Automatic damage-free transfer device and transfer method for two-dimensional material

Abstract

The invention relates to the field of preparation and transfer of two-dimensional materials, in particular to an automatic damage-free transfer device and method for a two-dimensional material. The device comprises an ink-jet centrifugal film-making system, a mechanical sampling system, a cabin system, a liquid injection system, a porous liquid discharge circulating system, a target substrate piston lifting platform and a mechanical sample feeding system, and is characterized in that a uniform transfer medium film with controllable thickness is formed by a rotary centrifugal technology; the two-dimensional material is transferred without damage by combining full-process mechanical sample transfer and accurate liquid control, so that the influence of shearing force on the material is remarkably reduced, and damage and pollution are effectively avoided. The transfer efficiency is improved through an automatic process, stable transfer of a large-area two-dimensional material can be achieved, continuous preparation of a multi-layer film is supported, and the method is suitable for large-scale industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of preparation and transfer of two-dimensional materials, in particular to an automatic non-damage transfer device and method for two-dimensional materials, which is suitable for non-damage and automatic transfer of large-area two-dimensional materials grown by chemical vapor deposition (CVD) method to various target substrates, and can be widely applied in the fields of preparation and packaging of optoelectronic devices and integrated circuits. BACKGROUND

[0002] Two-dimensional materials are materials with a thickness of only one or a few atomic layers, which have unique structure and excellent physical and chemical properties, and have good application prospects in the fields of preparation and packaging of optoelectronic devices and integrated circuits. At present, chemical vapor deposition (CVD) is the most effective method for industrial production of large-area high-quality two-dimensional materials, however, two-dimensional materials grown by CVD need to be transferred to target substrates for application.

[0003] The traditional two-dimensional material transfer technology (such as wet transfer, dry transfer, etc.) has the following problems: (1) uneven transfer medium coating. For example, spin coating method easily leads to uneven film thickness, causing stress concentration and material damage; (2) mechanical damage. Shear force during manual operation or mechanical peeling causes two-dimensional material to wrinkle and tear; (3) low degree of automation. It relies on manual operation, which is low in efficiency and difficult to realize mass production.

[0004] The patent with publication number CN116161613A proposes a two-dimensional material transfer device and method, which realizes clean transfer through vacuum lamination and electrostatic force, although it avoids organic polymer residues, but there is no full-process mechanical transmission system, and sample transmission relies on manual assistance, which is easy to cause mechanical damage. The patent with publication number CN112762835A proposes a micro-control platform for non-destructive fixed-point transfer of two-dimensional materials by solid-liquid method, which realizes precise position control through three-dimensional displacement table and imaging monitoring, but lacks uniform transfer medium coating system, and cannot avoid material wrinkles during the transfer process. The patent with publication number CN119663434A proposes a clean and non-destructive two-dimensional semiconductor material transfer method, which improves cleanliness through inorganic protective layer and organic support layer, but still has the problem of poor film thickness uniformity when using spin coating method to prepare organic support layer. The patent with publication number CN119650414A proposes a two-dimensional material desolvation non-destructive precise transfer method, which uses traditional spin coating process to prepare polymethyl methacrylate (PMMA) support film, and the spin coating process is easy to cause uneven film thickness, causing stress concentration; it relies on manual picking and transferring of PDMS, which has low automation degree and cannot guarantee the stability of the transmission process. The patent with publication number CN109133174A proposes a two-dimensional material transfer method and application of two-dimensional material, which uses a pure physical transfer method of pressurization-dripping-drying, although it avoids chemical reagent pollution, but relies on manual operation to align the substrate, has no automatic transmission mechanism, and is easy to cause material damage due to shear force caused by human intervention; it can only realize single sample transfer at a time, has no batch processing capability, and has very low productivity, which cannot meet the preparation needs of flexible substrates and multi-layer films.

[0005] Although the existing patents involve centrifugal film preparation, they do not solve the problems of shear force influence and full-process automatic control. In view of the above problems, it is urgent to design and develop an automatic non-damage transfer device for two-dimensional materials. SUMMARY

[0006] The purpose of the present application is to provide an automatic non-damage transfer device and method for two-dimensional materials, which solves the problems of uneven thickness of transfer medium, mechanical damage and low automation degree in existing two-dimensional material transfer technology, and can realize efficient and non-damage automatic transfer of large-area two-dimensional materials grown by CVD.

[0007] The technical scheme of the present application is: An automatic non-damage transfer device for two-dimensional materials, which comprises a mechanical sampling system, an inkjet centrifugal film preparation system, a cabin system, a liquid injection system, a multi-hole liquid drainage circulation system, a target substrate piston lifting table and a mechanical sample feeding system, and the specific structure is as follows: The three transfer cabins of the cabin system are linearly arranged along the y-axis direction, the inner cavity bottom of each transfer cabin is provided with an injection nozzle of a liquid injection system and a drainage port of a multi-hole drainage circulation system, and the target substrate piston lifting platform is arranged above the cabin system; The mechanical sampling system is located at the input end of the cabin system, a first guide rail of the mechanical sampling system is laid along the y-axis, a first guide rail slider and a sampling table are arranged on the first guide rail, one end of the first guide rail is connected to the first transfer cabin of the cabin system, the inkjet centrifugal membrane preparation system is located on one side of the mechanical sampling system, the sampling table of the mechanical sampling system corresponds to the rotating drum of the inkjet centrifugal membrane preparation system, a first stepper motor drives a first ball screw to drive the first guide rail slider to move horizontally along the first guide rail, thereby realizing horizontal transmission of the sampling table, and the first stepper motor is used to feed the transfer medium / two-dimensional material / target substrate laminated composite film into the first transfer cabin of the cabin system at a constant speed; The mechanical sampling system is located at the input end of the cabin system, a first guide rail of the mechanical sampling system is laid along the y-axis, a first guide rail slider and a sampling table are arranged on the first guide rail, one end of the first guide rail is connected to the first transfer cabin of the cabin system, the inkjet centrifugal membrane preparation system is located on one side of the mechanical sampling system, the sampling table of the mechanical sampling system corresponds to the rotating drum of the inkjet centrifugal membrane preparation system, a first stepper motor drives a first ball screw to drive the first guide rail slider to move horizontally along the first guide rail, thereby realizing horizontal transmission of the sampling table, and the first stepper motor is used to feed the transfer medium / two-dimensional material / target substrate laminated composite film into the first transfer cabin of the cabin system at a constant speed;

[0008] The automatic non-invasive transfer device for two-dimensional materials, the mechanical sampling system includes a first stepper motor, a first guide rail slider, a sampling table, a first sample holder, a first ball screw and a first guide rail, the inkjet centrifugal membrane preparation system is used for preparing a transfer medium film on the surface of the two-dimensional material / target substrate, and includes a rotating drum and a nozzle or a needle, the two-dimensional material is tightly attached to the inner wall of the rotating drum under the centrifugal force provided by the rotating drum, and the nozzle or the needle is translated to coat the transfer medium solution under the control of a program; the first stepper motor is connected to the first ball screw, the first ball screw passes through the first guide rail slider and is connected thereto, the first guide rail slider is placed in and in sliding fit with the clamping groove of the first guide rail, the first guide rail is placed along the y-axis, and the rotation of the first stepper motor drives the first guide rail slider to move horizontally along the first guide rail; the sampling table is fixed on the first guide rail slider, and the first sample holder is placed on the sampling table, the rotating drum is placed on one side of the first guide rail close to the first stepper motor, the rotating shaft of the rotating drum is parallel to the x direction, the central axis of the nozzle or the needle is perpendicular to the inner wall of the rotating drum, and the side of the first guide rail away from the first stepper motor is connected to the first transfer cabin.

[0009] The automated non-destructive transfer device for two-dimensional materials includes a chamber system comprising a first transfer chamber, a second transfer chamber, and a third transfer chamber, arranged sequentially along the y-direction; a liquid injection system comprising a first injection nozzle corresponding to the first transfer chamber, a second injection nozzle corresponding to the second transfer chamber, and a third injection nozzle corresponding to the third transfer chamber; and a porous drainage and circulation system comprising a first drain port, a second drain port, and a third drain port corresponding to the first transfer chamber, a fourth drain port, a fifth drain port, and a sixth drain port corresponding to the second transfer chamber, and a seventh drain port, an eighth drain port, and a ninth drain port corresponding to the third transfer chamber. The liquid injection system is used for etching the target substrate, cleaning and removing the transfer medium, and cleaning the etched substrate and the two-dimensional material after removing the transfer medium. The liquid injection system contains a temperature control module with a temperature range of 15-150℃, an injection volume adjustment range of 10-1000mL, and a flow rate adjustment range of 0.1-10mL / min. It supports continuous or intermittent injection modes and can precisely control the injection volume and flow rate of the liquid to ensure uniform distribution of the injected liquid. The porous drainage and circulation system is used to recover cleaning waste liquid and wastewater. It can work in conjunction with the liquid injection system to control the injection and recovery of the solution, thereby circulating and cleaning the two-dimensional material. The liquid level sensor monitors the liquid level in the chamber in real time and dynamically adjusts the injection flow rate and drainage speed. The recovered liquid is filtered through a filter membrane and then recycled.

[0010] The automated, non-destructive transfer device for two-dimensional materials includes a target matrix piston lifting platform comprising a second stepper motor, a second guide rail, a second ball screw, a second guide rail slider, a fixing block, a cable chain, a third stepper motor, a cable chain fixing block, a third guide rail, a third ball screw, a third guide rail slider, a sample holder fixing block, a sample holder fixing sleeve, a sample holder fixing shaft, and a second sample holder. The second guide rail is positioned above the transfer chamber along the y-direction. The second guide rail slider is placed in a slot of the second guide rail and slides within the slot. The second ball screw passes through the second guide rail slider and is connected to the second stepper motor. The rotation of the second stepper motor drives the second guide rail slider to move horizontally. A fixing block is mounted on the second guide rail slider. One end of the cable chain is fixed to the cable chain fixing block, and the direction of movement is... Parallel to the second guide rail, the drag chain fixing block is installed on the groove-free surface of the third guide rail. The third guide rail is installed on the fixing block along the z-axis. The third guide rail slider is placed in the groove of the third guide rail and is in sliding engagement with the groove of the third guide rail. The third ball screw passes through the third guide rail slider and is connected to the third stepper motor. The rotation of the third stepper motor drives the third guide rail slider to move up and down. The sample holder fixing block is installed on the third guide rail slider. The sample holder fixing sleeve is vertically installed on the sample holder fixing block. One end of the sample holder fixing shaft passes through the sample holder fixing sleeve to make it parallel to the third guide rail. The other end of the sample holder fixing shaft is connected to the second sample holder. The second stepper motor and the third stepper motor cooperate to rotate, so that the second sample holder can be controllably raised, lowered and translated in the first transfer chamber, the second transfer chamber and the third transfer chamber. The second sample holder has detachable slots on its surface to support the fixing of target substrates of different sizes, and the slot spacing is adjustable. These slots are used to fix the target substrates and move them precisely up and down. The dimensions of the target substrates are: length 5-100cm, width 5-50cm, and thickness 0.1-3mm. The slot spacing is adjustable from 1 to 10mm. The second sample holder rotates at a constant speed, causing the two-dimensional material / transfer medium film to wrap around the sample holder surface where the target substrate is placed. The second sample holder retrieves different target substrates in the first, second, and third transfer chambers. The three transfer chambers are each equipped with different etching solutions, cleaning solutions, and processing times to support parallel processing of different processes. The three transfer chambers are used to prepare three multilayer composite films of transfer medium / two-dimensional material / target substrate. Alternatively, the same target substrate on the second sample holder can be retrieved from the three transfer chambers to obtain a multilayer composite film of transfer medium / two-dimensional material.

[0011] The automated, non-destructive transfer device for two-dimensional materials includes a mechanized sample delivery system comprising a fourth guide rail, a fourth ball screw, a third sample holder, a sample delivery stage, a fourth guide rail slider, and a fourth stepper motor. The fourth guide rail is positioned along the y-axis, and the fourth guide rail slider is placed in a slot on the fourth guide rail and slides within the slot. The fourth ball screw passes through the fourth guide rail slider and is connected to the fourth stepper motor. The rotation of the fourth stepper motor drives the fourth guide rail slider to move horizontally along the fourth guide rail. The sample delivery stage is fixed on the fourth guide rail slider, and the third sample holder is placed on the sample delivery stage. The side of the fourth guide rail away from the fourth stepper motor is connected to the third transfer chamber. The surface of the second sample holder is provided with detachable slots to support the fixing of target substrates of different sizes, and the slot spacing is adjustable.

[0012] An automated, non-destructive transfer method for two-dimensional materials includes the following steps: (1) Using an inkjet centrifugal film-forming system, a uniform transfer medium film with controllable thickness and area is formed on the surface of a two-dimensional material / target substrate to obtain a transfer medium / two-dimensional material / target substrate laminated composite film; (2) Using the first sample holder, the sampling stage and the second sample holder of the target matrix piston lifting stage of the mechanized sampling system, the transfer medium / two-dimensional material / target matrix laminated composite film is automatically sent into the transfer chamber of the chamber system at a constant speed of 1 to 10 mm / s without friction with the outside world. (3) The etching solution is injected into the transfer chamber through the injection nozzle of the liquid injection system. By precisely controlling the injection volume and flow rate, the parameters of the injection nozzle are adjusted to ensure that the etching solution is evenly distributed throughout the transfer process, and to avoid uneven etching that could lead to damage to the two-dimensional material. The target substrate is removed by chemical etching, so that the transfer medium / two-dimensional material is separated from the target substrate, thus avoiding local over-etching or under-etching. (4) The etching solution is quickly recovered by using the drain port of the porous drainage circulation system to prevent liquid residue from contaminating or doping the two-dimensional material. The residual liquid after circulation is used again for etching and separation of the target substrate. At the same time, deionized water is injected through the liquid injection system at a rate of 1-5 mL / s to remove the residual etching solution adsorbed on the surface of the two-dimensional material and prevent liquid residue from contaminating or doping the two-dimensional material. (5) Using the second sample holder of the target substrate piston lifting platform, the target substrate placed on the second sample holder is moved up and down precisely to retrieve the transfer medium / two-dimensional material film floating on the surface of deionized water. The speed of the lifting platform is controlled to gradually attach the transfer medium / two-dimensional material film to the target substrate in a shear-free environment to obtain a transfer medium / two-dimensional material / target substrate multilayer composite film. In addition, the sample holder is rotated at a constant speed by program control so that the two-dimensional material / transfer medium film is wrapped around the sample holder surface where the target substrate is placed, and finally a multilayer two-dimensional material / transfer medium / target substrate roll is obtained. (6) Use a porous drainage circulation system to drain deionized water, lower the target matrix piston lifting platform, and then use a liquid injection system to inject transfer medium cleaning fluid into the transfer chamber so that the transfer medium dissolves in the cleaning fluid and separates from the two-dimensional material / target matrix composite. By controlling the injection volume and speed, ensure that the transfer medium cleaning fluid is evenly distributed to avoid uneven or incomplete cleaning or excessive flow rate of the cleaning fluid during the cleaning process, which may cause damage to the two-dimensional material. Then use a porous drainage circulation system to drain the transfer medium cleaning fluid, and slowly inject deionized water again to remove the transfer medium cleaning fluid adsorbed on the surface of the two-dimensional material to prevent liquid residue from contaminating or doping the two-dimensional material. (7) Using the sample delivery stage of the mechanized sample delivery system, the second sample tray carrying the transfer medium / two-dimensional material / target matrix laminated composite film is automatically taken out of the transfer chamber at a constant speed. After the two-dimensional material and the target matrix are tightly bonded, i.e. there is no peeling phenomenon on the surface, the two-dimensional material transfer operation without damage is completed. The tight bonding between the two-dimensional material and the target matrix is ​​achieved by heat treatment. The heat treatment temperature is 25 to 220°C and the time is 5 min to 2 h.

[0013] The automated, non-destructive transfer method for two-dimensional materials, step (1) includes the following specific operation process: Ⅰ: Place the flexible two-dimensional material / target substrate on the inner wall of the rotating drum. The rotating drum drives the two-dimensional material / target substrate to rotate, so that the two-dimensional material / target substrate obtains centrifugal force due to rotation, thereby sticking tightly to the inner wall of the rotating drum and maintaining stability. The rotation speed of the rotating drum 210 is 100~1000 rpm. II: Using a nozzle or needle with an aperture of 50–300 μm, a 5–20 wt% polymethyl methacrylate, polyvinylidene fluoride, rosin, or paraffin transfer medium solution is sprayed onto the surface of a rotating two-dimensional material under constant film-forming liquid pressure. A program-controlled mechanical device is used to move the nozzle or needle horizontally along the direction of the roller's rotation axis at a speed of 0.5–10 mm / s. The distance the nozzle or needle moves is the width of the transfer medium film. Centrifugal force and shear force are used to form a uniform liquid film of the transfer medium on the surface of the two-dimensional material. III: The transfer medium liquid film is cured by an external curing device. During the curing process, the rotation state and speed of the rotating drum remain constant, i.e., the film-forming substrate is kept in a stable centrifugal force field. After curing, a uniform transfer medium layer is formed on the surface of the two-dimensional material. The curing process includes one or more of the following: nitrogen blowing, heating and drying, vacuum evaporation, and natural volatilization. Among them, heating and drying uses an external light wave tube with an orange visible light wavelength of 620-760nm, a power of 5-200W, a temperature range of 50-120℃, and a time of 5-30min; nitrogen blowing has a flow rate of 0.5-5L / min and a time of 30s-5min; vacuum evaporation has a pressure of 0.01-0.1MPa and a time of 5-20min; natural volatilization is carried out at room temperature for 10-30min. Depending on the requirements and strength limitations of the transfer medium, steps II and III may be repeated once or twice, or steps II and III may be performed once or twice after changing to other transfer medium solutions or changing film-forming parameters, in order to obtain single-layer transfer medium film materials of different thicknesses or multilayer transfer medium film materials of different compositions with a thickness of 50–500 nm; the two-dimensional materials to be transferred include graphene, black phosphorus, silicene, germanene, boron nitride, transition metal sulfides, transition metal halides or ternary materials of the MA2Z4 family grown by chemical vapor deposition; in ternary materials MA2Z4, M = transition metal, A = main group element, and Z = chalcogenide.

[0014] In the automated non-destructive transfer method for two-dimensional materials, in step (3), the etching solution injection rate is 0.1-10 mL / min, and the etching solution is one or more combinations of FeCl3 aqueous solution, NaOH aqueous solution, and dilute hydrochloric acid. The concentration of FeCl3 aqueous solution is 0.1-1 mol / L, the concentration of NaOH aqueous solution is 0.1-10 mol / L, and the concentration of dilute hydrochloric acid is 5-20 wt%. The etching solution recovery rate in step (4) is controlled to be 10-50 mL / s according to the target substrate material.

[0015] In the automated non-destructive transfer method for two-dimensional materials, in step (4), the speed of the target substrate piston lifting platform is 0.1-5 mm / s, and the target substrate includes polyethylene naphthalate, methyl methacrylate, hydroxyethyl methacrylate, polyethylene terephthalate, gallium nitride, glass, quartz, silicon wafer or sapphire.

[0016] In the automated non-destructive transfer method for two-dimensional materials, in step (6), the cleaning solution includes one or more of acetone, N-methylpyrrolidone, tetrahydrofuran or alcohol, the injection rate of the transfer medium cleaning solution is 0.2 to 2 mL / s, the recovery rate is 1 to 10 mL / s, and the speed of lowering the target substrate piston lifting platform is 1 to 20 mm / s.

[0017] The design concept of this invention is: This invention uses an inkjet centrifugal membrane fabrication system as its core, utilizing centrifugal force to ensure uniform coating of the transfer medium and solve the problem of membrane thickness control. It is supported by a fully mechanized transmission system (sampling, sample delivery, and lifting platform), avoiding mechanical damage through low-friction, high-precision transmission. The invention employs a parallel structure of three transfer chambers to achieve simultaneous processing of multiple samples or continuous preparation of multilayer membranes, increasing production capacity. Finally, a porous drainage and circulation system ensures reagent recycling and precise liquid control, reducing costs and preventing contamination.

[0018] The advantages and beneficial effects of this invention are: 1. High-precision control of transfer medium film thickness: This invention adopts inkjet centrifugal film forming technology. The constant centrifugal force of the rotating drum makes the two-dimensional material adhere tightly to the inner wall. Combined with the automated control of the printhead or needle to uniformly transfer and coat, high-precision control of the transfer medium film thickness is achieved. Moreover, since the film is formed under the centrifugal force field, the uneven thickness problem of the traditional spin coating method is greatly eliminated, and the risk of wrinkles or cracks in the material is greatly reduced.

[0019] 2. Fully automated control to avoid shear force damage: The mechanized sampling system, sample delivery system and sample holder of this invention work together to transmit or transfer samples at a constant speed, avoiding shear force damage caused by manual intervention; the flow rate and injection volume of the etching solution or cleaning solution are precisely controlled by the liquid injection system to ensure uniform distribution.

[0020] 3. The resulting two-dimensional material film is uniform, intact and clean: The target substrate lifting platform of this invention adheres to the film at a uniform speed and ultra-low speed to prevent local stress concentration, so as to achieve uniform pressure distribution and achieve damage-free transfer; the etching solution is quickly recovered by using a porous drainage circulation system, and then combined with circulation cleaning, which greatly eliminates pollution and doping.

[0021] 4. Low cost, high capacity and wide applicability to materials: This invention recycles and reuses etching or cleaning solutions through a porous drainage and circulation system, reducing reagent consumption, lowering production costs and reducing waste liquid pollution; the three transfer chambers support simultaneous processing of multiple samples or continuous retrieval of multilayer films from a single target substrate, significantly improving capacity; in addition, it supports non-destructive transfer of various two-dimensional materials such as graphene, black phosphorus, transition metal sulfides, and ternary materials, covering the mainstream two-dimensional material systems. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the structure of the automated non-destructive transfer device of the present invention.

[0023] Figure 2 This is a front view of the automated non-destructive transfer device of the present invention.

[0024] Figure 3 This is a top view of the automated, non-destructive transfer device of the present invention.

[0025] Figure 4 This is a side view of the automated non-destructive transfer device of the present invention.

[0026] Figure 5 This is a schematic diagram of the main process of the two-dimensional material non-destructive transfer method provided in the embodiments of the present invention.

[0027] Figure label: 110-160 is a mechanized sampling system, including: 110-first stepper motor, 120-first guide rail slider, 130-sampling stage, 140-first sample holder, 150-first ball screw, 160-first guide rail; 210 and 220 are inkjet centrifugal film-forming systems, including: 210 - rotating drum; 220 - printhead or needle; 310-330 is the compartment system, including: 310-first transfer compartment, 320-second transfer compartment, and 330-third transfer compartment; 410-430 is a liquid injection system, including: 410 corresponding to the first injection nozzle of the first transfer chamber 310; 420 corresponding to the second injection nozzle of the second transfer chamber 320; and 430 corresponding to the third injection nozzle of the third transfer chamber 330. 511-513, 521-523, and 531-533 constitute a porous drainage and circulation system, including: 511-513 corresponding to the first, second, and third drainage ports of the first transfer chamber 310; 521-523 corresponding to the fourth, fifth, and sixth drainage ports of the second transfer chamber 320; and 531-533 corresponding to the seventh, eighth, and ninth drainage ports of the third transfer chamber 330. 611-615, 621-626, and 631-634 are the target substrate piston lifting platform, including: 611-second stepper motor; 612-second guide rail; 613-second ball screw; 614-second guide rail slider; 615-fixing block; 621-drag chain; 622-third stepper motor; 623-drag chain fixing block; 624-third guide rail; 625-third ball screw; 626-third guide rail slider; 631-sample holder fixing block; 632-sample holder fixing sleeve; 633-sample holder fixing shaft; 634-second sample holder; 710-760 is a mechanized sample feeding system, including: 710-fourth guide rail; 720-fourth ball screw; 730-third sample holder; 740-sample feeding stage; 750-fourth guide rail slider; 760-fourth stepper motor. Detailed Implementation

[0028] like Figures 1-4 As shown, the automated non-destructive transfer device for two-dimensional materials developed in this invention includes a mechanized sampling system (110-160), an inkjet centrifugal film-forming system (210-220), a chamber system (310-330), a liquid injection system (410-430), a porous drainage and circulation system (511-513, 521-523, 531-533), a target substrate piston lifting platform (611-615, 621-626, 631-634), and a mechanized sample delivery system (710-760), etc., with the specific structure as follows: The mechanized sampling system includes a first stepper motor 110, a first guide rail slider 120, a sampling stage 130, a first sample holder 140, a first ball screw 150, and a first guide rail 160. The first stepper motor 110 drives the first guide rail slider 120 to move along the first guide rail 160 by driving the first ball screw 150, thereby realizing the horizontal transmission of the sampling stage 130. This system is used to deliver the transfer medium / two-dimensional material / target matrix laminated composite film into the chamber system at a constant speed. The inkjet centrifugal film-forming system is used to prepare transfer medium films on the surface of two-dimensional materials / target substrates. It includes a rotating drum 210 and an ink nozzle or needle 220. Centrifugal force provided by the rotating drum 210 causes the two-dimensional material to adhere tightly to the inner wall of the drum 210. The program-controlled ink nozzle or needle 220 then translates and coats the transfer medium solution. Subsequently, curing is performed by an external curing device. The chamber system includes a first transfer chamber 310, a second transfer chamber 320, and a third transfer chamber 330, arranged sequentially along the y-direction. The bottom of each of the three transfer chambers is provided with a first injection nozzle 410, a second injection nozzle 420, and a third injection nozzle 430, as well as corresponding drain ports 511-513, 521-523, and 531-533, for the injection and recovery of etching solution and cleaning solution. The liquid injection system is used to inject etching fluid and cleaning fluid into the transfer chamber. It includes a first injection nozzle 410 corresponding to the first transfer chamber 310, a second injection nozzle 420 corresponding to the second transfer chamber 320, and a third injection nozzle 430 corresponding to the third transfer chamber 330. This system is used for etching the target substrate, cleaning and removing the transfer medium, and cleaning the etched substrate and the two-dimensional material after removing the transfer medium. The liquid injection system is independently equipped with an external control system and includes a temperature control module (temperature range 15–150℃). The injection volume is adjustable from 10 to 1000 mL, and the flow rate is adjustable from 0.1 to 10 mL / min. It supports continuous / intermittent injection modes and can precisely control the injection volume and flow rate of the liquid to ensure uniform distribution of the injected liquid. The porous drainage and circulation system includes drainage ports corresponding to the first transfer chamber 310 (first drainage port 511, second drainage port 512, third drainage port 513), the second transfer chamber 320 (fourth drainage port 521, fifth drainage port 522, sixth drainage port 523), and the third transfer chamber 330 (seventh drainage port 531, eighth drainage port 532, ninth drainage port 533). The drainage ports facilitate rapid recovery of the etching solution, preventing residual liquid from contaminating or doping the two-dimensional material. The recovered liquid can be recycled. Furthermore, it is used to recover cleaning waste liquid and wastewater. It can coordinate with the liquid injection system to control the injection and recovery of the solution, thereby circulating and cleaning the two-dimensional material. A liquid level sensor (accuracy ±0.1mm) monitors the liquid level in the chamber in real time and feeds it back to the control system, dynamically adjusting the injection flow rate (error ≤0.1mL / min) and drainage speed. The recovered liquid is filtered through a filter membrane and then recycled, with a single-cycle recovery efficiency ≥95% (volume percentage). The target substrate piston lifting platform includes a second stepper motor 611, a second guide rail 612, a second ball screw 613, a second guide rail slider 614, a fixing block 615, a cable chain 621, a third stepper motor 622, a cable chain fixing block 623, a third guide rail 624, a third ball screw 625, a third guide rail slider 626, a sample holder fixing block 631, a sample holder fixing sleeve 632, a sample holder fixing shaft 633, and a second sample holder 634. The second guide rail 612 is placed above the transfer chamber along the y-direction. The second guide rail slider 614 is placed in the slot of the second guide rail 612 and is in sliding engagement with the slot of the second guide rail 612. The second ball screw 613 passes through the second guide rail slider 614 and is connected to the second stepper motor 611. The rotation of the second stepper motor 611 drives the second guide rail slider 614 to move horizontally. The fixing block 615 is installed on the second guide rail slider 614. One end of the cable chain 621 is fixed to the cable chain fixing block 623, and its movement direction is parallel to the second guide rail 612. The third guide rail 624 is mounted on the fixing block 615 along the z-axis. The third guide rail slider 626 is placed in the slot of the third guide rail 624 and is in sliding fit with the slot of the third guide rail 624. The third ball screw 625 passes through the third guide rail slider 626 and is connected to the third stepper motor 622. The rotation of the third stepper motor 622 drives the third guide rail slider 626 to move up and down. The sample holder fixing block 631 is mounted on the third guide rail slider 626. The sample holder fixing block 631 is connected to the second sample holder 634 through the sample holder fixing sleeve 632 and the sample holder fixing shaft 633. The surface of the second sample holder 634 is provided with a detachable slot to support the fixing of target substrates of different sizes (length 5-100cm, width 5-50cm, thickness 0.1-3mm). The slot spacing is adjustable (adjustment range 1-10mm) to fix the target substrate and make it move up and down precisely. The sample holder can also be controlled by the program to rotate at a constant speed so that the two-dimensional material / transfer medium film is wrapped around the sample holder surface where the target substrate is placed. The second sample holder 634 can retrieve samples from the first transfer chamber 310, the second transfer chamber 320, and the third transfer chamber 330 using different target substrates. Each of the three transfer chambers is independently equipped with an external liquid injection system control and temperature control module (temperature range 15-150℃). The etching solution type (such as FeCl3, NaOH, HCl, etc.), cleaning solution type, and processing time can be set separately, supporting parallel processing of different processes. The three transfer chambers can be used to prepare three stacked composite films of transfer medium / two-dimensional material / target substrate; or the same target substrate on the sample holder can be retrieved multiple times in the three transfer chambers to obtain a multilayer transfer medium / two-dimensional material composite film. During the preparation of multilayer films, the interlayer cleaning time is 30s-10min, and the alignment accuracy is ≤±0.1mm (x / y direction). The damaged area of ​​the two-dimensional material after transfer is less than 2%, which not only has high quality but also good consistency and is easy to scale up.

[0029] In this invention, the core function of the cable chain 621 is to extend / bend synchronously with the movement of the target base piston lifting platform, protecting internal cables (such as motor control lines, sensor signal lines, etc.). The specific process is as follows: One end (fixed end) of the cable chain 621 is fixed to the slotless surface of the third guide rail 624 (the third guide rail 624 is mounted on the fixed block 615 along the z-axis) through the cable chain fixing block 623, keeping the position stationary and providing stable support for the cable chain; the other end (follower end) of the cable chain 621 is connected to the moving part (third guide rail slider 626) of the target base piston lifting platform and moves synchronously with the moving part; during the horizontal movement phase, when the stepper motor 611 drives the guide rail slider 614 to move horizontally along the y-direction, the fixed block 615 and the third guide rail 624 move horizontally together. In the vertical motion phase, when the third stepper motor 622 drives the third guide rail slider 626 to move up and down along the z-axis, the follower end of the drag chain 621 moves up and down synchronously with the third guide rail slider 626, while the fixed end remains in a fixed position relative to the second sample holder 634. The drag chain 621 extends and retracts smoothly along the y-direction. In the vertical motion phase, when the horizontal and vertical motions occur simultaneously, the drag chain 621 combines extension and retraction with bending, always conforming to the motion trajectory. The internal cables are constrained within the drag chain 621 channel, ensuring stable signal transmission and cable lifespan.

[0030] The mechanized sample delivery system includes a fourth guide rail 710, a fourth ball screw 720, a third sample holder 730, a sample delivery stage 740, a fourth guide rail slider 750, and a fourth stepper motor 760. The fourth guide rail 710 is placed along the y-axis, and the fourth guide rail slider 750 is placed in a slot of the fourth guide rail 710 and is in sliding engagement with the slot. The fourth ball screw 720 passes through the fourth guide rail slider 750 and is connected to the fourth stepper motor 760. The rotation of the fourth stepper motor 760 drives the fourth guide rail slider 750 to move horizontally along the fourth guide rail 710. The sample delivery stage 740 is fixed on the fourth guide rail slider 750 and is used to place the sample holder 730 and carry the sample holder away from the chamber system. In addition, the fourth guide rail slider of the mechanized sampling system is made of polytetrafluoroethylene and is used with silicone-based grease, with a friction coefficient of ≤0.02; the fourth ball screw has a precision grade of C3 and a positioning error of ≤0.005mm. Through low friction and high precision transmission, the shear force during sample transmission can be significantly reduced.

[0031] The first stepper motor 110 is connected to the first ball screw 150. The first ball screw 150 passes through and is connected to the first guide rail slider 120. The first guide rail slider 120 is placed in the slot of the first guide rail 160 and is in sliding engagement with the slot of the first guide rail 160. The first guide rail 160 is placed along the y-axis. The rotation of the first stepper motor 110 can drive the first guide rail slider 120 to move horizontally along the first guide rail 160. The sampling stage 130 is fixed on the first guide rail slider 120, and the first sample holder 140 is placed on it. The rotating drum 210 is placed on the side of the first guide rail 160 near the first stepper motor 110. The rotation axis of the rotating drum 210 is parallel to the x-direction. The central axis of the ink nozzle or needle 220 is perpendicular to the inner wall of the rotating drum 210. The side of the first guide rail 160 away from the first stepper motor 110 is connected to the first transfer chamber 310. The first transfer chamber 310, the second transfer chamber 320 and the third transfer chamber 330 are arranged in a row along the y-direction. The bottom of the three chambers has a first injection nozzle 410, a second injection nozzle 420, a third injection nozzle 430 and a first drain port 511, a second drain port 512, a third drain port 513, a fourth drain port 521, a fifth drain port 522, a sixth drain port 523, a seventh drain port 531, an eighth drain port 532 and a ninth drain port 533, respectively. The second guide rail 612 is placed above the compartment system along the y-direction. The second guide rail slider 614 is placed in the slot of the second guide rail 612 and slides in cooperation with the slot. The second ball screw 613 passes through the second guide rail slider 614 and is connected to the second stepper motor 611. The rotation of the second stepper motor 611 can drive the second guide rail slider 614 to move horizontally along the second guide rail 612. A fixing block 615 is installed on the second guide rail slider 614. One end of the cable chain 621 is fixed to the cable chain fixing block 623, and its movement direction is parallel to the second guide rail 612. The third guide rail... 624 is mounted on the fixed block 615 and placed along the z-axis. The third guide rail slider 626 is placed in the slot of the third guide rail 624 and is in sliding engagement with the slot of the third guide rail 624. The third ball screw 625 passes through the third guide rail slider 626 and is connected to the third stepper motor 622. The rotation of the third stepper motor 622 can drive the third guide rail slider 626 to move up and down along the third guide rail 624. The drag chain fixing block 623 is mounted on the slotless surface of the third guide rail 624. One end of the drag chain 621 is connected to the drag chain fixing block 623. The movement direction of the drag chain 621 is parallel to the second guide rail 612.The sample holder fixing block 631 is mounted on the third guide rail slider 626, and the sample holder fixing sleeve 632 is vertically mounted on the sample holder fixing block 631. One end of the sample holder fixing shaft 633 passes through the sample holder fixing sleeve 632 to make it parallel to the third guide rail 624, and the other end of the sample holder fixing shaft 633 is connected to the second sample holder 634. The second stepper motor 611 and the third stepper motor 622 cooperate to rotate, which can controllably raise, lower and translate the second sample holder 634 in the first transfer chamber 310, the second transfer chamber 320 and the third transfer chamber 330. The fourth guide rail 710 is placed along the y-axis. The fourth guide rail slider 750 is placed in the slot of the fourth guide rail 710 and slides in contact with the slot. The fourth ball screw 720 passes through the fourth guide rail slider 750 and is connected to the fourth stepper motor 760. The rotation of the fourth stepper motor 760 can drive the fourth guide rail slider 750 to move horizontally along the fourth guide rail 710. The sample delivery stage 740 is fixed on the fourth guide rail slider 750. The third sample holder 730 can be placed on the sample delivery stage 740. The side of the fourth guide rail 710 away from the fourth stepper motor 760 is connected to the third transfer chamber 330. The surface of the second sample holder 634 is provided with a detachable slot to support the fixing of target substrates of different sizes, and the slot spacing is adjustable.

[0032] like Figures 1-5 As shown, the automated, non-destructive transfer method for two-dimensional materials of the present invention is described in detail below: (1) Utilization Figures 1-4 A two-dimensional material transfer chamber inkjet centrifugal film-forming system forms a uniform transfer medium film with controllable thickness and area on the surface of a two-dimensional material / target substrate, resulting in a transfer medium / two-dimensional material / target substrate laminated composite film. The specific process includes: Ⅰ: Place the flexible two-dimensional material / target substrate on the inner wall of the rotating drum 210. The rotating drum 210 drives the two-dimensional material / target substrate to rotate, so that the two-dimensional material / target substrate obtains centrifugal force due to rotation, thereby sticking tightly to the inner wall of the rotating drum 210 and maintaining stability. The rotation speed of the rotating drum 210 is 100~1000 rpm. II: Using a nozzle or needle 220 with an aperture of 50–300 μm, a transfer medium solution with a concentration of 5–20 wt% (e.g., polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), rosin, paraffin, etc.) is sprayed onto the surface of a rotating two-dimensional material under constant film-forming liquid pressure. A program-controlled mechanical device moves the nozzle or needle 220 horizontally along the direction of the roller's rotation axis at a speed of 0.5–10 mm / s. The distance the nozzle or needle 220 moves is the width of the transfer medium film. Centrifugal force and shear force are used to form a uniform liquid film of the transfer medium on the surface of the two-dimensional material. III: The transfer medium liquid film is cured by an external curing device. During the curing process, the rotation state and speed of the rotating drum 210 are kept constant, that is, the film-forming substrate is kept in a stable centrifugal force field. After curing, a uniform transfer medium layer (protective layer) is formed on the surface of the two-dimensional material. The curing process includes, but is not limited to, one or a combination of two or more of the following: nitrogen blowing, heating and drying, vacuum evaporation, and natural volatilization. Among them, heating and drying uses an external light wave tube with an orange visible light wavelength of 620-760nm, a power of 5-200W, a temperature range of 50-120℃, and a time of 5-30min; nitrogen blowing has a flow rate of 0.5-5L / min and a time of 30s-5min; vacuum evaporation has a pressure of 0.01-0.1MPa and a time of 5-20min; natural volatilization is carried out at room temperature (25℃) for 10-30min.

[0033] Depending on the requirements and strength limitations of the transfer medium, steps II and III may be repeated once or more, or steps II and III may be performed once or more after changing the transfer medium solution or altering the film-forming parameters, to obtain single-layer transfer medium films of varying thicknesses or multilayer transfer medium films of varying compositions with thicknesses ranging from 50 to 500 nm. The two-dimensional materials to be transferred include, but are not limited to: graphene, black phosphorus, silicene, germanene, boron nitride, transition metal sulfides, transition metal halides, and ternary materials of the MA2Z4 family (M = transition metals, such as molybdenum (Mo) and tungsten (W); A = main group elements, such as silicon (Si) and germanium (Ge); Z = chalcogens, such as nitrogen (N), phosphorus (P), and arsenic (As)).

[0034] (2) Using the first sample holder 140 and the sampling stage 130 of the mechanized sampling system and the second sample holder 634 of the target matrix piston lifting stage, the transfer medium / two-dimensional material / target matrix laminated composite film is automatically sent into the transfer chamber of the chamber system at a constant speed of 1 to 10 mm / s without friction with the outside world. (3) The etching solution is injected into the transfer chamber through the injection nozzle of the liquid injection system. By precisely controlling the injection volume and flow rate, the parameters of the injection nozzle are adjusted to ensure that the etching solution is evenly distributed throughout the transfer process, and to avoid uneven etching that could lead to damage to the two-dimensional material. The target substrate is removed by chemical etching to separate the transfer medium / two-dimensional material from the target substrate, thus avoiding local over-etching or under-etching. The etching solution injection rate is 0.1 to 10 mL / min. The etching solution is one or more of the following: FeCl3 aqueous solution (0.1 to 1 mol / L), NaOH aqueous solution (0.1 to 10 mol / L), and dilute hydrochloric acid (5 to 20 wt%). The speed of the etch solution recovery in step (4) is controlled to be 10 to 50 mL / s according to the target substrate material. (4) The etching solution is quickly recovered through the drain port of the porous drainage circulation system to prevent liquid residue from contaminating or doping the two-dimensional material. The residual liquid after circulation can be reused for etching and separation of the target substrate. At the same time, deionized water is slowly injected through the liquid injection system at a rate of 1-5 mL / s to remove residual etching solution adsorbed on the surface of the two-dimensional material and prevent liquid residue from contaminating or doping the two-dimensional material. The speed of the target substrate piston lifting stage is only 0.1-5 mm / s, which can ensure uniform pressure distribution and avoid local stress concentration. The target substrate includes, but is not limited to: polyethylene naphthalate (PEN), methyl methacrylate (PMMA), hydroxyethyl methacrylate (HEMA), polyethylene terephthalate (PET), gallium nitride (GaN), glass, quartz, silicon wafer or sapphire; (5) Using the second sample holder 634 of the target substrate piston lifting platform, the target substrate placed in the second sample holder 634 is moved up and down precisely to retrieve the transfer medium / two-dimensional material film floating on the surface of deionized water. The speed of the lifting platform is controlled to gradually attach the transfer medium / two-dimensional material film to the target substrate in a shear-free environment to obtain a transfer medium / two-dimensional material / target substrate multilayer composite film. In addition, the sample holder can be rotated at a constant speed by program control to make the two-dimensional material / transfer medium film wrap around the sample holder surface where the target substrate is placed in advance, and finally a multilayer two-dimensional material / transfer medium / target substrate roll material is obtained.

[0035] (6) Using a porous drainage circulation system, deionized water is drained, the target matrix piston lifting platform is lowered, and then the transfer medium cleaning solution is injected into the transfer chamber using a liquid injection system, so that the transfer medium dissolves in the cleaning solution and separates from the two-dimensional material / target matrix composite. By controlling the injection volume and speed, the transfer medium cleaning solution is ensured to be evenly distributed to avoid uneven or incomplete cleaning or damage to the two-dimensional material due to excessively fast flow rate of the cleaning solution during the cleaning process. Then, the transfer medium cleaning solution is drained using a porous drainage circulation system, and deionized water is slowly injected again to remove the transfer medium cleaning solution adsorbed on the surface of the two-dimensional material, preventing liquid residue from contaminating or doping the two-dimensional material. The cleaning solution used includes, but is not limited to, one or more of acetone, N-methylpyrrolidone (NMP), tetrahydrofuran (THF), or alcohol. The injection speed of the transfer medium cleaning solution is 0.2 to 2 mL / s, the recovery speed is 1 to 10 mL / s, and the speed of lowering the target matrix piston lifting platform is 1 to 20 mm / s.

[0036] (7) Using the sample delivery stage 740 of the mechanized sample delivery system, the second sample holder 634 carrying the multilayer composite film of transfer medium / two-dimensional material / target substrate is automatically removed from the transfer chamber at a constant speed. After the two-dimensional material and the target substrate are tightly bonded, i.e., there is no peeling phenomenon on the surface, the two-dimensional material transfer operation without damage is completed. The tight bonding between the two-dimensional material and the target substrate is achieved by heat treatment. The heat treatment temperature is 25-220℃ and the time is 5min-2h.

[0037] The accompanying drawings and embodiments described in this specification provide a more detailed description of specific implementations of the present invention. The following embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0038] Example 1

[0039] In this embodiment, the two-dimensional material / target substrate used is graphene / copper foil, and an aluminum alloy cylinder with an inner diameter of 200mm and a width of 150mm is used as a rotating drum. The rotation of the drum causes the graphene / copper foil to adhere to the inner wall of the aluminum alloy drum.

[0040] like Figure 5 As shown, the specific implementation process for automated, non-destructive transfer of two-dimensional materials includes the following steps: (1) Utilization Figures 1-4 An inkjet centrifugal film-forming system in an automated, non-destructive transfer apparatus forms a uniform PMMA film with controllable thickness and area on the surface of graphene / copper foil, resulting in a PMMA / graphene / copper foil composite film. The specific process includes: Ⅰ: Place the flexible graphene / copper foil on the inner wall of an aluminum alloy rotating drum with an inner diameter of 200mm and a width of 150mm. The rotating drum drives the graphene / copper foil to rotate. Set the speed to 1000rpm. The centrifugal force obtained by the rotation of the graphene / copper foil will cause it to stick tightly to the inner wall of the rotating drum and remain stable. II: Using a needle with an aperture of 180μm, under constant film-forming liquid pressure, a PMMA ethyl lactate solution (5wt%) is sprayed onto the rotating graphene surface. A program-controlled mechanical device is used to move the needle horizontally along the direction of the roller's rotation axis for coating. The nozzle speed is 3mm / s. The distance the nozzle moves is the width of the PMMA film. Centrifugal force and shear force are used to form a uniform liquid film of the transfer medium on the surface of the two-dimensional material. III: The PMMA liquid film is heated and dried by a light wave tube (wavelength 700nm, power 25w, heating at 80℃ for 15min). During the heating and drying process, the rotation state of the rotating drum is kept unchanged, that is, the graphene / copper foil is kept in a stable centrifugal force field. After curing, a uniform PMMA layer with a thickness of about 150nm is formed on the graphene surface. (2) Using the sample holder, sampling stage and target matrix piston lifting stage of the mechanized sampling system, the PMMA / graphene / copper foil composite is automatically fed into the transfer chamber of the chamber system at a constant speed of 5 mm / s without friction with the outside world. (3) Inject 0.2 mol / L FeCl3 etching solution into the transfer chamber. By precisely controlling the injection of 30 mL and the flow rate of 5 mL / min, ensure that the FeCl3 etching solution is evenly distributed throughout the transfer process. Use chemical etching to remove the Cu foil substrate and avoid local over-etching or under-etching. (4) The FeCl3 etching solution is rapidly recovered at a rate of 20 mL / s to prevent liquid residue from contaminating or doping the graphene. The recovered FeCl3 etching solution can be reused for etching copper foil. At the same time, deionized water is slowly injected at a rate of 3 mL / s to remove residual etching solution adsorbed on the graphene surface. (5) Using the sample holder of the target substrate piston lifting platform, the polyethylene terephthalate (PET) placed on the sample holder is precisely moved up and down, and the PMMA / graphene film floating on the deionized water surface is retrieved at a speed of 1 mm / s. The PMMA / graphene film is gradually bonded to the PET to obtain the PMMA / graphene / PET composite film. (6) Using the drain outlet of the porous drainage circulation system, quickly drain deionized water at a rate of 10 mL / s and lower the target substrate piston lifting platform at a rate of 5 mm / s. Then, use the liquid injection system to inject acetone cleaning solution into the transfer chamber at a rate of 1 mL / s. Take care to avoid uneven cleaning or excessive acetone flow rate during cleaning, which may cause graphene damage. Use the drain outlet of the porous drainage circulation system to drain acetone cleaning solution at a rate of 5 mL / s, and then slowly inject deionized water at a rate of 1 mL / s to remove the acetone cleaning solution adsorbed on the graphene surface, to prevent acetone residue from contaminating or doping the graphene. (7) Using a mechanized sample delivery system, the graphene / PET composite film sample holder is automatically carried out of the transfer chamber at a constant speed. Heat treatment is used to achieve a tight bond between graphene and PET for 15 minutes at 80°C, completing one non-destructive graphene transfer operation. After the above steps, the final sample obtained is a graphene / PET composite film. The integrity of the transferred graphene is 99.8%, and the alignment accuracy is ±0.03 mm. The electron mobility of the transferred graphene, measured at 25°C under vacuum, is approximately 3700 cm⁻¹. 2 •V -1 •s -1 .

[0041] Example 2

[0042] The difference from Example 1 is that the two-dimensional material / target substrate composite used in this example is molybdenum disulfide (MoS2) / sapphire, the transfer medium is rosin, the etching solution is 2 mol / L NaOH injected at a rate of 1 mL / min, the curing treatment is N2 blowing at a flow rate of 2 L / min for 1 min, the target substrate is a silicon wafer, the heat treatment temperature in step (7) is 40 °C and the time is 120 min, and the rest of the steps are the same as in Example 1.

[0043] After the above steps, the final sample obtained is a MoS2 / silicon wafer composite. Optical microscopy observation shows that the integrity of the transferred MoS2 is 98.6%, with an alignment accuracy of ±0.07 mm. The electron mobility of the transferred monolayer MoS2, measured at 25℃ under vacuum, is 59.15 cm⁻¹. 2 •V -1 •s -1 .

[0044] Example 3

[0045] The difference from Example 1 is that the two-dimensional material / target substrate used in this example is MoSi2N4 / copper, the transfer medium is paraffin and the nozzle translation speed is 1 mm / s, the etching solution is 10 wt% dilute hydrochloric acid and the flow rate is 5 mL / min, the curing treatment is vacuum evaporation, the target substrate is GaN, the transfer medium cleaning solution is N-methylpyrrolidone (NMP), the heat treatment temperature in step (7) is 50°C and the time is 1 h, and the rest of the steps are the same as in Example 1.

[0046] After the above steps, the obtained target sample is a MoSi2N4 / GaN composite. Optical microscopy observation shows that the integrity of the transferred MoSi2N4 is 98.9%, with an alignment accuracy of ±0.07 mm. The electron mobility of the transferred MoSi2N4, measured at 25℃ under vacuum, is approximately 496 cm⁻¹. 2 •V -1 •s -1 .

[0047] Example 4

[0048] The difference from Example 1 is that in this example, after a uniform PMMA layer is formed on the graphene surface in step III of the centrifugal inkjet transfer medium preparation process, the transfer medium is replaced with PVDF, and the operation process of steps II and III is repeated. The difference is that the first rotating drum speed is 1000 rpm; the speed is adjusted to 800 rpm during the second film formation. The film thicknesses of the two formations are approximately 150 nm and 180 nm, respectively, indicating that the parameter adjustment within the range is feasible. The cleaning step (6) is repeated twice, and the cleaning solutions for the transfer medium in the two formations are N-methylpyrrolidone (NMP) and alcohol, respectively. All other steps are the same as in Example 1.

[0049] Following the above steps, a PVDF / PMMA / graphene / copper foil composite was prepared. The final sample obtained after transfer was a graphene / PET composite film. Optical microscopy revealed that the integrity of the transferred graphene was 99.7%, with an alignment accuracy of ±0.05 mm. The electron mobility of the transferred graphene, measured at 25℃ under vacuum, was approximately 4400 cm⁻¹. 2 •V -1 •s -1 .

[0050] Example 5

[0051] The difference from Example 1 is that in this example, after a uniform PMMA layer is formed on the graphene surface in step III of the centrifugal inkjet transfer medium preparation process, the operation process of steps I, II and III is repeated twice to prepare three PMMA / graphene / copper foils. Using the sample holder, sampling stage and target substrate piston lifting stage of the mechanized sampling system, the three PMMA / graphene / copper foil composites are sent into the first transfer chamber 310, the second transfer chamber 320 and the third transfer chamber 330 respectively at a constant speed without friction with the outside world. In step (5), the corresponding PMMA / graphene films are retrieved with sample holders with PET, PEN and sapphire respectively. The sample retrieved by sapphire in the third transfer chamber 330 is subjected to heat treatment in step (7) at a temperature of 220°C and a treatment time of 30 min. All other steps are the same as in Example 1.

[0052] After the above steps, graphene / PET, graphene / PEN, and graphene / sapphire composites were finally obtained. Optical microscopy revealed that the integrity of the transferred graphene was above 99.5%, and the alignment accuracy was ≤ ±0.06 mm. The electron mobilities of the three graphene sheets, measured at 25℃ under vacuum, were 5400, 5500, and 5300 cm⁻¹, respectively. 2 •V -1 •s -1 .

[0053] Example 6

[0054] The difference from Example 1 is that in step (5) of this example, three PMMA / graphene films are sequentially retrieved from three different first transfer chambers 310, second transfer chamber 320 and third transfer chamber 330 using a sample holder with PET. After each retrieval, interlayer cleaning is performed, and deionized water is injected and discharged. The cleaning time is 2 minutes. All other steps are the same as in Example 1.

[0055] After the above steps, a composite film with a structure of graphene / graphene / graphene / PET was finally obtained. Optical microscopy revealed that the integrity of the transferred graphene was 98.6%, with an alignment accuracy of ±0.07 mm. The electron mobilities of the graphene, measured at 25℃ under vacuum, were approximately 3200, 3300, and 3400 cm⁻¹, respectively. 2 •V -1 •s -1 .

[0056] Example 7

[0057] The difference from Example 1 is that the roller rotation speed was set to 100 rpm (lower limit) and 1000 rpm (upper limit), respectively. Nozzle parameters: orifice diameter was set to 50 μm (lower limit) and 300 μm (upper limit); translation speed was set to 0.5 mm / s (lower limit) and 10 mm / s (upper limit), respectively. Liquid flow rate: etching solution injection rate was set to 0.1 mL / min (lower limit) and 10 mL / min (upper limit); drainage rate was set to 10 mL / s (lower limit) and 50 mL / s (upper limit), respectively; platform speed was set to 0.1 mm / s (lower limit) and 5 mm / s (upper limit), respectively. Two complete independent film-forming processes were performed, each using the upper and lower limits of the main parameters. All other steps were the same as in Example 1.

[0058] After the above steps, two composite films with a graphene / PET structure were finally obtained. Optical microscopy revealed that the integrity of the transferred graphene was 98.3% and 99.5%, respectively, with alignment accuracy ≤ ±0.08 mm. The electron mobilities of the graphene, measured at 25℃ under vacuum, were approximately 2500 and 2900 cm⁻¹, respectively. 2 •V -1 •s -1 .

[0059] The results show that this invention employs a combined structure of an inkjet centrifugal film-forming system, a mechanized sampling system, a chamber system, a liquid injection system, a porous drainage and circulation system, a target substrate piston lifting platform, and a mechanized sample delivery system. Its core is the formation of a uniform transfer medium film with controllable thickness through rotary centrifugation technology. Combined with fully mechanized sample transport and precise liquid control, it achieves damage-free transfer of two-dimensional materials, significantly reducing the impact of shear force on the material and effectively avoiding breakage and contamination. This device improves transfer efficiency through automation, enabling stable transfer of large-area two-dimensional materials and supporting the continuous preparation of multilayer films, making it suitable for large-scale industrial production.

Claims

1. An automated non-invasive transfer device of two-dimensional materials, characterized in that, The device comprises a mechanized sampling system, an inkjet centrifugal membrane preparation system, a cabin system, a liquid injection system, a multi-hole drainage circulation system, a target substrate piston lifting platform, and a mechanized sample feeding system, and has the following specific structure: The three transfer cabins of the cabin system are linearly arranged along the y-axis direction, the inner cavity bottom of each transfer cabin is provided with an injection nozzle of the liquid injection system and a drainage port of the multi-hole drainage circulation system, and the target substrate piston lifting platform is cross-mounted above the cabin system; The mechanized sampling system is located at the input end of the cabin system, the first guide rail of the mechanized sampling system is laid along the y-axis, the first guide rail is provided with a first guide rail slider and a sampling table, one end of the first guide rail is connected to the first transfer cabin of the cabin system, the inkjet centrifugal membrane preparation system is located on one side of the mechanized sampling system, the sampling table of the mechanized sampling system corresponds to the rotating drum of the inkjet centrifugal membrane preparation system, the first stepper motor drives the first ball screw to drive the first guide rail slider to move horizontally along the first guide rail, thereby realizing the horizontal transmission of the sampling table and feeding the transfer medium / two-dimensional material / target substrate laminated composite film into the first transfer cabin of the cabin system at a constant speed; The mechanized sample feeding system is located at the output end of the output end of the cabin system, the fourth guide rail of the mechanized sample feeding system is laid along the y-axis, the fourth guide rail is provided with a fourth guide rail slider and a sample feeding table, one end of the fourth guide rail is connected to the third transfer cabin of the cabin system, the fourth stepper motor drives the fourth ball screw to drive the fourth guide rail slider to move horizontally along the fourth guide rail, thereby realizing the horizontal transmission of the sample feeding table and taking the sample carrier away from the cabin system.

2. The automated non-destructive transfer of two-dimensional materials apparatus of claim 1, wherein, The mechanized sampling system comprises a first stepper motor, a first guide rail slider, a sampling table, a first sample carrier, a first ball screw, and a first guide rail, the inkjet centrifugal membrane preparation system is used for preparing a transfer medium film on the surface of a two-dimensional material / target substrate, and comprises a rotating drum and a nozzle or needle, the centrifugal force provided by the rotating drum makes the two-dimensional material adhere to the inner wall of the rotating drum, and the nozzle or needle controlled by a program translates to coat the transfer medium solution; the first stepper motor is connected to the first ball screw, the first ball screw passes through the first guide rail slider and is connected thereto, the first guide rail slider is placed in the clamping groove of the first guide rail and is in sliding fit with the clamping groove of the first guide rail, the first guide rail is placed along the y-axis, and the rotation of the first stepper motor drives the first guide rail slider to move horizontally along the first guide rail; the sampling table is fixed on the first guide rail slider, the first sample carrier is placed on the sampling table, the rotating drum is placed on one side of the first guide rail close to the first stepper motor, the rotating shaft of the rotating drum is parallel to the x direction, the central axis of the nozzle or needle is perpendicular to the inner wall of the rotating drum, and the side of the first guide rail away from the first stepper motor is connected to the first transfer cabin.

3. The automated non-destructive transfer of two-dimensional materials apparatus of claim 1, wherein, The chamber system comprises a first transfer chamber, a second transfer chamber and a third transfer chamber arranged in sequence along the y direction; the liquid injection system comprises a first injection nozzle corresponding to the first transfer chamber, a second injection nozzle corresponding to the second transfer chamber and a third injection nozzle corresponding to the third transfer chamber; the multi-hole liquid discharge circulation system comprises a first liquid discharge port, a second liquid discharge port and a third liquid discharge port corresponding to the first transfer chamber, a fourth liquid discharge port, a fifth liquid discharge port and a sixth liquid discharge port corresponding to the second transfer chamber, and a seventh liquid discharge port, an eighth liquid discharge port and a ninth liquid discharge port corresponding to the third transfer chamber; The liquid injection system is used for etching the target substrate, removing the transfer medium and cleaning the two-dimensional material after etching the substrate and removing the transfer medium. The liquid injection system comprises a temperature control module with a temperature range of 15-150 DEG C, an injection amount adjustment range of 10-1000 mL, a flow rate adjustment range of 0.1-10 mL / min, supports continuous or intermittent injection mode, can accurately control the injection amount and flow rate of the liquid, and ensures uniform distribution of the injected liquid; the multi-hole liquid discharge circulation system is used for recycling the cleaning waste liquid and waste water, can cooperatively control the injection and recovery of the solution with the liquid injection system, and then performs cyclic cleaning on the two-dimensional material, monitors the liquid height in the chamber in real time through a liquid level sensor, dynamically adjusts the injection flow rate and the liquid discharge speed, and recycles the filtered liquid for reuse.

4. The automated non-destructive transfer of two-dimensional materials apparatus of claim 1, wherein, The target substrate piston lifting platform comprises a second stepper motor, a second guide rail, a second ball screw, a second guide rail sliding block, a fixed block, a drag chain, a third stepper motor, a drag chain fixed block, a third guide rail, a third ball screw, a third guide rail sliding block, a sample holder fixing block, a sample holder fixing sleeve, a sample holder fixing shaft and a second sample holder. The second guide rail is placed above the transfer chamber along the y direction. The second guide rail sliding block is placed in the clamping groove of the second guide rail and is in sliding fit with the clamping groove of the second guide rail. The second ball screw is connected with the second stepper motor through the second guide rail sliding block. The second stepper motor rotates to drive the horizontal movement of the second guide rail sliding block. The fixed block is installed on the second guide rail sliding block. One end of the drag chain is fixed on the drag chain fixed block, and the movement direction is parallel to the second guide rail. The drag chain fixed block is installed on the clamping groove-free surface of the third guide rail. The third guide rail is installed on the fixed block along the z axis. The third guide rail sliding block is placed in the clamping groove of the third guide rail and is in sliding fit with the clamping groove of the third guide rail. The third ball screw is connected with the third stepper motor through the third guide rail sliding block. The third stepper motor rotates to drive the up-down movement of the third guide rail sliding block. The sample holder fixing block is installed on the third guide rail sliding block. The sample holder fixing sleeve is installed vertically on the sample holder fixing block. The sample holder fixing shaft passes through the sample holder fixing sleeve to make it parallel to the third guide rail. The other end of the sample holder fixing shaft is connected with the second sample holder. The second stepper motor and the third stepper motor rotate in cooperation to make the second sample holder controllably lift and translate in the first transfer chamber, the second transfer chamber and the third transfer chamber. The second sample holder is provided with detachable clamping grooves, which support fixation of target substrates of different sizes and the spacing of the clamping grooves is adjustable. The target substrate has a size of 5-100 cm in length, 5-50 cm in width, and 0.1-3 mm in thickness, and the spacing of the clamping grooves is adjustable in a range of 1-10 mm. The second sample holder rotates at a constant speed, so that the two-dimensional material / transfer medium film is wound on the surface of the sample holder on which the target substrate is placed in advance. The second sample holder is used to pick up different target substrates in the first transfer cabin, the second transfer cabin, and the third transfer cabin, respectively. The three transfer cabins are provided with etching liquid types, cleaning liquid types, and processing times, respectively, to support parallel processing of different processes. The three transfer cabins are used to prepare three transfer medium / two-dimensional material / target substrate laminated composite films. Alternatively, the same target substrate on the second sample holder is used to pick up in the three transfer cabins, respectively, to obtain a multi-layer transfer medium / two-dimensional material composite film.

5. The automated non-destructive transfer of two-dimensional materials apparatus of claim 1, wherein, The mechanized sample feeding system comprises a fourth guide rail, a fourth ball screw, a third sample holder, a sample feeding table, a fourth guide rail slider, and a fourth stepper motor. The fourth guide rail is placed along the y-axis. The fourth guide rail slider is placed in the clamping groove of the fourth guide rail and is in sliding cooperation with the clamping groove of the fourth guide rail. The fourth ball screw is connected with the fourth stepper motor through the fourth guide rail slider. The fourth stepper motor rotates to drive the fourth guide rail slider to move horizontally along the fourth guide rail. The sample feeding table is fixed on the fourth guide rail slider. The third sample holder is placed on the sample feeding table. The side of the fourth guide rail away from the fourth stepper motor is connected with the third transfer cabin. The surface of the second sample holder is provided with detachable clamping grooves, which support fixation of target substrates of different sizes and the spacing of the clamping grooves is adjustable.

6. An automated non-invasive transfer method of two-dimensional materials using the apparatus of any one of claims 1 to 5, characterized in that, The method comprises the following steps: (1) A uniform transfer medium film with controllable thickness and area is formed on the surface of the two-dimensional material / target substrate by using the inkjet centrifugal film forming system, and a transfer medium / two-dimensional material / target substrate laminated composite film is obtained. (2) The transfer medium / two-dimensional material / target substrate laminated composite film is automatically fed into the transfer cabin of the cabin system at a constant speed of 1-10 mm / s by using the first sample holder, the sample feeding table, and the second sample holder of the target substrate piston lifting table under the premise of no friction with the outside world. (3) The injection nozzle of the liquid injection system is used to inject etching liquid into the transfer cabin. By accurately controlling the injection amount and flow rate and adjusting the parameters of the injection nozzle, it is ensured that the etching liquid is uniformly distributed during the entire transfer process, and damage to the two-dimensional material caused by uneven etching is avoided. The target substrate is removed by using the chemical etching method, so that the transfer medium / two-dimensional material is separated from the target substrate, and local over-etching or under-etching is avoided. (4) The etching liquid is quickly recovered by using the drainage port of the multi-hole drainage circulation system to prevent liquid residues from causing pollution or doping to the two-dimensional material. The residual liquid after circulation is used again for etching and separation of the target substrate. At the same time, deionized water is injected by using the liquid injection system at a speed of 1-5 mL / s to remove the residual etching liquid adsorbed on the surface of the two-dimensional material and prevent liquid residues from causing pollution or doping to the two-dimensional material. (5) The second sample holder of the target substrate piston lifting platform is used to realize the accurate up-down movement of the target substrate pre-placed on the second sample holder, to fish the transfer medium / two-dimensional material film floating on the surface of deionized water, to control the lifting platform speed, and to gradually paste the transfer medium / two-dimensional material film on the target substrate in a shear-free environment, so as to obtain a transfer medium / two-dimensional material / target substrate laminated film; In addition, the sample holder is controlled to rotate at a constant speed through a program, so that the two-dimensional material / transfer medium film is wound on the surface of the sample holder pre-placed with the target substrate, and finally a multi-layer two-dimensional material / transfer medium / target substrate roll is obtained; (6) The deionized water is discharged by using the multi-hole liquid discharge circulation system, the target substrate piston lifting platform is lowered, and then the transfer medium cleaning liquid is injected into the transfer cabin by using the liquid injection system, so that the transfer medium is dissolved in the cleaning liquid and separated from the two-dimensional material / target substrate composite; by controlling the injection amount and speed, the uniform distribution of the transfer medium cleaning liquid is ensured, and the non-uniform and incomplete cleaning or the too fast flow rate of the cleaning liquid in the cleaning process is avoided to cause damage to the two-dimensional material; then the transfer medium cleaning liquid is discharged by using the multi-hole liquid discharge circulation system, and the deionized water is slowly injected again to remove the transfer medium cleaning liquid adsorbed on the surface of the two-dimensional material, so as to prevent liquid residue from causing pollution or doping to the two-dimensional material; (7) The sample feeding platform of the mechanized sample feeding system automatically takes the second sample holder carrying the transfer medium / two-dimensional material / target substrate laminated film out of the transfer cabin at a constant speed, and the two-dimensional material and the target substrate are combined tightly, that is, there is no peeling phenomenon on the appearance, so that the two-dimensional material damage-free transfer operation is completed; the tight combination between the two-dimensional material and the target substrate is realized through heat treatment, the heat treatment temperature is 25-220℃, and the heat treatment time is 5min-2h.

7. The automated, non-destructive transfer method of two-dimensional materials according to claim 6, wherein, The specific operation process of step (1) includes: I: The flexible two-dimensional material / target substrate is placed on the inner wall of the rotating drum, the two-dimensional material / target substrate is rotated by the rotating drum, the centrifugal force obtained by the two-dimensional material / target substrate due to rotation is used to tightly adhere to the inner wall of the rotating drum and keep stable, and the rotating speed of the rotating drum 210 is 100-1000rpm; II: A nozzle or needle with a pore size of 50-300μm is used to spray a polymethyl methacrylate, polyvinylidene fluoride, rosin or paraffin transfer medium solution with a concentration of 5-20wt% to the surface of the rotating two-dimensional material under the condition of constant film-forming liquid pressure, a mechanical device controlled by a program is used to translate the nozzle or needle in the horizontal direction of the drum rotation axis, and the speed is 0.5-10mm / s; the translation distance of the nozzle or needle is the width of the transfer medium film, and the centrifugal force and shear force are used to form a uniform liquid film of the transfer medium on the surface of the two-dimensional material; III: solidifying the liquid film of the transfer medium by an external solidifying device, keeping the rotation state and speed of the rotating roller unchanged during the solidifying process, i.e. keeping the film-forming substrate in a stable centrifugal field, and forming a uniform transfer medium layer on the surface of the two-dimensional material after the solidifying is completed, the solidifying process including one or more than two combinations of nitrogen blowing, heating and drying, reduced pressure evaporation, and natural volatilization; wherein the heating and drying uses an external light wave tube, the external light wave tube uses orange visible light with a wavelength of 620-760 nm, a power of 5-200 W, a temperature range of 50-120℃, and a time of 5-30 min; the nitrogen blowing has a flow rate of 0.5-5 L / min and a time of 30 s-5 min; the reduced pressure evaporation has a pressure of 0.01-0.1 MPa and a time of 5-20 min; and the natural volatilization has an ambient temperature of room temperature and a time of 10-30 min; According to the use requirements and intensity limitations of the transfer medium, the operation processes of steps II and III are repeated one or more than two times, or other transfer medium solutions are replaced or the film-forming parameters are changed, and the operation processes of steps II and III are executed one or more than two times to obtain a single-layer transfer medium film material with a thickness of 50-500 nm or a multi-layer transfer medium film material with different components; the two-dimensional material to be transferred includes graphene, black phosphorus, silicene, germanene, boron nitride, transition metal sulfide, transition metal halide, or ternary material MA2Z4 family; in the ternary material MA2Z4, M=transition metal, A=main group element, and Z=sulfur family element.

8. The automated, non-destructive transfer method of two-dimensional materials according to claim 6, wherein, In step (3), the etching liquid injection speed is 0.1-10 mL / min, the etching liquid is one or more than two combinations of FeCl3 aqueous solution, NaOH aqueous solution, and dilute hydrochloric acid, the concentration of the FeCl3 aqueous solution is 0.1-1 mol / L, the concentration of the NaOH aqueous solution is 0.1-10 mol / L, and the concentration of the dilute hydrochloric acid is 5-20 wt%, and the speed of the recovered etching liquid in step (4) is controlled according to the target substrate material.

9. The automated, non-destructive transfer method of two-dimensional materials according to claim 6, wherein, In step (4), the speed of the target substrate piston lifting platform is 0.1-5 mm / s, and the target substrate includes polyethylene naphthalate, methyl methacrylate, hydroxyethyl methacrylate, polyethylene terephthalate, gallium nitride, glass, quartz, silicon wafer, or sapphire.

10. The automated, non-destructive transfer method of two-dimensional materials according to claim 6, wherein, In step (6), the cleaning liquid includes one or more than two of acetone, N-methyl pyrrolidone, tetrahydrofuran, or alcohol, the injection speed of the transfer medium cleaning liquid is 0.2-2 mL / s, the recovery speed is 1-10 mL / s, and the speed of the target substrate piston lifting platform is reduced by 1-20 mm / s.

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