Mxene phase titanium carbide film synthesis device and mxene phase titanium carbide film synthesis method with the device

Abstract

The present invention relates to a device (1) for synthesizing MXene phase titanium carbide films and to a method (100) for synthesizing MXene phase titanium carbide films using the device (1).

Description

[0001] MXENE PHASE TITANIUM CARBIDE FILM SYNTHESIS DEVICE AND MXENE PHASE TITANIUM CARBIDE FILM SYNTHESIS METHOD

[0002] WITH THE DEVICE

[0003] Technical Field

[0004] The present invention relates to a device for synthesizing MXene phase titanium carbide films and to a method for synthesizing MXene phase titanium carbide films using the device.

[0005] Background of the Invention

[0006] MXenes are a class of two-dimensional inorganic compounds composed of atomically thin layers of transition metal nitrates, carbides or carbonitrides. Due to their atomic arrangement and two-dimensional nature, these compounds exhibit special properties that are not found in bulk materials. Typically, these materials are synthesized from MAX phases by a top-down selective etching approach, which results in the addition of many unwanted radical compounds to the produced MXene films. Conventionally, MXene phase titanium carbide has been synthesized by a hydrogen fluoride acid etching in which the MAX phase has the formula Ti3AlC2, and the acid selectively attacks the aluminium layers. The dissolved aluminium layer leaves an accordion-like structure due to the MAX phase, which typically consists of repeating layers. During the process of separating MXene titanium carbide layers during high temperature or additional operations, it was found that the MXene phase titanium carbide layers obtained by using the above-mentioned method were small in area and contained a significant amount of defects due to the acid treatment. For this reason, in order to overcome the above-mentioned shortcomings, there is a need for a novel device and method for growing MXene phase titanium carbide films with high electrical conductivity, good coating and low defects and contamination.

[0007] The Chinese patent document no. CN115938818, an application included in the state of the art, discloses a preparation method of a high- volumetric- specificcapacitance flexible nitrogen-doped titanium carbide MXene film electrode. The method comprises the steps of: firstly, selectively etching an Al layer in TFAICT. processing to obtain a single-layer or few-layer TrTA nanosheet colloidal solution, adding the colloidal solution into absolute ethyl alcohol, and centrifuging to obtain a TisC2 precipitate; adding the mixture into an ethanol solution containing urea; transferring the mixed solution into a polytetrafluoroethylene lining for sealing, reacting in an air dry oven to obtain nitrogen-doped TisC2 precipitate, namely N-Ti3C2, adding deionized water into the precipitate for ultrasonic treatment, and performing vacuum suction filtration and natural air drying on an N-TisC2 colloidal solution to obtain a flexible self-supporting nitrogen-doped TisC2film; the synthesis process is simple and easy to operate, and the prepared flexible self-supporting nitrogen-doped TisC2 thin film electrode has ultrahigh volumetric specific capacitance, can be used for flexible and miniature supercapacitors, and has good application prospects in the field of energy storage.

[0008] Summary of the Invention

[0009] An object of the present invention is to realize a device for synthesizing MXene phase titanium carbide films and a method for synthesizing MXene phase titanium carbide films using the device.

[0010] Another object of the present invention is to enable the obtained titanium carbide to be used in applications such as transparent conductors, sensors, supercapacitors, radar absorbing materials, energy storage, and electromagnetic interference shields.

[0011] A further object of the present invention is to deposit MXene-type titanium carbide on a substrate and to improve the quality of the deposited films.

[0012] Detailed Description of the Invention

[0013] “Mxene Phase Titanium Carbide Film Synthesis Device and Mxene Phase Titanium Carbide Film Synthesis Method With The Device” realized to fulfil the objectives of the present invention is shown in the figures attached, in which:

[0014] Figure 1 is a drawing of the inventive device.

[0015] Figure 2 is a view of the flow chart of the inventive method.

[0016] The components illustrated in the figures are individually numbered, where the numbers refer to the following:

[0017] 1. Device

[0018] 2. Reaction chamber

[0019] 3. Plasma source

[0020] 4. First gas inlet

[0021] 5. Second gas inlet

[0022] 6. Controller

[0023] A. Substrate support

[0024] B . Plasma electrode plate

[0025] C. Metallic mesh

[0026] X. RF generator

[0027] Y. Substrate The inventive device (1) for depositing a titanium carbide film in the MXene phase on a substrate comprises a reaction chamber (2) which comprises a substrate support (A) for heating and supporting the substrate (Y); a remote plasma source (3) which is connected to the reaction chamber (2) and the RF generator (X), and is configured to generate a plasma inside the device but outside the reaction chamber (2); a first gas inlet (4) which is connected to the reaction chamber (2) and enables the plasma gas (source gas) used for plasma generation between the plasma electrode plate (B) positioned at the upper parts of the substrate support (A) in the reaction chamber (2) and the metallic mesh (C), an electrode used for generating plasma, to be carried; a second gas inlet (5) which is connected to the reaction chamber (2) and enables the titanium-containing precursor to be carried into the reaction chamber (2); and at least one controller (6) which controls the processes of flowing one or more titanium-containing precursors into the substrate (Y), flowing a source gas into a remote plasma source, partially or completely decomposing the carbon-containing precursor in the source gas and forming hydrogen radicals with a part of the hydrogen source gas mixture, flowing the formed species into the substrate (Y) and forming a MXene phase titanium carbide film by reacting with the titanium-containing precursor in the substrate (Y), regulating the flow rates of the source gas and titanium-containing precursors, regulating the temperature of the reaction chamber, the plasma power and the pressure of the chamber.

[0028] 100. Method

[0029] The inventive method (100) for depositing MXene phase titanium carbide on a substrate comprises the steps of: heating the reaction chamber (2) by vacuumization (101); forming a plasma by introducing hydrogen into the first gas inlet (4) (102); performing, during step (102), a short injection of titanium-containing precursor from the second gas inlet (5) into the reaction chamber (2) (103); purging the reaction chamber (2) with an inert gas by shutting off the hydrogen flow (104); forming a plasma by introducing the plasma gas, a carbon-containing precursor with hydrogen or without hydrogen, into the first gas inlet (4) (105); obtaining the MXene phase titanium carbide film deposited substrate by the reaction of carbon- and titanium-containing precursors on the substrate (Y) on the substrate support (A) (106); purging the reaction chamber (2) with an inert gas by shutting off the flows of carbon-containing precursor and hydrogen (if any) (107); repeating steps (102) to (107) several times (108); and applying heat treatment to the MXene titanium carbide film deposited substrate (109).

[0030] At the step of heating the reaction chamber (2) by vacuumization (101) of the inventive method (100), the reaction chamber (2) is heated to a temperature above 450°C by being vacuumized with a vacuum pump.

[0031] At the step of forming a plasma by introducing hydrogen into the first gas inlet (4) (102) of the inventive method (100), the hydrogen proceeds at a constant flow rate from the first gas inlet (4) to the plasma electrode plate (B) over a certain period of time. A plasma is ignited between the plasma electrode plate (B) and the metallic mesh (C) once the flow starts. Hydrogen continues its flow into the reaction chamber (2) through the perforated metal mesh, where the radicals produced by hydrogen and plasma can react with the substrate (Y).

[0032] At the step of introducing the titanium-containing precursor into the second gas inlet (5) (103) of the inventive method (100), titanium IV chloride (TiCU) is introduced into the second gas inlet (5) as a titanium-containing precursor. TiCU forms different intermediate complexes by reacting with the substrate (Y) with hydrogen and its radicals.

[0033] At the step of purging the reaction chamber (2) with an inert gas by shutting off the hydrogen flow (104) of the inventive method (100), the remote plasma source

[0034] (3) is switched off and the reaction chamber is purged by being exposed to an inert gas flow for a few seconds.

[0035] At the step of forming a plasma by introducing the plasma gas, a carbon- containing precursor with hydrogen or without hydrogen, into the first gas inlet

[0036] (4) (105) of the inventive method (100), the used precursor may only contain carbon or consist of a mixture of hydrogen and carbon. In one embodiment of the invention, methane (CH4) and / or CH4+H2 is used as a carbon- and / or hydrogencontaining precursor. This mixture passes at a constant flow rate from the first gas inlet (4) through the plasma electrode plate (B). A plasma is ignited between the plasma electrode plate (B) and the metallic mesh (C) once the flow starts. The plasma causes the decomposition of part of the CH4 flow, which produces species such as CH3 + H+veya CH2 + H2 veya CH + H2 + H+veya C + 2H2. The plasma also generates H+ radicals from hydrogen decomposition. This mixture of CH4 and H2 and the decomposition species thereof continues their flow into the reaction chamber through the perforated metal mesh (C). There, some species can react directly with the substrate and / or with the intermediate complexes formed in step (103).

[0037] At the step of obtaining the MXene phase titanium carbide film deposited substrate by the reaction of carbon- and titanium-containing precursors on the substrate (Y) on the substrate support (A) (106) of the inventive method (100), the substrate (Y), any one of monocrystalline silicon, silica glass, aluminium oxide or titanium oxide, on which the MXene phase titanium carbide film is intended to be deposited, is placed on the substrate support (A). The plasma radicals obtained in step (105) and the intermediate complexes obtained in step (103) react on the substrate (Y) and the crude MXene phase titanium carbide film deposited substrate is obtained.

[0038] At the step of purging the reaction chamber (2) with an inert gas by shutting off the flows of carbon-containing precursor and hydrogen (if any) (107) of the inventive method (100), the remote plasma source (3) is switched off and the reaction chamber is purged by being exposed to an inert gas flow for a few seconds.

[0039] At the step of repeating steps (102) to (107) several times (108) of the inventive method (100), the observable MXene titanium carbide film deposited substrate is obtained by repeating steps (102), (103), (104), (105), (106) and (107).

[0040] At the step of applying heat treatment to the MXene titanium carbide film deposited substrate (109) of the inventive method (100), a heat treatment is applied to the MXene titanium carbide film deposited substrate in order to increase the film quality in terms of conductivity, to reduce or completely remove the chlorine and / or hydroxyl groups remaining from the deposited films, and to increase the film crystallinity by means of the device (1). The heat treatment temperature is above 450°C. The heat treatment can be carried out under high vacuum, under an atmosphere consisting of hydrogen gas or under an atmosphere consisting of a mixture of hydrogen and an inert gas.

[0041] With the MXene titanium carbide film deposited substrate obtained by the inventive method (100), many properties such as high- volume capacity, high electrical conductivity, high plane mechanical strength and high flexibility are obtained. These properties enable MXene titanium carbide to be used in applications such as energy storage, supercapacitors, transparent conductors, sensors, electromagnetic interference prevention coatings and composite materials. Within these basic concepts; it is possible to develop various embodiments of the inventive “Mxene Phase Titanium Carbide Film Synthesis Device (1) and Mxene Phase Titanium Carbide Film Synthesis Method (100) With the Device (1)”; the invention cannot be limited to examples disclosed herein and it is essentially according to claims.

Claims

CLAIMS1. A device (1) for depositing a titanium carbide film in the MXene phase on a substrate; characterized in that it comprises a reaction chamber (2) which comprises a substrate support (A) for heating and supporting the substrate (Y); a remote plasma source (3) which is connected to the reaction chamber (2) and the RF generator (X), and is configured to generate a plasma inside the device but outside the reaction chamber (2); a first gas inlet (4) which is connected to the reaction chamber (2) and enables the plasma gas (source gas) used for plasma generation between the plasma electrode plate (B) positioned at the upper parts of the substrate support (A) in the reaction chamber (2) and the metallic mesh (C), an electrode used for generating plasma, to be carried; a second gas inlet (5) which is connected to the reaction chamber (2) and enables the titanium-containing precursor to be carried into the reaction chamber (2); and at least one controller (6) which controls the processes of flowing one or more titanium-containing precursors into the substrate (Y), flowing a source gas into a remote plasma source, partially or completely decomposing the carbon-containing precursor in the source gas and forming hydrogen radicals with a part of the hydrogen source gas mixture, flowing the formed species into the substrate (Y) and forming a MXene phase titanium carbide film by reacting with the titanium-containing precursor in the substrate (Y), regulating the flow rates of the source gas and titanium-containing precursors, regulating the temperature of the reaction chamber, the plasma power and the pressure of the chamber.

2. A method (100) for depositing MXene phase titanium carbide on a substrate; characterized in that it comprises the steps of: heating the reaction chamber (2) by vacuumization (101);forming a plasma by introducing hydrogen into the first gas inlet (4) (102); performing, during step (102), a short injection of titanium-containing precursor from the second gas inlet (5) into the reaction chamber (2) (103); purging the reaction chamber (2) with an inert gas by shutting off the hydrogen flow (104); forming a plasma by introducing the plasma gas, a carbon-containing precursor with hydrogen or without hydrogen, into the first gas inlet (4) (105); obtaining the MXene phase titanium carbide film deposited substrate by the reaction of carbon- and titanium-containing precursors on the substrate (Y) on the substrate support (A) (106); purging the reaction chamber (2) with an inert gas by shutting off the flows of carbon-containing precursor and hydrogen (if any) (107); repeating steps (102) to (107) several times (108); and applying heat treatment to the MXene titanium carbide film deposited substrate (109).

3. A method (100) according to Claim 2; characterized in that at the step of heating the reaction chamber (2) by vacuumization (101), the reaction chamber (2) is heated to a temperature above 450°C by being vacuumized with a vacuum pump.

4. A method (100) according to Claim 2; characterized in that at the step of forming a plasma by introducing hydrogen into the first gas inlet (4) (102), the hydrogen proceeds at a constant flow rate from the first gas inlet (4) to the plasma electrode plate (B) over a certain period of time; a plasma is ignited between the plasma electrode plate (B) and the metallic mesh (C) once the flow starts; hydrogen continues its flow into the reaction chamber (2) through the perforated metal mesh, where the radicals produced by hydrogen and plasma can react with the substrate (Y).

5. A method (100) according to Claim 2; characterized in that at the step of introducing the titanium-containing precursor into the second gas inlet (5) (103), titanium IV chloride (TiCU) is introduced into the second gas inlet (5) as a titanium-containing precursor and TiCU forms different intermediate complexes by reacting with the substrate (Y) with hydrogen and its radicals.

6. A method (100) according to Claim 2; characterized in that at the step of purging the reaction chamber (2) with an inert gas by shutting off the hydrogen flow (104), the remote plasma source (3) is switched off and the reaction chamber is purged by being exposed to an inert gas flow for a few seconds.

7. A method (100) according to Claim 2; characterized in that at the step of forming a plasma by introducing the plasma gas, a carbon-containing precursor with hydrogen or without hydrogen, into the first gas inlet (4) (105), the used precursor may only contain carbon or consist of a mixture of hydrogen and carbon.

8. A method (100) according to Claim 7; characterized in that in one embodiment of the invention, methane (CH4) and / or CH4+H2 is used as a carbon- and / or hydrogen-containing precursor.

9. A method (100) according to Claim 7; characterized in that the mixture passes at a constant flow rate from the first gas inlet (4) through the plasma electrode plate (B); a plasma is ignited between the plasma electrode plate (B) and the metallic mesh (C) once the flow starts; and the plasma causes the decomposition of part of the CH4 flow, which produces species such as CH3 + H+veya CH2 + H2 veya CH + H2 + H+veya C + 2H2.

10. A method (100) according to Claim 7; characterized in that the plasma generates H+ radicals from hydrogen decomposition; the mixture of CH4 and H2 and the decomposition species thereof continues their flow into the reactionchamber through the perforated metal mesh (C); and some species react directly with the substrate and / or with the intermediate complexes formed in step (103).

11. A method (100) according to Claim 2; characterized in that at the step of obtaining the MXene phase titanium carbide film deposited substrate by the reaction of carbon- and titanium-containing precursors on the substrate (Y) on the substrate support (A) (106), the substrate (Y), any one of monocrystalline silicon, silica glass, aluminium oxide or titanium oxide, on which the MXene phase titanium carbide film is intended to be deposited, is placed on the substrate support (A); the plasma radicals obtained in step (105) and the intermediate complexes obtained in step (103) react on the substrate (Y) and the crude MXene phase titanium carbide film deposited substrate is obtained.

12. A method (100) according to Claim 2; characterized in that at the step of purging the reaction chamber (2) with an inert gas by shutting off the flows of carbon-containing precursor and hydrogen (if any) (107), the remote plasma source (3) is switched off and the reaction chamber is purged by being exposed to an inert gas flow for a few seconds.

13. A method (100) according to Claim 2; characterized in that at the step of repeating steps (102) to (107) several times (108), the observable MXene titanium carbide film deposited substrate is obtained by repeating steps (102), (103), (104), (105), (106) and (107).

14. A method (100) according to Claim 2; characterized in that at the step of applying heat treatment to the MXene titanium carbide film deposited substrate (109), a heat treatment is applied to the MXene titanium carbide film deposited substrate in order to increase the film quality in terms of conductivity, to reduce or completely remove the chlorine and / or hydroxyl groups remaining from the deposited films, and to increase the film crystallinity by means of the device (1); the heat treatment temperature is above 450°C; the heat treatment is carried outunder high vacuum, under an atmosphere consisting of hydrogen gas or under an atmosphere consisting of a mixture of hydrogen and an inert gas.

15. MXene titanium carbide film deposited substrate obtained by method (100), which has the properties such as high-volume capacity, high electrical conductivity, high plane mechanical strength and high flexibility and is used in applications such as energy storage, supercapacitors, transparent conductors, sensors, electromagnetic interference prevention coatings and composite materials.

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