the growth cavity 401, placing the silicon wafer 102 on the substrate holder 205, horizontally withdrawing the second mechanical arm 303 from the growth cavity 401, passing through the transition cabin door 107, and returning to the vacuum transition cavity 301. The valve between the mechanical pump 106 and the growth chamber 401 is always opened, and the pressure in the growth chamber 401 is maintained at 1Pa or less. Then the four-way gas inlet system 405 opens the nitrogen or argon valve, controls the flow at 10-30 sccm, opens the heating device 404, and raises the temperature of the substrate holder 205 with the silicon wafer 102 to 700-800 ℃. The four-way gas inlet system 405 opens the valves for hydrogen, methane or acetylene at a flow rate of 20-30 sccm and 4-6 sccm respectively, and the gases enter the gas mixing chamber 406 and then enter the double-layer gas hole homogenizing device 403 to reach the silicon wafer 102 sample on the substrate holder 205. The vertical growth of carbon nanotubes is facilitated by the perpendicular orientation of the gas flow and temperature gradient to the sample 102. In addition, the metal nanoparticles on the silicon wafer 102 are also beneficial to the nucleation growth of the carbon nanotubes, and finally grow into a densely arranged carbon nanotube array.
e. Transferring the carbon nanotube array to a transfer transition system:
the transition port door 107 on the left side of the vacuum transition chamber 501 is opened and the third robot 503 moves horizontally to the substrate holder 205 in the growth chamber 401 to move the silicon wafer 102 sample into the vacuum transition chamber 501. The transition hatch 107 is closed and the third robot manipulator 503 is rotated 180 degrees. The vacuum transition chamber 501 is always connected to the mechanical pump 106, and maintains the air pressure below 1 Pa.
f. Film drawing, nanoparticle deposition, spinning and winding:
the transition port door 107 on the right side of the vacuum transition chamber 501 is opened and the third robot 503 moves the sample of the silicon wafer 102 horizontally onto the substrate holder 205 in the vacuum chamber 601. The blade mechanical arm 604 moves horizontally to the edge of the carbon nanotube array, the blade of the blade mechanical arm 604 lightly presses the carbon tube along the vertical direction, the carbon film is slowly lifted for 1mm while being kept for 30s, the carbon film is pulled out, then the blade mechanical arm 604 is pulled outwards at a constant speed (1-5 mm/min) along the horizontal direction, the carbon film is stretched to a roller 605, twisting is performed, and yarns are produced by the spinning device 607. Roller 605 is used to fix the position of the carbon film. The take-up device 608 is an axially fixed take-up drum and is also a driving force for guiding the twisting rotation. The carbon nanotube film moves while the nanoparticle deposition system 606 evaporates nanoparticles onto the carbon film. The electric control system controls the action processes of the vacuum system 202, the blade robot 604, the nanoparticle deposition system 606, the spinning device 607 and the winding device 608 through a PLC controller.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (7)
1. The utility model provides a arrange carbon nanotube spinning continuous production equipment in same direction as, including the sampling system, the metal catalysis membrane preparation system, carbon nanotube growth system and draw membrane coating film spinning winding system that arrange in proper order, be equipped with nanometer structure transition system between metal catalysis membrane preparation system and the carbon nanotube growth system, be equipped with transfer transition system, characterized by between carbon nanotube growth system and the draw membrane coating film spinning winding system:
the sample introduction system comprises: the device comprises a vacuum cavity, wherein a sample support with clamping grooves at two sides for clamping a silicon wafer is arranged in the vacuum cavity, and a first manipulator capable of transferring the sample support with the silicon wafer to a subsequent system is arranged above the sample support;
the metal catalytic membrane preparation system comprises: the vacuum chamber is internally provided with a substrate frame for placing a silicon wafer, an electron beam evaporation source is arranged below the substrate frame, and a substrate heater is arranged above the substrate frame;
the carbon nanotube growth system: the device comprises a vacuum growth cavity and a substrate frame arranged in the growth cavity, wherein a double-layer air hole gas homogenizing device is arranged above the substrate frame, a heating device is arranged below the substrate frame, and the top of the growth cavity is connected with a gas mixing cavity which is filled with four paths of gas for mixing;
the drawing film coating spinning winding system comprises: the device comprises a vacuum cavity, wherein a substrate frame, a spinning device and a winding device are arranged in the vacuum cavity, a nanoparticle deposition system is arranged above the substrate frame, a blade manipulator for pulling a carbon film from a carbon nanotube array on a silicon wafer is arranged at the discharge end of the substrate frame, a roller for guiding the carbon film to move is arranged between the blade manipulator and the spinning device, and yarns twisted by the spinning device are wound by the winding device in a rotating manner.
The nanostructure transition system: the device comprises a vacuum transition cavity, wherein a second mechanical arm for transferring a sample support between a vacuum cavity and a growth cavity is arranged in the vacuum transition cavity;
the transfer transition system: the device comprises a vacuum transition chamber, wherein a third mechanical hand for transferring a sample support between a growth cavity and a vacuum cavity is arranged in the vacuum transition chamber.
2. The apparatus for continuous production of aligned carbon nanotube filaments according to claim 1, wherein: the vacuum cavity, the vacuum transition cavity, the growth cavity and the bottom of the vacuum transition chamber are all connected with a mechanical pump for pumping vacuum; the vacuum chamber and the bottom of the vacuum chamber are both connected with a vacuum system for realizing high vacuum or low vacuum in the vacuum chamber and the vacuum chamber.
3. The apparatus for continuous production of aligned carbon nanotube filaments according to claim 1, wherein: the vacuum cavity, the vacuum transition cavity, the growth cavity and the vacuum transition chamber are respectively communicated through transition cabin doors capable of being controlled to be opened and closed.
4. The apparatus for continuous production of aligned carbon nanotube spinning as set forth in claim 1, wherein: the vacuum chamber body is internally provided with a multi-layer frame for placing the sample support, and the multi-layer frame is internally provided with a lifting device for lifting the sample support up and down.
5. The apparatus for continuous production of aligned carbon nanotube filaments according to claim 1, wherein: and a baffle plate for preventing impurities from being deposited on the surface of the silicon wafer is arranged between the electron beam evaporation source and the substrate frame, and condensate pipes for cooling the wall of the vacuum chamber are wound around the vacuum chamber.
6. The apparatus for continuous production of aligned carbon nanotube filaments according to claim 1, wherein: the gas mixing cavity is connected with a four-way gas inlet system for introducing four gases,
7. a manufacturing method for the in-line carbon nanotube spinning production using the continuous production apparatus as claimed in claim 1, comprising the steps of:
a. transferring the silicon wafer into a vacuum chamber of a metal catalytic film preparation system from a vacuum chamber of a sample injection system;
b. depositing a metal catalytic film: evaporating Fe or Ni material onto a silicon wafer deposited with silicon oxide with the thickness of 1 micron by using an electron beam evaporation source, wherein the thickness of Fe or Ni is 5-10 nm, and starting a substrate heater in the deposition process;
c. transferring the silicon wafer deposited with the metal catalytic film to a nano-structure transition system to form nano-particles on the silicon wafer;
d. growing a carbon nano tube array; opening the heating device, raising the temperature of the substrate frame to 700-80 ℃, enabling four paths of mixed gas in the gas mixing cavity to enter the double-layer gas hole homogenizing device to reach a silicon wafer sample on the substrate frame, and promoting the vertical growth of the carbon nano tube by utilizing the fact that the gas flow direction and the temperature gradient direction are perpendicular to the silicon wafer;
e. transferring the carbon nanotube array into a vacuum transition chamber of a transfer transition system;
f. film drawing, nanoparticle deposition, spinning and winding; the blade manipulator horizontally moves to the edge of the carbon nano tube array and presses the carbon nano tube along the vertical direction to pull out carbon filaments, then the nano particle deposition system starts to evaporate metal nano particles or oxide nano particles to deposit on a carbon nano tube film, the carbon nano tube film moves while being evaporated, the nano particles are evaporated while being evaporated, a rotating motor of a spinning device starts to rotate, the carbon nano tube is twisted and spun along with the twisting, and the carbon nano tube is rotated and wound by a winding device while being spun.
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| CN109913840B (en) * | 2019-05-06 | 2021-06-04 | 成都精密光学工程研究中心 | Be applied to multi-chamber coating device's manipulator and multi-chamber coating device |
| CN110937592B (en) * | 2019-11-08 | 2022-03-22 | 深圳烯湾科技有限公司 | Batch continuous production equipment for carbon nanotubes and preparation method thereof |
| CN110937591B (en) * | 2019-11-08 | 2022-03-22 | 深圳烯湾科技有限公司 | Batch continuous production equipment for carbon nanotubes |
| CN110846622B (en) * | 2019-11-11 | 2022-03-29 | 深圳市华星光电半导体显示技术有限公司 | Vapor deposition apparatus and control method thereof |
| CN111172519A (en) * | 2020-01-17 | 2020-05-19 | 中国航发北京航空材料研究院 | Device and method for continuously preparing composite interface layer on surface of silicon carbide fiber |
| CN111762775A (en) * | 2020-06-29 | 2020-10-13 | 安徽贝意克智能科技有限公司 | Multi-tube type full-automatic continuous carbon nanotube preparation equipment |
| CN114702028A (en) * | 2022-03-04 | 2022-07-05 | 常州大学 | Preparation method of carbon nanotube film composite material |
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