WO2021110111A1 - Dlc制备装置和制备方法 - Google Patents
Dlc制备装置和制备方法 Download PDFInfo
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- WO2021110111A1 WO2021110111A1 PCT/CN2020/133768 CN2020133768W WO2021110111A1 WO 2021110111 A1 WO2021110111 A1 WO 2021110111A1 CN 2020133768 W CN2020133768 W CN 2020133768W WO 2021110111 A1 WO2021110111 A1 WO 2021110111A1
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- Prior art keywords
- gas
- dlc
- electric field
- reaction chamber
- preparation device
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- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/3244—Gas supply means
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32697—Electrostatic control
- H01J37/32706—Polarising the substrate
Definitions
- the present invention relates to the field of preparation of diamond-like films, and further relates to a transparent and hard DLC preparation device and preparation method.
- the DLC is suitable for being deposited on the surface of electronic equipment and its accessories for protection.
- Diamond Like Carbon is a metastable material containing sp3 and sp2 carbon bonds. It combines the excellent characteristics of diamond and graphite. It has high hardness, high resistivity, good optical properties and excellent The tribological properties. Diamond-like carbon films have a variety of different structural forms. Specially structured carbon nanomaterials (fullerene-like structure carbon, nano-amorphous carbon, graphene), because of its ultra-low friction coefficient, high hardness, good elastic recovery and Excellent wear resistance, as a class of high-performance solid lubricating materials, has received extensive attention from the scientific and industrial circles.
- One of the existing preparation methods of diamond-like films is a physical vapor deposition method, such as forming a coating by magnetron sputtering to obtain a DLC film; the other is a chemical vapor deposition method, such as using plasma enhanced Chemical vapor deposition (PECVD) deposits DLC film, which uses hydrocarbon gas such as methane, ethane, acetylene, benzene, butane, etc. as the carbon source, and the hydrocarbon gas undergoes activation, dissociation, deposition, etc. under the action of plasma A complex process is used to prepare a DLC film containing a certain amount of hydrogen.
- PECVD plasma enhanced Chemical vapor deposition
- the preparation process of DLC involves a complex reaction process, and the characteristics of the formation of DLC film are related to many factors, such as the composition ratio of raw materials, the control of specific process conditions, etc.
- the control of the same raw material process conditions also significantly affects the formation
- the characteristics of the DLC film, and the influence method is relatively complicated.
- the performance of the DLC film required is also different.
- it In the field of electronic equipment, such as smart phone screens, it not only needs to improve the rigidity of the surface, but also needs to maintain good light transmission performance. Affect the visual effects of electronic device screens.
- An advantage of the present invention is to provide a DLC preparation device and preparation method, which utilizes the synergistic effect of internal and external radio frequency electric fields and high-voltage pulsed electric fields to perform a plasma enhanced chemical deposition reaction (PECVD) to form a DLC film.
- PECVD plasma enhanced chemical deposition reaction
- Another advantage of the present invention is to provide a DLC preparation device and preparation method, which are formed by inductive coupling of a radio frequency electric field and a high-voltage pulsed electric field to cooperate to provide plasma-enhanced chemical deposition reaction conditions, and a DLC film is prepared under the reaction conditions by a reactive gas .
- Another advantage of the present invention is to provide a DLC preparation device and preparation method, which utilize the synergistic effects of radio frequency electric fields and high-voltage pulsed electric fields in different directions to perform plasma-enhanced chemical deposition reactions to form the DLC film.
- Another advantage of the present invention is to provide a DLC preparation device and preparation method, which use low-power radio frequency discharge to maintain a plasma environment and suppress arc discharge in the high-voltage discharge process, thereby improving the efficiency of chemical deposition.
- Another advantage of the present invention is to provide a DLC preparation device and preparation method, which control the performance of the DLC film by controlling the bias value, maintain a higher deposition efficiency, and obtain a DLC film with higher surface hardness and high transmittance. .
- Another advantage of the present invention is to provide a DLC preparation device and preparation method, which can change the ion concentration by controlling the radio frequency power to increase the coating efficiency.
- Another advantage of the present invention is to provide a DLC preparation device and preparation method, which adjust the glow phenomenon by controlling the cavity pressure to adjust the film formation rate and the film quality.
- Another advantage of the present invention is to provide a DLC preparation device and preparation method, which can obtain the target DLC by controlling process parameters such as the discharge characteristics of radio frequency and high-voltage pulses, the flow rate of the reaction gas, and the coating time.
- Another advantage of the present invention is to provide a DLC preparation device and preparation method, wherein in one embodiment, the directions of the radio frequency electric field and the high-voltage pulsed electric field are perpendicular to each other.
- Another advantage of the present invention is to provide a DLC preparation device and preparation method, wherein the DLC film is suitable for being deposited on the surface of electronic equipment and its accessories, and maintains good light transmittance.
- Another advantage of the present invention is to provide a DLC preparation device and preparation method, wherein the PECVD deposition process has a shorter reaction time and a higher deposition efficiency, so that the overall production efficiency is high, and it is suitable for large-scale production applications.
- One aspect of the present invention provides a DLC preparation device, which includes:
- a main body the main body has a reaction chamber, and the reaction chamber is used for placing a substrate;
- a plasma source unit and
- At least one gas supply part for supplying reaction gas to the reaction chamber, the plasma source unit is arranged outside the main body, and provides a radio frequency electric field to the reaction chamber to promote generation
- the plasma causes the reactive gas to be deposited on the surface of the substrate by PECVD to form a DLC film.
- the DLC preparation device includes a radio frequency power supply electrically connected to the plasma source unit to provide power to the plasma source unit.
- the plasma source unit includes an air intake frame, an isolation plate and an induction coil
- the air intake frame is hermetically arranged outside the main body
- the isolation The plate is located between the air intake frame and the induction coil.
- the DLC preparation device wherein the air inlet frame has a communication channel that communicates the reaction chamber of the main body and the gas supply part.
- the DLC preparation device wherein the air intake frame has at least one communication hole and a main channel, the main body has a window, the window communicates with the reaction chamber, and the main body The window communicates with the communication hole of the air intake frame and the main channel to form the communication channel.
- the DLC preparation device wherein the communication port and the main channel are located in a direction perpendicular to each other.
- the air inlet frame has at least one communication hole, an internal connection channel, an air distribution hole and a main channel
- the communication hole communicates with the outside and is used to input gas
- the The air distribution hole is provided inside the air intake frame and communicates with the main channel
- the internal connection channel communicates the communication hole and the air distribution hole, the window of the main body, and the air inlet frame
- the communication hole, the internal connection channel, the air distribution hole and the main channel communicate to form the communication channel.
- the DLC preparation device wherein a plurality of the internal connecting channels communicate with each other to form an internal annular channel.
- the plasma source unit further includes an outer cover plate, and the induction coil is clamped between the isolation plate and the outer cover plate.
- the air intake frame includes a main frame and a plug-in assembly
- the main frame is hermetically arranged on the outside of the main body
- the plug-in assembly is The isolation plate, the induction coil and the outer cover plate are inserted into the plug-in assembly.
- the DLC preparation device according to one embodiment, wherein the isolation plate is a ceramic sealing plate.
- the DLC preparation device wherein the plasma source unit is a radio frequency inductively coupled plasma source, which provides an inductively coupled electric field.
- the DLC preparation device includes a holding plate and a pulse power source, the holding plate is contained in the reaction chamber, and the holding plate is electrically connected to the A pulsed power supply is used to provide a pulsed electric field to the reaction chamber, and the substrate is suitable for being placed on the holding plate.
- the DLC preparation device wherein the holding electrode plate has an air hole communicating with two sides of the holding electrode plate.
- the DLC preparation device includes a plurality of holding plates, and the plurality of holding plates are arranged in parallel and spaced apart.
- the DLC preparation device according to an embodiment, wherein the pulse power supply voltage control range is -200V-5000V.
- the gas supply part includes a plasma source supply part
- the plasma source supply part is used to supply a plasma source gas to the reaction chamber to activate PECVD Deposition reaction.
- the DLC preparation device wherein the plasma source gas is selected from a combination: one or more of inert gas, nitrogen, and fluorocarbon gas.
- the gas supply part includes a reactive gas raw material supply part
- the reactive gas raw material supply part is used to provide a hydrocarbon gas C x H y to the reaction chamber
- the hydrocarbon gas C x H y is deposited on the surface of the substrate by PECVD to form the diamond-like carbon film.
- the gas supply part includes an auxiliary gas supply part
- the auxiliary gas supply part is used to provide an auxiliary gas to the reaction chamber
- the auxiliary gas is used for adjusting The CH content in the diamond-like carbon film reacts with the hydrocarbon gas C x H y to deposit on the surface of the substrate to form the diamond-like carbon film.
- auxiliary gas is selected from a combination: one or more of nitrogen, hydrogen, and fluorocarbon gas.
- the diamond-like carbon film preparation device includes a temperature detection module which is arranged at an equivalent position of the substrate placement position.
- Another aspect of the present invention provides a method for preparing a DLC film, which includes providing a reaction gas to a reaction chamber, and under the action of a radio frequency electric field and a pulsed electric field, the reaction gas is promoted to be deposited in the reaction chamber by PECVD.
- a DLC film is formed on the surface of a substrate in the room.
- the radio frequency electric field is turned on first, and then the pulsed electric field is turned on.
- the radio frequency electric field is an inductive coupling electric field.
- the method for preparing a DLC film includes the step of providing a plasma source gas to the reaction chamber to activate the PECVD deposition reaction, and the radio frequency electric field and the pulsed electric field act on the plasma at the same time. Body source gas.
- a holding plate is provided in the reaction chamber, and the holding plate is electrically connected to a pulsed power source to provide the pulsed electric field in the reaction chamber.
- the DLC film preparation method which includes the step of detecting the temperature of the equivalent position of the substrate for feedback control.
- Another aspect of the present invention provides a method for preparing a DLC film, which includes the steps:
- the radio frequency power supply is turned on first, and then the pulse power supply is turned on.
- the DLC film preparation method which includes the step of: setting a radio frequency electric field outside the pulsed electric field.
- radio frequency electric field is an inductive coupling electric field.
- step c) includes the step of: providing an auxiliary gas to the reaction chamber, the auxiliary gas is used to adjust the CH content in the diamond-like film, and the Hydrocarbon gas C x H y is reactively deposited on the surface of the substrate to form the diamond-like carbon film.
- the diamond-like carbon film preparation method which includes the steps of: extracting the gas in the reaction chamber and adjusting the pressure of the gas in the reaction chamber.
- the diamond-like carbon film preparation method which includes the step of detecting the temperature of the equivalent position of the substrate for feedback control.
- Fig. 1 is a block diagram of a DLC preparation method according to an embodiment of the present invention.
- Fig. 2 is a block diagram of a DLC preparation device according to the above-mentioned embodiment of the present invention.
- Fig. 3 is a schematic diagram of a DLC preparation device according to the above-mentioned embodiment of the present invention.
- FIGS 4A-4B are perspective views of one implementation of the DLC preparation device according to the above-mentioned embodiment of the present invention.
- Fig. 4C is a perspective view of another implementation of the DLC preparation device according to the above-mentioned embodiment of the present invention.
- Fig. 5A is an exploded schematic diagram of an embodiment of the DLC preparation device according to the foregoing embodiment of the present invention.
- 5B is a schematic diagram of a modified embodiment of the air intake frame of the DLC preparation device according to the above-mentioned embodiment of the present invention
- Fig. 6 is a schematic diagram of a modified embodiment of the DLC preparation device according to the above-mentioned embodiment of the present invention.
- Fig. 7 is a transmission electron micrograph of the diamond-like carbon film according to the above-mentioned embodiment of the present invention.
- the term “a” should be understood as “at least one” or “one or more”, that is, in one embodiment, the number of an element may be one, and in another embodiment, the number of the element The number can be multiple, and the term “one” cannot be understood as a restriction on the number.
- references to "one embodiment”, “embodiments”, “exemplary embodiments”, “various embodiments”, “some embodiments”, etc. indicate that such embodiments describing the invention may include specific features, structures, or characteristics , But not every embodiment must include this feature, structure, or characteristic. In addition, some embodiments may have some, all, or none of the described features of other embodiments.
- Fig. 1 is a block diagram of a DLC preparation method according to an embodiment of the present invention.
- Fig. 2 is a block diagram of a DLC preparation device according to the above-mentioned embodiment of the present invention.
- Fig. 3 is a schematic diagram of a DLC preparation device according to the above-mentioned embodiment of the present invention.
- the present invention provides a DLC preparation device, the DLC preparation device is used for PECVD reaction to prepare a DLC film, the DLC film is suitable for being deposited on the surface of a substrate to improve the substrate The surface properties. Furthermore, the DLC preparation device is used to form the DLC film by chemical deposition on the surface of the substrate by means of plasma enhanced chemical deposition (PECVD). In other words, the substrate is placed in the reaction chamber of the DLC preparation device for plasma enhanced chemical vapor deposition to form the DLC film on the surface of the substrate.
- PECVD plasma enhanced chemical deposition
- Substrate refers to a small or large area object to be coated or having a surface improved by the method of the present invention.
- the substrate referred to herein can be made of glass, plastic, inorganic material or any other material with a surface to be coated or modified.
- the substrate may be an electronic device and its accessories, for example but limited to a smart phone, a tablet computer, an e-reader, a wearable device, a television, a computer display screen, a glass screen, and a flexible screen.
- “Plasma” refers to a state where electrons, positive and negative ions, excited atoms, molecules, and free radicals are mixed.
- the DLC preparation device uses the hydrocarbon gas C x H y as the raw material of the reactive gas to perform plasma enhanced chemical vapor deposition to obtain the DLC film.
- the DLC film can improve the surface rigidity of the substrate, such as increasing the Mohs hardness, and can also improve the drop resistance and friction resistance of the substrate.
- the DLC is a nano film with a relatively small thickness, and the thickness range is for example but not limited to 10 to 2000 nm.
- the DLC preparation device vapor-deposits C x H y gas reaction raw materials on the surface of the substrate through the PECVD process, and the chemical deposition reaction process of plasma can make the thickness of the DLC film small, such as nanometer size, and During the PECVD deposition process, the targeted DLC film can be obtained by controlling the process parameters. For example, control to obtain the DLC of a predetermined thickness. That is to say, the DLC film of predetermined thickness is obtained under different predetermined reaction conditions, rather than arbitrary numerical selection.
- the reaction gas raw material can be a single gas or a mixture of two or more gases; preferably, the hydrocarbon gas is selected from methane, ethane, propane, butane, and ethylene that are gaseous under normal pressure. , Acetylene, propylene, propyne, can also be vapor formed by decompression or heating evaporation, such as benzene vapor, toluene vapor.
- the plasma-enhanced chemical vapor deposition (PECVD) process has many advantages: (1) Dry film formation does not require the use of organic solvents; (2) Plasma's etching effect on the substrate surface makes The deposited film has good adhesion to the substrate; (3) The coating can be uniformly deposited on the surface of the irregular substrate, and the gas permeability is extremely strong; (4) The coating can be designed well, compared to the liquid phase method with micron level control Precision, the chemical vapor method can control the coating thickness at the nanometer scale; (5) The coating structure is easy to design, the chemical vapor method uses plasma activation, and the composite coating of different materials does not need to design a specific initiator for initiation , Through the control of input energy, a variety of raw materials can be compounded together; (6) The compactness is good, and the chemical vapor deposition method tends to activate multiple active sites during the plasma initiation process, similar to one in a solution reaction. There are multiple functional groups on the molecule, and multiple functional groups form a
- the plasma enhanced chemical vapor deposition (PECVD) process generates plasma through glow discharge, and the discharge method includes microwave discharge, radio frequency discharge, ultraviolet, and electric spark discharge.
- a plasma source gas is passed into the DLC preparation device, which is used to activate the chemical deposition of the reactive gas raw material reaction.
- the plasma source gas is exemplified but not limited to inert gas, nitrogen, fluorocarbon gas, wherein the inert gas is exemplified but not limited to He and Ar, and the fluorocarbon gas is exemplified but not limited to carbon tetrafluoride.
- the plasma source gas can be a single gas or a mixture of two or more gases.
- the plasma source gas can be passed in at the same time as the reactive gas raw material, or can be passed in sequentially.
- the plasma source gas is passed in first, and then the reactive gas raw material is passed in.
- the plasma source gas may not be provided, that is, the reactive gas raw material is directly deposited on the surface of the substrate, and the amount of the reactive gas raw material required at this time is increased. And to a certain extent, it will affect the reaction speed.
- an auxiliary gas is passed into the DLC preparation device, and the auxiliary gas cooperates with the reaction gas raw material to form the DLC film, that is, it will be a component of diamond-like carbon film.
- the auxiliary gas is a non-hydrocarbon gas, that is , a gas other than C x H y , and contains elements other than C and H.
- the auxiliary gas is used to adjust the performance of the DLC film, such as adjusting rigidity and improving flexibility.
- the addition of the auxiliary gas can adjust the CC content and/or the content of CH and other bonds in the DLC film formed by pure hydrocarbon gas, and adjust the performance of the DLC film in combination with the characteristics of the auxiliary gas itself .
- the auxiliary gas is exemplified but not limited to nitrogen, hydrogen, and fluorocarbon gas.
- the auxiliary gas may be passed in simultaneously with the reaction gas raw material, or may be passed in successively.
- the auxiliary gas and the reaction gas raw material Simultaneous access.
- hydrogen-containing diamond-like carbon films, nitrogen-containing diamond-like carbon films, fluorine-containing diamond-like carbon films, etc., with different hydrogen contents can be prepared.
- the auxiliary gas can adjust the proportions of C-H bonds, C-N bonds, and N-H bonds in the DLC film, thereby changing the performance of the DLC.
- the addition of the auxiliary gas can adjust the performance of the DLC film, which increases and improves the performance while relatively weakening the rigidity and original performance of the DLC film. Therefore, it is necessary to balance the addition amount.
- the auxiliary gas is hydrogen
- the function of the auxiliary gas is to adjust the ratio of hydrocarbons in the DLC film, such as increasing the content of C-H bonds, and improving the flexibility of the DLC film.
- the auxiliary gas when the content of hydrogen is greater than a predetermined range, the auxiliary gas will destroy the rigidity of the DLC film, so the added content needs to be controlled.
- the hydrogen content is greater than 40%, its rigidity will decrease significantly.
- the DLC film with higher hydrogen content has higher lubricity and transparency than the DLC film with lower hydrogen content.
- a certain amount of hydrogen is conducive to the formation of SP3 bonds, which can increase the hardness to a certain extent, but with With the further increase of the hydrogen content, the hardness of the diamond-like carbon film will gradually decrease.
- the addition of the auxiliary gas can not only adjust the performance of the DLC film, it can also increase the ionization concentration of the PECVD reaction process, and promote the reaction to proceed more quickly.
- the DLC preparation device prepares the DLC film
- the combined action of a radio frequency electric field and a pulsed electric field is used to assist in completing the plasma-enhanced chemical deposition process.
- radio frequency and high voltage pulses are applied to the PECVD deposition process at the same time.
- low-power radio-frequency discharge is used to maintain the plasma environment and suppress arc discharge in the high-voltage discharge process, thereby improving the efficiency of chemical deposition.
- Radio frequency can make the entire coating process in a plasma environment by discharging inert gas and reactive gas raw materials, and the reactive gas raw materials are in a high-energy state;
- the function of pulsed high voltage is that the pulsed power supply generates a strong electric field during the discharge process and is active in a high-energy state
- the particles are accelerated to deposit on the surface of the substrate under the action of a strong electric field, forming an amorphous carbon network structure.
- the pulsed electric field is in a non-discharge state, it is beneficial for the DLC film deposited on the surface of the substrate to freely relax the amorphous carbon network structure.
- the carbon structure transforms into a stable phase---bent graphene sheet structure, and is buried Placed in the amorphous carbon network to form a transparent graphene-like structure. That is to say, the combination of the radio frequency electric field and the varying pulsed electric field enables the DLC film to be deposited on the surface of the substrate quickly and stably.
- FIG. 7 which is a transmission electron microscope image of the diamond-like carbon film according to the above-mentioned embodiment of the present invention, the DLC film is composed of amorphous and nanocrystalline structures.
- the DLC preparation device prepares the DLC film
- the plasma source gas, the reactive gas raw material, and the auxiliary gas are added to the DLC preparation device in stages, and accordingly, the radio frequency
- the electric field and the pulsed electric field are selectively applied to the reacted gas material in stages.
- the plasma source gas when the plasma source gas is added to the DLC preparation device, it can also be referred to as being in the first stage, applying a radio frequency electric field and a pulsed electric field.
- the plasma source gas forms part of the plasma under the action of the radio frequency electric field and the pulsed electric field, and the interaction between gas molecules, such as mutual impact, further promotes the generation of part of the plasma.
- the radio frequency electric field and the pulsed electric field are turned on, the radio frequency electric field is turned on first, and then the pulsed electric field is turned on.
- the reaction gas When the raw materials and the auxiliary gas raw materials are added, it can also be referred to as the second stage, and the radio frequency electric field and the pulse electric field are applied at the same time, that is, the radio frequency power supply and the pulse power supply are kept on.
- the radio frequency electric field and the pulse electric field are applied at the same time, that is, the radio frequency power supply and the pulse power supply are kept on.
- part of the reactive gas raw materials generates plasma under the action of the radio frequency electric field and the pulsed electric field, and part of the reactive gas generates plasma under the excitation of the plasma generated by the plasma source gas.
- auxiliary gas Part of the auxiliary gas generates plasma under the action of the radio frequency electric field and the pulsed electric field, and part of the auxiliary gas is excited to generate plasma under the action of other plasma, so that the DLC preparation device
- the plasma concentration continues to increase, thereby activating the plasma deposition reaction process, so that the DLC film can be quickly and effectively deposited on the surface of the substrate.
- the plasma-enhanced chemical vapor deposition process is a very complicated reaction process, and the reaction that occurs during the ionized deposition process is not limited to the above content.
- the plasma source gas When the plasma source gas is added to the DLC preparation device, it can also be said that it is in the first stage, and only the pulsed electric field is applied. In this stage, the plasma source gas forms at least part of the plasma under the action of the pulsed electric field, and the interaction between gas molecules, such as mutual collision, further promotes the generation of plasma.
- the reactive gas raw materials and the auxiliary gas raw materials When the reactive gas raw materials and the auxiliary gas raw materials are added, it can also be referred to as the second stage, and the radio frequency electric field and the pulse electric field are simultaneously applied. In this stage, part of the reactive gas raw materials generates plasma under the action of the radio frequency electric field and the pulsed electric field, and part of the reactive gas generates plasma under the excitation of the plasma generated by the plasma source gas.
- Part of the auxiliary gas generates plasma under the action of the radio frequency electric field and the pulsed electric field, and part of the auxiliary gas is excited by the action of other plasmas to generate plasma, so that the plasma in the DLC preparation device
- the body concentration is continuously increased, thereby activating the plasma deposition reaction process, so that the DLC film can be quickly and effectively deposited on the surface of the substrate.
- the radio frequency power supply and the high-voltage pulse power supply may be applied simultaneously or sequentially.
- the high-voltage pulse power is first applied, and when the reaction gas raw material is added, the radio frequency power is applied, so that the two electric fields work together in sequence.
- the radio frequency power is applied, and when the reaction gas raw material is added, the high-voltage pulse power is applied, so that the two electric fields work together in sequence.
- radio frequency electric field and pulsed electric field of the present invention affects the performance of the DLC film formed by deposition, and for different device structures, there are differences in the preferred way.
- the radio frequency electric field and pulsed electric field of the present invention are arranged inside and outside of the DLC film.
- the effect of simultaneously applying pulsed electric field and radio frequency electric field in the first and second stages of film formation is better than applying pulsed electric field or radio frequency electric field alone.
- the radio frequency electric field is turned on first, and then the pulsed electric field is turned on.
- the electric field is better than the method of turning on the radio frequency electric field and the pulse electric field at the same time, and the pulse electric field first, then the radio frequency electric field.
- the radio frequency electric field is turned on first, and then the pulse electric field is turned on.
- the gas is easier to start to generate plasma.
- the plasma source gas added in the first stage generates only part of the plasma, but due to its basic properties, such as inert gas, it will not be deposited on the substrate.
- the surface in other words, does not constitute a constituent of the diamond-like carbon film.
- the plasma source forms plasma, the plasma acts on the surface of the substrate to produce an etching effect on the surface of the substrate, that is, to remove residues on the surface of the substrate, and is the deposition of the reactive gas raw material Prepare the basics.
- the plasma source has an etching effect on the surface of the substrate, so that the DLC film is more firmly deposited on the surface of the substrate.
- the plasma source gas added in the first stage generates only part of the plasma, which not only has an etching effect on the substrate, but also deposits on the surface of the substrate, such as
- the two-stage reaction raw material gases jointly carry out a deposition reaction.
- nitrogen gas and fluorocarbon gas which together with the reaction gas raw material hydrocarbon gas in the second stage, carry out a deposition reaction, which can adjust the proportions of CH bonds, CN bonds, and NH bonds in the DLC film, thereby changing the Describe the performance of the DLC film.
- reaction source gas and the auxiliary gas are vapor-deposited together on the surface of the substrate to form the DLC film.
- the combined action of radio frequency and high-voltage pulses enhances the deposition efficiency, so that a protective film can be effectively deposited on the surface of the substrate, that is, the DLC film is formed by a chemical deposition reaction in a relatively short time. This improves the production efficiency, so that the DLC film can be mass-produced industrially.
- the gas flow rate entering the device is controlled to control the deposition rate and the deposition thickness of the DLC film.
- the gas flow rate of the plasma source gas, the reactive gas raw material, and the auxiliary gas is controlled.
- process parameters such as the pressure in the reaction chamber, the amount of radio frequency power, the pulse voltage, the duty cycle, and the coating time are controlled to obtain the expected DLC film.
- the performance of the DLC film obtained can be controlled by adjusting and controlling the gas flow, the pressure in the reaction chamber, the radio frequency power, the pulse voltage, the duty cycle, and the coating time, etc., to control the performance of the DLC film, including thickness, hardness, Transparency, etc.
- the reaction temperature in the preparation device is controlled, for example, the temperature around the substrate is detected by a temperature detection module, and other process parameters are feedback and adjusted so that the temperature is controlled at a predetermined value.
- the temperature in the preparation device ranges from 25°C to 100°C. Preferably, the temperature range is 25°C to 50°C.
- Fig. 2 is a block diagram of a DLC preparation device according to an embodiment of the present invention.
- Fig. 3 is a schematic diagram of a DLC preparation device according to the above-mentioned embodiment of the present invention.
- 4A-4B are perspective views of one implementation of the DLC preparation device according to the above-mentioned embodiment of the present invention.
- Fig. 5A is an exploded schematic diagram of an embodiment of the DLC preparation device according to the foregoing embodiment of the present invention.
- the present invention provides a DLC preparation device, the DLC preparation device is used to prepare the DLC film, and further, the DLC device is used to pass in the reaction gas for PEDVD deposition, forming on the surface of the substrate The DLC film.
- the DLC preparation device includes a main body 10, and has a reaction chamber 100 for accommodating the substrate and for introducing gas for deposition reaction, and the main body 100 forms the reaction chamber 100.
- the reaction chamber 100 is a closed chamber, that is, the reaction chamber 100 will not circulate gas in an uncontrolled state.
- the plurality of gas supply parts 20 includes a plasma source supply part 21, a reactive gas raw material supply part 22 and an auxiliary gas supply part 23.
- the plasma source supply part 21 is controllably connected to the reaction chamber 100, and the plasma source supply part 21 is used to supply the plasma source gas to the reaction chamber 100.
- the plasma source gas is exemplified but not limited to inert gas, nitrogen, fluorocarbon gas, wherein the inert gas is exemplified but not limited to He and Ar, and the fluorocarbon gas is exemplified but not limited to carbon tetrafluoride.
- the plasma source gas may be a single gas or a mixture of two or more gases.
- the reaction gas raw material supply part 22 is controllably connected to the reaction chamber 100, and the reaction gas raw material supply part 22 is used to supply the reaction gas raw material to the reaction chamber 100.
- the reaction gas raw material is a hydrocarbon gas C x H y , in C x H y , x is an integer of 1-10, and y is an integer of 1-20.
- the reaction gas raw material can be a single gas or a mixture of two or more gases; preferably, the hydrocarbon gas is selected from methane, ethane, propane, butane, and ethylene that are gaseous under normal pressure. , Acetylene, propylene, propyne, can also be vapor formed by decompression or heating evaporation, such as benzene vapor, toluene vapor.
- the auxiliary gas supply part 23 is controllably communicated with the reaction chamber 100, and the auxiliary gas supply part 23 is used to supply the auxiliary gas to the reaction chamber 100.
- the auxiliary gas is exemplified but not limited to hydrogen, nitrogen, fluorocarbon gas.
- the plasma source supply part 21 includes a plurality of supply pipes 26 for supplying different plasma source gases. More specifically, the number of supply pipes 26 or the number of connections of the plasma source supply part 21 is determined by the plasma source gas that needs to be passed in. That is to say, when the type of plasma source gas that needs to be passed is 1, the number of supply pipes 26 of the plasma source supply part 21 is 1, and when the type of plasma source gas that needs to be passed When the number is 2, the number of the supply pipes 26 of the plasma source supply part 21 is 2, and so on.
- each supply pipe 26 of the plasma source supply part 21 supplies a single gas, that is, one supply pipe 26 only passes through one type of gas instead of multiple gases or mixed gases. , Can prevent the pre-reaction between the gases, and facilitate the control of the amount of gas introduced.
- multiple gases may be passed into the pipeline, or the same gas may be passed into multiple pipelines.
- the multiple supply pipes 26 of the plasma source supply part 21 include one supply pipe 26, and the supply pipe 26 is used to pass the plasma into the reaction chamber.
- Body source gas for example, in one embodiment, the supply pipe 26 of the plasma source supply part 21 is used to supply argon.
- the reactive gas raw material supply part 22 includes a plurality of supply lines 26 for supplying different reactive gas raw materials. More specifically, the number of supply pipes 26 or the number of connections of the reactive gas raw material supply part 22 is determined by the reactive gas raw material that needs to be passed in. That is to say, when the gas type of the reactive gas raw material that needs to be passed is 1, the number of supply pipes 26 of the reactive gas raw material supply part 22 is 1, and when the gas of the reactive gas raw material that needs to be passed When the number of types is 2, the number of supply pipes 26 of the reactive gas raw material supply part 22 is 2, and so on.
- each supply pipe 26 of the reactive gas raw material supply part 22 supplies a single gas, that is, one supply pipe 26 only passes through one type of gas, rather than multiple gases or mixed gases. In this way, pre-reaction between gases can be prevented, and the amount of gas introduced can be easily controlled.
- multiple gases may be passed into the pipeline, or the same gas may be passed into multiple pipelines.
- the reactive gas raw material supply part 22 includes two supply pipes 26, which are respectively used to pass two different gases.
- one of the pipes supplies methane.
- the other said pipeline is used to supply acetylene.
- the auxiliary gas supply part 23 includes a plurality of supply pipes 26 for supplying different auxiliary gases. More specifically, the number of supply pipes 26 or the number of connections of the auxiliary gas supply part 23 is determined by the auxiliary gas that needs to be passed in. That is, when the gas type of the auxiliary gas that needs to be passed is 1, the number of supply pipes 26 of the auxiliary gas supply part 23 is 1, and when the number of gas types of the auxiliary gas that needs to be passed is At 2 o'clock, the number of supply pipes 26 of the auxiliary gas supply part 23 is 2, and so on.
- each supply pipe 26 of the auxiliary gas supply part 23 supplies a single gas, that is, one supply pipe 26 only passes through one type of gas instead of multiple gases or mixed gases. It can prevent the pre-reaction between the gases, and facilitate the control of the amount of gas introduced.
- multiple gases may be passed into the pipeline, or the same gas may be passed into multiple pipelines.
- the auxiliary gas supply part 23 includes a supply pipe 26, and the supply pipe 26 is used to pass the auxiliary gas into the reaction chamber.
- the supply line 26 of the auxiliary gas supply part 23 is used to supply hydrogen.
- the diamond-like carbon thin film preparation device includes a confluence area 25, the confluence area 25 is connected to the reaction chamber 100, and the confluence area 25 is used to connect the gas supply part 20 Confluence of gases.
- the merging portion communicates with the plasma source supply portion 21, the reactive gas raw material supply portion 22 and the auxiliary gas supply portion 23.
- the introduced gas is fed into the reaction chamber 100 after being merged through the confluence area.
- each of the supply parts can also independently send gas into the reaction chamber 100.
- the gas supply part 20 includes a control valve 24 for controlling the on-off of the gas. Furthermore, the gas supply unit 20 includes a plurality of control valves 24, which are respectively provided in the plasma source supply unit 21, the reactive gas material supply unit 22, and the supply line 26 of the auxiliary gas material supply unit. , To separately control the gas flow in each pipeline.
- the diamond-like film preparation device includes a radio frequency power supply 30 and a pulse power supply 40.
- the radio frequency power supply 30 is used to provide a radio frequency electric field to the reaction chamber 100
- the pulse power supply 40 is used to supply the reaction chamber 100 with a radio frequency electric field. Provide a pulsed electric field.
- FIGS. 4A-4B are perspective views of one implementation of the DLC preparation device according to the above-mentioned embodiment of the present invention.
- Fig. 4C is a perspective view of another implementation of the DLC preparation device according to the above-mentioned embodiment of the present invention.
- Fig. 5A is an exploded schematic diagram of an embodiment of the DLC preparation device according to the foregoing embodiment of the present invention.
- Fig. 5B is a modified embodiment of the air intake frame.
- Fig. 6 is a schematic diagram of a modified embodiment of the DLC preparation device according to the above-mentioned embodiment of the present invention.
- the DLC preparation device includes a plasma source unit 50 which is electrically connected to the radio frequency power source 30 so as to obtain electric energy from the radio frequency power source 30 to generate a radio frequency electric field.
- the plasma source unit 50 is disposed on the outside of the main body 10.
- the plasma source unit 50 is disposed on at least one side of the main body 10.
- the plasma source unit may be arranged on any one or more of the six sides of the main body 10, and when the main body 10 has a cylindrical structure
- the plasma source unit can be arranged on the annular side surface and/or both bottom surfaces of the main body 10.
- the main body 10 further includes a box body 11 and a control door 12, and the control door 12 is used to control the opening or closing of the box body 11.
- the main body 10 is provided with a suction port 101, and the suction port 101 is provided on a side surface of the box body 11.
- the air suction port 101 is provided on the back side of the box 11, that is, the side opposite to the control door 12.
- the air suction port 101 is provided on the top side of the box 11, that is, on the top side adjacent to the control door 12.
- the control door 12 can be directed toward the outside, that is, toward the operator, the plasma source unit 50 is located on an adjacent side, and the suction port 101 is located on the upper side, that is, the DLC preparation The top side of the device.
- the plasma source unit 50 is a radio frequency inductively coupled plasma source (RF-ICP) for providing an inductively coupled electric field to the reaction chamber 100 to generate plasma .
- RF-ICP radio frequency inductively coupled plasma source
- the plasma source unit 50 includes an air inlet frame 51, an isolation plate 52, and an induction coil 53, and the air inlet frame 51 is hermetically connected to the main body 10, more specifically, the air inlet frame 51 It is pressed against one side of the main body 10.
- the isolation plate 52 is arranged between the air intake frame 51 and the induction coil 53.
- the air intake frame 51 has at least one communication channel 5100, the communication channel 5100 is used to communicate the main body and the gas supply part, so as to facilitate the gas supply part to the main body
- the reaction chamber is fed with gaseous materials.
- the main body 10 has a window 1001, and the window 1001 communicates with the reaction chamber 100 and the outside.
- the communication channel 5100 communicates with the window 1001. That is, during operation, the gas supply part 20 supplies gas, and the gas enters the gas inlet frame 51, and enters the reaction chamber through the communication channel 5100 and the window 1001 of the gas inlet frame 51 100.
- the air intake frame 51 has at least one communication hole 5101 and a main channel 5102, and the communication hole 5101 communicates with the main channel 5102 to form the communication channel 5100. More specifically, the communication hole 5101 is arranged in the lateral direction of the air intake frame 51, that is, the plane where the communication hole 5101 is located is substantially parallel to the outer surface of the main body 10.
- the main channel 5102 is arranged in the longitudinal direction of the air intake frame 51, that is, the direction of the main channel 5102 is perpendicular to the outer surface of the main body 10.
- the direction in which the gas enters the gas inlet frame 51 is different from the direction in which the gas enters the reaction chamber 100. More specifically, the direction in which the gas enters the gas inlet frame 51 and the direction in which the gas enters the reaction chamber 100 are different. The directions are perpendicular to each other.
- the gas supply part 20 needs to be connected to the air inlet frame 51 through a pipeline, and the isolation plate 52 and the induction coil 53 are directly installed on the outside of the air inlet frame 51.
- the air intake frame 51 provides installation positions for the isolation plate 52 and the induction coil 53, and the incoming gas forms plasma through the inductive coupling electric field generated by the induction coil 53, therefore,
- the gas inlet channel that is, the communication hole 5101, is arranged in the lateral direction, and the main channel 5102, the gas inlet channel of the reaction chamber 100, is arranged in the longitudinal direction, which makes the external space of the main body 10 more efficient. , So that the main volume of the DLC preparation device is not too large, reducing the occupation of the placement space.
- the size of the main channel 5102 is greater than the diameter of the communicating hole 5101, or in other words, the capacity of the main channel 5102 is greater than the capacity of the communicating hole 5101. It is worth mentioning that the communicating hole 5101 is for gas to enter Through the smaller size of the channel, the gas flow rate can be controlled more accurately.
- the air inlet channel is a channel through which plasma is formed through the action of the induction coil 53. A larger space makes the area of the induction electric field larger, and more gas molecules or ions have a stronger interaction.
- the communicating hole 5101 may have a straight extending shape, a curve or other irregular shapes, that is, the inside of the communicating hole 5101 may extend linearly along the side of the air intake frame 51, or it may be The curve runs through the side of the air intake frame 51.
- the number of the communicating holes 5101 may be one or more.
- one communicating hole 5101 is provided on the four sides of the air intake frame 51 to communicate with the main channel. 5102, so that the side space of the air intake frame 51 can be used.
- the air intake frame 51 has a plurality of mounting holes 5105, and the mounting holes 5105 are used to mount the air intake frame to the main body 10 through fixing elements, for example, but not limited to, passing through the mounting holes by screws 5105 fixes the air intake frame to the main body 10.
- the air intake frame 51 further has an internal connection channel 5103, and the internal connection channel 5103 is arranged in The inside of the air intake frame 51 communicates with two adjacent communicating holes 5101 inside.
- the inner side of the air intake frame 51 has at least one inner air hole 5104, and the inner air hole 5104 communicates with the inner connecting channel 5103 and the main air inlet channel 5102. That is to say, in this embodiment of the present invention, the communication hole 5101 is not directly connected to the main channel 5102, but is connected to the main channel 5102 through the internal connection channel 5103 and the internal air hole 5104. .
- a plurality of the inner cloth air holes 5104 are respectively arranged at different positions inside the air intake frame 51, for example, but not limited to, the inside of the four frames of the air intake frame 51, so as to enter more evenly.
- the air intake frame 51 has a plurality of the internal connecting passages 5103, which are respectively connected in the same way to form an inner annular passage 5200, so that gas can be sent through any one of the communication holes 5101.
- the gas is delivered to the main channel 5102 through any one of the air distribution holes 5104 on the other side.
- different gases can be pre-merged in the inner connecting channel 5103 or the formed inner annular channel 5200, so that the gas is more fully mixed, and can be reacted preliminarily to form more plasma.
- the number of the air distribution holes 5104 can be more than the number of the communication holes 5101, which can enter the main channel 5102 more quickly or with a larger amount of air, and form more plasma in the main channel, and enter The reaction chamber 100.
- the air intake frame 51 may have a communication hole 5101 for air intake, that is, when multiple gases need to be transported, they may first merge through the communication hole 5101 enters, or may enter the internal connecting channel 5103 through the same communicating hole 5101 one after another, and then disperse to various positions of the main channel 5102 through the internal air holes 5104.
- the isolation plate 52 blocks one of the ports of the main channel 5102 to isolate the main channel 5102 of the air intake frame 51 and the induction coil 53, that is, gas enters through the communication hole 5101, It enters the reaction chamber 100 through the main channel 5102 without flowing to the side of the induction coil 53. Further, the isolation plate 52 seals and isolates the gas but does not isolate the electric field, that is, the gas in the main channel 5102 or the gas in the reaction chamber 100 can receive the induction electric field effect of the induction coil 53.
- the isolation plate 52 is a ceramic sealing plate, so as to reduce the influence of the induction electric field fed from the induction coil 53 into the main channel 5102 and the reaction chamber 100.
- the plasma source unit 50 further includes an outer cover 54 which is arranged on the outside of the induction coil 53, in other words, the induction coil 53 is clamped on the isolation plate 52 ⁇ The outer cover 54.
- the air intake frame 51 includes a main frame body 511 and a plug-in assembly 512.
- the main frame body 511 is hermetically arranged on the outside of the main body 10, and the plug-in assembly 512 is arranged on the main frame.
- the isolation plate 52, the induction coil 53, and the outer cover 54 are sequentially inserted into the plug assembly 512, so that the isolation plate 52, The induction coil 53 and the outer cover 54 are detachably fixed to the main frame 511.
- the DLC preparation device includes a holding plate 60 which is electrically connected to the pulse power source 40 so as to obtain electric energy from the pulse power source 40 to generate a pulsed electric field.
- the holding plate 60 is arranged in the reaction chamber 100 so as to provide a pulsed electric field to the reaction chamber 100.
- the holding electrode plate is a flat plate-shaped structure, which is suitable for placing the substrate. In other words, the sample to be deposited is placed on the holding plate 60 for deposition.
- the holding plate 60 is used to place the substrate, and on the other hand, it is used to provide a pulsed electric field, that is, to provide a pulsed electric field at the position of the substrate, that is, from the The bottom and the surrounding of the substrate provide pulse electric field action, which is more direct.
- the diamond-like carbon film preparation device uses the combined action of a radio frequency electric field and a high-voltage pulsed electric field to assist in completing the plasma-enhanced chemical deposition process.
- radio frequency and high voltage pulses are applied to the PECVD deposition process at the same time.
- low-power radio frequency discharge is used to maintain the plasma environment, and the arc discharge in the high-voltage discharge process is suppressed to improve the efficiency of chemical deposition.
- Arc discharge is a form of discharge that is further enhanced by glow discharge. Its instantaneous current can reach tens or even hundreds of amperes or more.
- radio frequency electric field and the pulsed electric field cooperate with each other to optimize the deposition process and reduce the damage to the substrate to be deposited.
- the plasma source unit 50 can make the entire coating process in a plasma environment by discharging the plasma source gas and reactive gas raw materials, and the reactive gas raw materials are in a high-energy state; the pulse power supply 40 and the holding plate 60
- the function of the pulsed high voltage is that the pulsed power supply 40 generates a strong electric field during the discharge process, and the active particles in the high-energy state are accelerated by the strong electric field to deposit on the surface of the substrate, forming an amorphous carbon network structure.
- the pulse power supply 40 and the holding electrode plate 60 are in a non-discharge state, it is beneficial for the DLC film deposited on the surface of the substrate to relax the amorphous carbon network structure freely, and the carbon structure becomes a stable phase under the action of thermodynamics.
- the bent graphene sheet structure is transformed and embedded in the amorphous carbon network to form a transparent graphene-like structure. That is to say, the combination of the radio frequency electric field and the changing pulse electric field enables the DLC film to be deposited on the surface of the substrate quickly and stably.
- the combined action of the radio frequency electric field and the high-voltage pulsed electric field enhances the deposition efficiency, so that the protective film can be effectively deposited on the surface of the electronic device screen, that is to say, the DLC film is formed by the chemical deposition reaction in a relatively short time. Therefore, the production efficiency is improved, so that the DLC film can be mass-produced industrially.
- magnetron sputtering coating is usually used to form the diamond-like carbon film DLC.
- the magnetron sputtering process is a kind of PVD process, which uses a bulk graphite target as the carbon Source, its ionization efficiency and deposition efficiency are low, so it will be limited in some occasions.
- the PECVD carbon source is a gas, and the ionization is performed by the external DC pulse power supply 40 and the radio frequency power supply 30. The degree of ionization and the deposition efficiency are improved, and a high-hardness DLC film can be formed. At the same time, the cost is higher. low.
- the carbon source target is a gas, which does not require a heating process, the deposited film is thinner, and the deposition time is shorter. Therefore, the heat accumulation in the whole process is less, the reaction temperature is lower, and it can be controlled. At 25°C ⁇ 100°C, it is suitable for coating some electronic equipment.
- the DLC preparation device is used to perform PECVD chemical deposition in the reaction chamber 100, and through the combined action of radio frequency and high-voltage pulses, A relatively simple process can be adopted, and the deposition rate can be effectively increased, thereby enabling the diamond-like carbon film to be widely used in mass industrial production.
- the holding electrode plate 60 has an air hole which communicates with two sides of the holding electrode plate 60.
- the pores are used for the gas entering the reaction chamber 100 to pass through to generate electric discharge.
- the gas introduced into the confluence part enters the reaction chamber 100 along the gas inlet channel of the inductively coupled plasma source (ICP)
- the gas is directed around the holding plate 60 The gas produces a discharge effect, which promotes the gas to be ionized to generate plasma.
- the holding electrode plate 60 is provided with a plurality of air holes, which are arranged in an array on the holding electrode plate 60, so that the air flow can evenly enter and reach the upper part of the holding electrode plate 60 located below, and counteract the air flow. Produce a relatively uniform electric field effect.
- the air holes may be straight through holes, and may also be connected to the holes on both sides of the holding electrode plate 60 in a curved or broken line manner.
- the cross-sectional shape of the air hole may be a circle, a square, a polygon, or other curved shapes.
- a plurality of the holding plates 60 are arranged in parallel at intervals.
- the distance between two adjacent object plates 60 is a predetermined distance.
- the choice of the distance between two adjacent object plates 60 requires consideration of the application of the substrate on the two adjacent object plates 60 on the one hand.
- Electric field conditions need to consider the space utilization rate, that is, the number and quantity of samples that can be deposited at one time. For example, the distance is too large, the pulsed electric field has a poor effect, which affects the ionization efficiency and deposition efficiency, and the space utilization rate is low. The distance is too small and the pulse electric field is too strong, which will affect the performance of the substrate such as electronic equipment, and is not conducive to the picking and placement of samples, and the work efficiency is low.
- the distance between two adjacent electrode plates 60 is 10-200 mm.
- the distance between two adjacent electrode plates 60 is 20 mm-150 mm.
- the distance between two adjacent electrode plates 60 is 20mm-30mm, 30mm-40mm, 40mm-50mm, 50mm-60mm, 60mm-70mm, 70mm-80mm, 80mm-90mm, 90mm-100mm, 100mm-110mm, 110mm-120mm, 120mm-130mm, 130mm-140mm or 140mm-150mm.
- the position and number of the plasma source unit 50 outside the main body 10 can be adjusted as needed.
- the number of the plasma source unit 50 is one, which is set at One side of the main body 10, and further, the plasma source unit 50 is disposed on a side of the main body 10 that is perpendicular to the holding electrode plate 60, refer to FIG. 3.
- the two plasma source units 50 are respectively symmetrically arranged on two sides of the main body 10, and further, the two plasma source units 50 They are respectively arranged on two sides of the main body 10 perpendicular to the object plate 60.
- the DLC preparation device includes a pump system 70 connected to the reaction chamber 100 to adjust the gas pressure in the reaction chamber 100.
- the pump system 70 includes a pressure regulating valve 71 for regulating the pressure in the reaction chamber 100.
- the pump system 70 can be used to pump the gas in the reaction chamber 100 so that its pressure decreases or tends to a predetermined pressure range.
- the pump system 70 can be used to deliver gas into the reaction chamber 100 to Provide gas reaction materials.
- the DLC preparation device includes a temperature detection module 80 for detecting the temperature in the reaction chamber 100 to feedback control other process parameters of the diamond-like carbon film preparation device.
- the temperature detection module 80 is a thermocouple.
- the temperature detection module 80 is set at an equivalent position of the placement position of the substrate, so as to detect the real-time reaction temperature of the substrate.
- the temperature detection module 80 is arranged directly below the sample placement position of the storage plate 60, or the temperature detection module 80 is installed around the sample placement position on the storage plate 60, or the temperature The detection module 80 is arranged directly above the sample placed on the holding plate 60, or the temperature detection module 80 is set at a position of the holding plate 60 where the sample is placed, such as in the air hole under the substrate.
- the control range of the reaction temperature in the reaction chamber 100 of the DLC preparation device is 25°C-100°C.
- the temperature range is 25°C to 50°C.
- the influence on the substrate is small, and it is suitable for products that are not resistant to high temperatures, such as electronic products.
- the materials used in mainstream electronic products are polymer materials, which have poor resistance to heat deformation and generally have a temperature resistance below 100°C.
- the coating process needs to ensure that the performance of the raw materials is changed, so Low temperature technology is a hard requirement for electronic product processing.
- the reaction temperature is detected in real time by a thermocouple placed at an equivalent position to the product, and the reaction temperature is controlled so that it will not affect the electronic equipment.
- the diamond-like carbon film it can be formed on a separate part of a product, such as on an unassembled electronic screen, or on an assembled product, such as on a screen assembled into an electronic device. The process conditions More flexible.
- the DLC preparation device includes a control unit 90 that controls the reaction conditions in the preparation device.
- the control unit 90 controls the gas supply of the plasma source supply unit and the reaction
- the control unit 90 can obtain the targeted diamond-like carbon film by controlling process parameters such as the discharge characteristics of radio frequency and high-voltage pulses, the flow rate of the reactive gas, and the coating time.
- control unit 90 can control the electrode discharge characteristics of the pulse power supply 40 and the radio frequency power supply 30, and can control the gas flow rate, coating time and other process parameters of each of the gas supply units 20, so as to easily obtain the targeted DLC. film.
- the preparation process of ion exchange reinforced glass in the prior art is cumbersome, requiring high temperature heating of potassium nitrate plasma salt to form an ion bath, and the ion exchange time is long and the cost is relatively high.
- the DLC preparation device uses the PECVD method to directly deposit diamond-like carbon films on the surface of substrates such as glass, which can be completed at room temperature, and the required time is short, which is conducive to cost control; on the other hand, the method of the present invention
- the DLC preparation device in the embodiment uses radio frequency and high voltage pulse assisted plasma chemical vapor deposition, uses low power radio frequency discharge to maintain the plasma environment, suppresses arc discharge in the high voltage discharge process, and is similar to magnetron sputtering in the prior art.
- the physical vapor deposition method has a lower substrate temperature and can be applied to the coating of some electronic devices that are not resistant to high temperatures.
- the mobile phone glass screen is strengthened, the mobile phone glass can be assembled first and then DLC vapor deposition coating, that is to say, the DLC film is set after the electronic device is manufactured, and the process flexibility is high; on the other hand,
- the control unit 90 controls the synergistic effect of multiple parameters, and the preparation process has good process controllability.
- a method for preparing a DLC film which includes the following steps:
- the preparation method of the DLC film may include the following processes:
- Step (1) Cleaning and activating the sample surface: place the substrate after ultrasonic treatment in alcohol and acetone in the sample chamber and then evacuate it to below 1.5 ⁇ 10 -3 Pa, and pass the high-purity helium substrate in the plasma source gas Perform etching and cleaning.
- the radio frequency power supply 30 and the high-voltage pulse power supply 40 are turned on, the plasma source gas glow discharge generates plasma, and the substrate is etched, cleaned and activated for 10 minutes. That is, one embodiment of step (A)-step (B).
- Step (2) Depositing DLC film: After cleaning, prepare transparent hard hydrogen-containing diamond-like carbon film by using radio frequency and high-voltage pulses to assist plasma chemical vapor deposition: pass a carbon and hydrogen source as a reactive gas source, and turn on the RF power supply 30 and the high-voltage pulse power supply 40, or keep the power supply in the on state in step (1) to perform deposition. After the thin film is deposited, it is turned off and the vacuum is released to take out the sample. That is, one embodiment of step (C)-step (D).
- the diamond-like carbon thin film preparation device includes a multi-layer electrode group, so multiple or a larger number of the substrates can be placed at a time and suitable for large-area coating needs, thereby performing batch coating process.
- step (1) the sample surface is cleaned and activated, the flow rate of argon gas is 50sccm-200sccm, the pressure range of the reaction chamber 100 is controlled to below 30mtorr, the high-voltage pulse power supply is 40 voltage-1000V, and the duty ratio is 10 %, cleaning time 10min.
- step (1) in one embodiment, the effects of radio frequency electric field and high-voltage pulsed electric field are required to pretreat the surface of the substrate, that is, in the implementation process of step (B), only the pulse power supply 40 is turned on, so that The electrode plate 60 can discharge.
- the plasma source gas such as argon or helium
- the plasma source gas generates plasma under the action of a high-voltage pulse electric field and a radio frequency electric field, and performs a plasma vapor deposition process on the surface of the substrate.
- Micro-etching is performed on the surface of the substrate, that is, a small amount of surface layer is peeled off, but due to its inert effect, it cannot deposit and stay on the surface of the substrate.
- Step (1) prepares ionization conditions for the deposition of the reactive gas raw materials, and causes the surface of the substrate to be slightly etched to clean the surface, so that the subsequently deposited diamond-like carbon film is more firmly bonded to the surface of the substrate.
- the flow rate of the gas added to the reaction chamber 100 corresponds to the corresponding pressure, and too high or too low pressure will affect the ionization effect. Too low pressure cannot achieve the cleaning effect, and too high pressure may damage the substrate. The length of the cleaning time affects the cleaning effect, and the cleaning time is too short to achieve the cleaning effect. The time course will have the risk of over-etching, and it will increase the entire process cycle and increase the process cost.
- the flow rate of argon or helium is 50sccm-200sccm
- the pressure in the reaction chamber is controlled to be 50-150mtorr
- the voltage of the high-voltage pulse power supply is 40-200V ⁇ -5000V, duty ratio of 10% to 60%, cleaning time of 5 to 15 minutes, within these ranges, the above-mentioned various factors can be better adjusted to make it beneficial to the entire deposition process of the DLC film.
- a transparent hard hydrogen-containing diamond-like carbon film is prepared by a method of radio frequency and high-voltage pulse voltage-assisted plasma chemical vapor deposition.
- This method can maintain the plasma environment of the entire coating stage by radio frequency, and by applying a pulsed high voltage to the sample substrate, during the discharge process of the pulse power supply 40, the active particles can be deposited on the surface of the substrate under the action of a strong electric field to form amorphous carbon Network structure.
- the process of non-discharge is a process of free relaxation of the amorphous carbon network structure.
- the carbon structure transforms into a stable phase---nanocrystalline graphene sheet structure under the action of thermodynamics, and is embedded in the amorphous carbon network to form Transparent amorphous/nanocrystalline graphene sheet-layer composite structure.
- the film forming gas 99.999% methane, argon, hydrogen and 99.5% acetylene are used as the film forming gas (the carbon source is provided by methane or acetylene, and it can be doped with argon or hydrogen.
- the ratio of carbon source and doping gas can be from 5:1 to 1: 5 adjustment), 30 to 500 SCCM reactant gas is supplied from the gas supply unit 20, and the chamber pressure is set to 0.5 to 10 Pa.
- 100-700W is applied to the inductively coupled plasma source (ICP) 50 to generate an inductive oscillating electromagnetic field in the reaction chamber 100, and ionize the passing gas to form plasma.
- a bias voltage of -600-1200V is applied to the cathode electrode plate to accelerate the pulling of the plasma formed by the inductively coupled plasma source (ICP), thus forming a transparent hard nanocomposite film on the substrate.
- the pressure control range within 100 is 50-150mTorr
- the RF power supply 30 power range is 50-300W
- the bias pulse power supply is 40 voltage-200V—-5000V, duty cycle 10%-80%, coating time 5-30min, and finally get 5- 1000nm transparent hard hydrogen-containing diamond-like carbon film.
- the ratio of the different gas flow rates introduced affects the atomic ratio of the DLC film and the performance of the film.
- the CH 4 gas flow rate is 40-100 sccm and C 2 gas flow rate is 40-100 sccm
- the H 2 gas flow rate is 50-200 sccm
- the Ar gas flow rate is 40-100 sccm
- the H 2 gas flow rate is 40-100 sccm
- the rigidity of the DLC film is better, and the flexibility of the DLC film can be adjusted by hydrogen and maintained The predetermined deposition reaction rate.
- the power electric field of the radio frequency power supply 30 and the power supply voltage of the pulsed electric field affect the temperature rise, ionization rate, and deposition rate of the ionization process.
- the radio frequency power supply 30 The power range is 50-300W
- the bias pulse power supply is 40 voltage-200V-5000V
- the duty cycle is 10%-80%.
- the magnitude of the negative bias is directly related to the ionization of the gas and the migration ability when it reaches the surface of the product.
- High voltage means higher energy, and high hardness coatings can be obtained.
- high ion energy will have a strong bombardment effect on the substrate product, so bombardment pits will be generated on the surface on a microscopic scale.
- high-energy bombardment will accelerate the temperature rise, which may cause excessive temperature and damage the product. Therefore, it is necessary to balance the bias value, reaction temperature and reaction rate.
- the frequency of the radio frequency is 20-300KHz, and the higher pulse frequency can avoid the continuous accumulation of charges on the surface of the insulating product, suppress the large arc phenomenon and increase the coating thickness limit.
- the coating time is too short, the film formed is thinner and has poor hardness performance, while the coating time is too long and the thickness increases, but the transparency is affected.
- the coating time is 5-30 minutes, the thickness, hardness and transparency can be balanced, and finally a 5-1000nm transparent hard hydrogen-containing diamond-like carbon film can be obtained.
- the temperature control range in the reaction chamber 100 is 25°C to 100°C.
- the temperature range is 25°C to 50°C.
- the DLC film is formed, and the film formation under the predetermined conditions described in the above embodiment is used as an example, and the film formation under conditions other than the conditions is used as an example.
- the film characteristics of the DLC film in each case were measured.
- the apparatus of the structure demonstrated in the said embodiment with reference to FIG. 1 was used as a film-forming apparatus.
- a 6.5-inch quartz glass screen is used as the base material.
- the glass screen needs to be ultrasonically cleaned with absolute ethanol and acetone for 20 minutes, then dried with nitrogen, clamped in the vacuum chamber, and the pressure in the chamber is evacuated to less than 1.5 ⁇ 10 -3 Pa through the evacuation system, and then pass in 100SCCM high-purity argon gas, turn on the bias power (DC pulse) and RF power, the chamber pressure is controlled at 25mtorr, the bias power voltage is 500-900V, the duty cycle is 10%, the frequency is 80kHz, and the substrate is cleaned for 10 minutes .
- a film is plated on the substrate, and as shown in each of the examples and comparative examples described below, the DLC film is plated by the ICP-enhanced CVD method.
- the first set of examples methane and argon combination
- the coating gas was a combination of CH 4 and Ar with a purity of 99.999%.
- the coating conditions gas pressure, gas flow rate, power supply conditions, and coating time
- Table 2 also describes the characteristics of the film layer under different coating conditions (film thickness, hardness, light transmittance).
- the pressure of the chamber of this series of embodiments is maintained at 25 mtorr, and the embodiments are carried out by setting different bias values to carry out the experiment.
- the bias power supply and the radio frequency power supply are separately used.
- Comparing Example 2 with Comparative Example 1 and Comparative Example 2 it can be found that the film deposited by ICP without bias voltage has a slow film formation speed and poor hardness performance, while those obtained by only applying bias voltage without using ICP technology The performance and quality index of the film is worse than that of Example 1. This is due to the comprehensive use of ICP and bias electrode technology to obtain a composite structure of amorphous carbon and nanocrystalline graphene (as shown in Figure 7).
- Example 4 a combination of C 2 H 2 with a gas purity of 99.9% and Ar with 99.999% was selected as the reaction gas.
- the coating conditions gas pressure, gas flow rate, power supply conditions, and coating time
- Table 3 also describes the characteristics (film thickness, hardness, light transmittance) of the film layer under different coating conditions.
- the pressure of the chamber of this series of embodiments is maintained at 25 mtorr, the bias power supply voltage value is set to 900V, and the embodiments are carried out by setting different radio frequency powers to carry out the experiment.
- the bias power supply and the radio frequency power supply separately, compare the comparative examples 1 and 2, and compare the influence of different power supply combinations on the quality of the film under different carbon sources.
- the coating gas is a combination of C 2 H 2 and H 2 with a purity of 99.999%.
- the coating conditions gas pressure, gas flow rate, power supply conditions, and coating time
- Table 4 also describes the characteristics (film thickness, hardness, light transmittance) of the film layer under different coating conditions.
- the bias value is set to 900V
- the radio frequency power is 300W
- the experiment is carried out by setting different chamber pressures.
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Abstract
DLC制备装置和制备方法,其中所述DLC制备装置包括一主体(10),一等离子体源单元(50)和至少一气体供给部(20);所述主体(10)具有一反应腔室(100),所述反应腔室(100)用于放置一基体;所述气体供给部(20)用于向所述反应腔室(100)提供反应气体,所述等离子体源单元(50)被设置于所述主体(10)外部,向所述反应腔室(100)提供射频电场,以促进产生等离子体,使得所述反应气体通过PECVD方式沉积于所述基体的表面形成一DLC膜。
Description
本发明涉及类金刚石薄膜制备领域,更进一步,涉及一透明硬质的DLC制备装置和制备方法,所述DLC适于被沉积于电子设备及其配件的表面进行防护作用。
类金刚石薄膜(Diamond Like Carbon,DLC)是一种包含有sp3和sp2碳键的亚稳态材料,兼具了金刚石和石墨的优良特性,其具有高硬度、高电阻率、良好光学性能以及优秀的摩擦学特性。类金刚石薄膜具有多种不同的结构形式,特殊结构的碳纳米材料(类富勒烯结构碳,纳米非晶碳,石墨烯),因其具有超低摩擦系数、高硬度、良好的弹性恢复以及优良的耐磨性,已作为一类高性能固体润滑材料而受到了科学界和工业界的广泛关注。
现有的类金刚石薄膜的制备方法中的其中一种是物理气相沉积方法,比如通过磁控溅射方式形成镀膜,由此得到DLC膜;另一种是化学气相沉积方法,比如利用等离子体增强化学气相沉积(PECVD)沉积DLC膜,它是以碳氢气体如甲烷、乙烷、乙炔、苯、丁烷等为碳源,在等离子体的作用下碳氢气体经过活化、解离、沉积等复杂过程,制得含有一定氢的DLC膜。
另一方面,DLC的制备过程涉及复杂的反应过程,形成DLC膜的特性与众多因素有关,比如原材料的成分比例,具体工艺条件的控制等,其中对于相同的原料工艺条件的控制也明显影响形成的DLC膜的特性,且影响方式相对复杂。而对于不同的镀膜产品,其需要的DLC膜的性能也不同,在电子设备领域,如应用于智能手机屏幕时,其不仅需要提高其表面的刚性,还需要保持良好的透光性能,而不影响电子设备屏幕的视觉效果。
发明内容
本发明的一个优势在于提供一DLC制备装置和制备方法,其利用内外配置 的射频电场和高压脉冲电场协同作用来进行等离子体增强化学沉积反应(PECVD)形成DLC膜。
本发明的另一个优势在于提供一DLC制备装置和制备方法,其由感应耦合形成的射频电场和高压脉冲电场来配合提供等离子体增强化学沉积反应条件,由反应气体在该反应条件下制备DLC膜。
本发明的另一个优势在于提供一DLC制备装置和制备方法,其利用不同方向的射频电场和高压脉冲电场协同作用来进行等离子体增强化学沉积反应形成所述DLC膜。
本发明的另一个优势在于提供一DLC制备装置和制备方法,其利用低功率射频放电维持等离子体环境,抑制高压放电过程的弧光放电,由此提高化学沉积效率。
本发明的另一个优势在于提供一DLC制备装置和制备方法,其通过控制偏压值来控制DLC膜的性能,保持较高的沉积效率,获得较高的表面硬度和高透过率的DLC膜。
本发明的另一个优势在于提供一DLC制备装置和制备方法,其通过控制射频功率来改变离子浓度,增加镀膜效率。
本发明的另一个优势在于提供一DLC制备装置和制备方法,其通过控制腔体压力来调节辉光现象,以调节成膜速率和膜层质量。
本发明的另一个优势在于提供一DLC制备装置和制备方法,其能够通过控制射频和高压脉冲的放电特性、反应气体的流量以及镀膜时间等工艺参数,来获得目标DLC。
本发明的另一个优势在于提供一DLC制备装置和制备方法,其中在一个实施例中,所述射频电场和高压脉冲电场的方向相互垂直。
本发明的另一个优势在于提供一DLC制备装置和制备方法,其中所述DLC膜适于被沉积于电子设备及其配件的表面,且保持良好的透光性。
本发明的另一个优势在于提供一DLC制备装置和制备方法,其中PECVD沉积过程反应时间较短,沉积效率较高,使得整体生产效率高,适于大规模生产应用。
本发明的一方面提供一DLC制备装置,其包括:
一主体,所述主体具有一反应腔室,所述反应腔室用于放置一基体;
一等离子体源单元;和
至少一气体供给部,所述气体供给部用于向所述反应腔室提供反应气体,所述等离子体源单元被设置于所述主体外部,向所述反应腔室提供射频电场,以促进产生等离子体,使得所述反应气体通过PECVD方式沉积于所述基体的表面形成一DLC膜。
根据一个实施例所述的DLC制备装置,其包括一射频电源,所述射频电源电连接所述等离子体源单元,为所述等离子体源单元提供电源。
根据一个实施例所述的DLC制备装置,其中所述等离子体源单元包括一进气框、一隔离板和一感应线圈,所述进气框被密封地设置于所述主体外部,所述隔离板位于所述进气框和所述感应线圈之间。
根据一个实施例所述的DLC制备装置,其中所述进气框具有一连通通道,连通所述主体的所述反应腔室和所述气体供给部。
根据一个实施例所述的DLC制备装置,其中所述进气框具有至少一连通孔和一主通道,所述主体具有一窗口,所述窗口连通所述反应腔室,所述主体的所述窗口和所述进气框的所述连通孔以及所述主通道连通形成所述连通通道。
根据一个实施例所述的DLC制备装置,其中所述连通口和所述主通道位于相互垂直的方向。
根据一个实施例所述的DLC制备装置,其中所述进气框具有至少一连通孔、一内连通道、一布气孔和一主通道,所述连通孔连通外部,用于输入气体,所述布气孔被设置于所述进气框内侧并且连通所述主通道,所述内连通道连通所述连通孔和所述布气孔,所述主体的所述窗口、所述进气框的所述连通孔、所述内连通道、所述布气孔和所述主通道连通形成所述连通通道。
根据一个实施例所述的DLC制备装置,其中多个所述内连通道相互连通形成一内环形通道。
根据一个实施例所述的DLC制备装置,其中所述等离子体源单元进一步包括一外盖板,所述感应线圈被夹持于所述隔离板和所述外盖板之间。
根据一个实施例所述的DLC制备装置,其中所述进气框包括一主框体和一插接组件,所述主框体被密封地设置于所述主体的外部,所述插接组件被设置于所述主框体的外部,所述隔离板、所述感应线圈和所述外盖板被插接于所述插接组件。
根据一个实施例所述的DLC制备装置,其中所述隔离板是陶瓷密封板。
根据一个实施例所述的DLC制备装置,其中所述等离子体源单元是一种射频感应耦合等离子体源,提供感应耦合电场。
根据一个实施例所述的DLC制备装置,其中所述DLC制备装置包括一置物极板和一脉冲电源,所述置物极板被容纳于所述反应腔室内,所述置物极板电连接所述脉冲电源,用于向所述反应腔室提供脉冲电场,所述基体适于被放置于所述置物极板。
根据一个实施例所述的DLC制备装置,其中所述置物极板具有一气孔,连通所述置物极板的两侧。
根据一个实施例所述的DLC制备装置,其包括多个置物极板,多个所述置物极板平行间隔地布置。
根据一个实施例所述的DLC制备装置,其中所述脉冲电源电压控制范围为-200V—-5000V。
根据一个实施例所述的DLC制备装置,其中所述气体供给部包括一等离子体源供给部,所述等离子体源供给部用于向所述反应腔室提供一等离子体源气体,以激活PECVD沉积反应。
根据一个实施例所述的DLC制备装置,其中所述等离子体源气体选自组合:惰性气体、氮气、氟碳气体中的一种或多种。
根据一个实施例所述的DLC制备装置,其中所述气体供给部包括一反应气体原料供给部,所述反应气体原料供给部用于向所述反应腔室提供一碳氢气体C
xH
y,所述碳氢气体C
xH
y通过PECVD方式沉积于所述基体表面,以形成所述类金刚石薄膜。
根据一个实施例所述的DLC制备装置,其中所述气体供给部包括一辅助气体供给部,所述辅助气体供给部用于向所述反应腔室提供一辅助气体,所述辅助气体用于调节所述类金刚石薄膜中的C-H含量,与所述碳氢气体C
xH
y反应沉积于所述基体的表面形成所述类金刚石薄膜。
根据一个实施例所述的DLC制备装置,其中所述辅助气体选自组合:氮气、氢气、氟碳气体中的一种或多种。
根据一个实施例所述的类金刚石薄膜制备装置,其包括一温度检测模块,所述温度检测模块被设置于所述基体放置位置的等效位置。
本发明的另一方面提供一DLC膜制备方法,其包括,向一反应腔室提供一反应气体,在一射频电场和一脉冲电场的作用下,促使反应气体通过PECVD方式沉积于所述反应腔室内的一基体的表面形成一DLC膜。
根据一个实施例所述的DLC膜制备方法,其中在控制过程中,先打开射频电场,后打开脉冲电场。
根据一个实施例所述的DLC膜制备方法,其中所述射频电场被设置于所述脉冲电场外部。
根据一个实施例所述的DLC膜制备方法,其中所述射频电场是感应耦合电场。
根据一个实施例所述的DLC膜制备方法,其中包括步骤:向所述反应腔室提供一等离子体源气体,以激活PECVD沉积反应,所述射频电场和所述脉冲电场同时作用于所述等离子体源气体。
根据一个实施例所述的DLC膜制备方法,其中包括步骤:向所述反应腔室提供一辅助气体,所述辅助气体用于调节所述类金刚石薄膜中的C-H含量,与所述碳氢气体C
xH
y反应沉积于所述基体的表面形成所述DLC膜。
根据一个实施例所述的DLC膜制备方法,其中在所述反应腔室内设置一置物极板,所述置物极板电连接一脉冲电源,以在所述反应腔室内提供所述脉冲电场。
根据一个实施例所述的DLC膜制备方法,其中包括步骤:检测所述基体等效位置的温度,以反馈控制。
本发明的另一方面提供一DLC膜制备方法,其包括步骤:
a)向一装载了基体的反应腔室通入一等离子体源气体;
b)打开脉冲电源和射频电源,分别提供射频电场和脉冲电场,激活所述等离子体源气体产生等离子体;和
c)向所述反应腔室中通入一碳氢气体C
xH
y,在所述基体表面沉积DLC膜。
根据一个实施例所述的DLC膜制备方法,其中在所述步骤b)中,先打开射频电源,后打开脉冲电源。
根据一个实施例所述的DLC膜制备方法,其中包括步骤:在脉冲电场外部设置射频电场。
根据一个实施例所述的DLC膜制备方法,其中所述射频电场是感应耦合电 场。
根据一个实施例所述的DLC膜制备方法,其中步骤c)包括步骤:向所述反应腔室提供一辅助气体,所述辅助气体用于调节所述类金刚石薄膜中的C-H含量,与所述碳氢气体C
xH
y反应沉积于所述基体的表面形成所述类金刚石薄膜。
根据一个实施例所述的类金刚石薄膜制备方法,其中包括步骤:抽取所述反应腔室中的气体,调节所述反应腔室中的气体压强大小。
根据一个实施例所述的类金刚石薄膜制备方法,其中包括步骤:检测所述基体等效位置的温度,以反馈控制。
图1是根据本发明的一个实施例的DLC制备方法框图。
图2是根据本发明的上述实施例的DLC制备装置框图。
图3是根据本发明的上述实施例的DLC制备装置简图。
图4A-4B是根据本发明的上述实施例的DLC制备装置的一种实施方式立体图。
图4C是根据本发明的上述实施例的DLC制备装置的另一种实施方式立体图。
图5A是根据本发明的上述实施例的DLC制备装置的一种实施例方式的分解示意图。
图5B是根据本发明的上述实施例的DLC制备装置的进气框的变形实施例的示意图
图6是根据本发明的上述实施例的DLC制备装置的变形实施方式简图。
图7是根据本发明的上述实施例的类金刚石薄膜的透射电镜图。
以下描述用于揭露本发明以使本领域技术人员能够实现本发明。以下描述中的优选实施例只作为举例,本领域技术人员可以想到其他显而易见的变型。在以下描述中界定的本发明的基本原理可以应用于其他实施方案、变形方案、改进方案、等同方案以及没有背离本发明的精神和范围的其他技术方案。
本领域技术人员应理解的是,在本发明的揭露中,术语“纵向”、“横向”、“上”、 “下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”等指示的方位或位置关系是基于附图所示的方位或位置关系,其仅是为了便于描述本发明和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作,因此上述术语不能理解为对本发明的限制。
可以理解的是,术语“一”应理解为“至少一”或“一个或多个”,即在一个实施例中,一个元件的数量可以为一个,而在另外的实施例中,该元件的数量可以为多个,术语“一”不能理解为对数量的限制。
对“一个实施例”、“实施例”、“示例实施例”、“各种实施例”、“一些实施例”等的引用指示这样的描述本发明的实施例可包括特定特征、结构或特性,但是不是每个实施例必须包括该特征、结构或特性。此外,一些实施例可具有对其它实施例的描述的特征中的一些、全部或没有这样的特征。
图1是根据本发明的一个实施例的DLC制备方法框图。图2是根据本发明的上述实施例的DLC制备装置框图。图3是根据本发明的上述实施例的DLC制备装置简图。
参考图1-图5A,本发明提供一DLC制备装置,所述DLC制备装置用于进行PECVD反应,从而制备一DLC膜,所述DLC膜适于被沉积一基体的表面,以改善所述基体的表面性能。更进一步,所述DLC制备装置用于通过等离子体增强化学沉积(PECVD)方式向所述基体表面化学沉积形成所述DLC膜。换句话说,所述基体被放置于所述DLC制备装置的反应腔室中进行等离子体增强化学气相沉积而在所述基体的表面形成所述DLC膜。
“基体”是指待镀膜的小面积或者大面积物件或者具有通过本发明的方法改进的表面。本文中所指的基体可以是由玻璃、塑料、无机材料或者具有待镀膜的或者改进的表面的任何其它材料。所述基体可以是电子设备及其配件,举例地但限于智能手机、平板电脑、电子阅读器、可穿戴设备、电视机、电脑显示屏、玻璃屏幕、柔性屏。
“等离子体”是指电子,正、负离子,激发态原子、分子以及自由基混杂的状态。
进一步,根据本发明的一个实施例,所述DLC制备装置以碳氢气体C
xH
y作为反应气体原料,进行等离子体增强化学气相沉积得到所述DLC膜。
所述DLC膜能够提高所述基体的表面刚性,比如提高莫氏硬度,也可以提 高所述基体的耐摔性能以及耐摩擦性能。所述DLC是纳米膜,具有较小的厚度,其厚度范围举例地但不限于10~2000nm。
所述DLC制备装置通过PECVD工艺将C
xH
y气体反应原料气相沉积于所述基体的表面,借助等离子体的化学沉积反应过程,可以使得所述DLC膜的厚度较小,如纳米尺寸,且在PECVD沉积过程中能够通过控制工艺参数来获取目标性的所述DLC膜。比如,控制获取预定厚度的所述DLC。也就是说,预定厚度的所述DLC膜分别是在不同的预定反应条件下获得,而不是任意数值的选取。
C
xH
y中x为1-10的整数,y为1-20的整数。所述反应气体原料可以是单一气体,也可以是两种或者两种以上的气体混合物;优选地,所述碳氢气体选自常压下为气态的甲烷、乙烷、丙烷、丁烷、乙烯、乙炔、丙烯、丙炔,也可以是经过减压或者加热蒸发形成的蒸气,比如苯蒸气、甲苯蒸气。
等离子体增强化学气相沉积(PECVD)工艺相较于现有的其它沉积工艺具有很多优点:(1)干式成膜不需要使用有机溶剂;(2)等离子体对基体表面的刻蚀作用,使所沉积上的薄膜与基体粘结性好;(3)可以对不规则基体表面均匀沉积镀膜,气相渗透性极强;(4)涂层可设计性好,相比于液相法微米级控制精度,化学气相法可在纳米级尺度进行涂层厚度的控制;(5)涂层结构设计容易,化学气相法使用等离子体激活,对不同材料的复合涂层不需要设计特定的引发剂进行引发,通过输入能量的调控即可将多种原材料复合在一起;(6)致密性好,化学气相沉积法在等离子体引发过程中往往会对多个活性位点进行激活,类似于溶液反应中一个分子上有多个官能团,分子链之间通过多个官能团形成交联结构;(7)作为一种镀膜处理技术手段,其普适性极好,镀膜的对象、镀膜使用的原材料选择的范围都很广。
所述等离子体增强化学气相沉积(PECVD)工艺通过辉光放电产生等离子体,放电的方法包括微波放电、射频放电、紫外、电火花放电等。
进一步,根据本发明的一个实施例,所述DLC制备装置在制备所述DLC膜时,向所述DLC制备装置中通入一等离子体源气体,其用于激活所述反应气体原料的化学沉积反应。所述等离子体源气体举例地但限于惰性气体、氮气、氟碳气体,其中惰性气体举例地但不限于He、Ar,氟碳气体举例地但不限于四氟化碳。所述等离子体源气体是可以单一气体,也可以是两种或者两种以上的气体的混合物。所述等离子源气体可以与所述反应气体原料同时通入,也可以先后通入。 优选地,先通入所述等离子体源气体,而后再通入所述反应气体原料。当然,在本发明的一个实施例中,也可以没有所述等离子体源气体,也就是说,直接由所述反应气体原料沉积于所述基体表面,此时需要的反应气体原料的量增加,以及在一定程度上会影响反应速度。
进一步,根据本发明的一个实施例,所述DLC制备装置在制备所述DLC膜时,在所述DLC制备装置中通入一辅助气体,所述辅助气体与所述反应气体原料配合形成所述DLC膜,也就是说,其将作为类金刚石薄膜的组成部分。所述辅助气体是非碳氢气体,即C
xH
y之外的气体,含有C、H之外的元素。所述辅助气体用于调节所述DLC膜的性能,比如调节刚性提高柔韧性。通过所述辅助气体的添加可以调节单纯碳氢气体形成的所述DLC膜中的C-C含量和/或C-H以及其它键的含量,以及结合所述辅助气体自身的特征来调整所述DLC膜的性能。
所述辅助气体举例但不限于氮气,氢气,氟碳气体,所述辅助气体可以与所述反应气体原料同时通入,也可以先后通入,优选地,所述辅助气体与所述反应气体原料同时通入。也就是说,由此可以制得不同氢含量的含氢类金刚石薄膜或者含氮类金刚石薄膜、含氟类金刚石薄膜等。所述辅助气体可以调节所述DLC膜中的C-H键、C-N键、N-H键的比例含量,由此改变所述DLC的性能。
值得一提的是,所述辅助气体的加入能够调节所述DLC膜的性能,其在增加改善性能同时会相对弱化所述DLC膜的刚性以及原本的性能,因此需要平衡添加量。发明人发现,当加入所述辅助气体时,可以改善所述DLC膜的预定性能,但是当所述辅助气体的加入量增加到一定程度时,所述DLC膜的硬度会明显下降。比如,当所述辅助气体是氢气时,所述辅助气体的作用是调节所述DLC膜中的碳氢比例,比如增加C-H键的含量,提高所述DLC膜的柔韧性。值得一提的是,当所述氢气的含量大于预定范围时,所述辅助气体会破坏所述DLC膜的刚性,因此需要控制加入的含量。当氢气含量大于40%时,其刚性会明显下降。含氢量较高的DLC膜相较于含氢量较低的DLC膜有着更高的润滑性和透明性,一定量的氢有利于SP3键的形成,在一定程度上可以提高硬度,但随着氢含量的进一步提高,类金刚石薄膜的硬度会逐步下降。
还值得一提的是,所述辅助气体的加入不仅能够调整所述DLC膜的性能,其还能够增加PECVD反应过程的离化浓度,促使反应更加快速地进行。
进一步,根据本发明的一个实施例,在所述DLC制备装置在制备所述DLC膜时,采用射频电场和脉冲电场的共同作用来辅助完成等离子体增强化学沉积过程。优选地,射频和高压脉冲同时作用于PECVD沉积过程。在射频和高压脉冲共同作用的过程中,利用低功率射频放电维持等离子体环境,抑制高压放电过程的弧光放电,由此提高化学沉积效率。
射频可通过对惰性气体、反应气体原料的放电使整个镀膜过程处于等离子体环境,反应气体原料处于高能量状态;脉冲高电压的作用是脉冲电源在放电过程中产生强电场,处于高能状态的活性粒子受到强电场作用加速沉积于基体表面,形成非晶态碳网络结构。脉冲电场处于不放电的状态时,利于沉积在基体表面的DLC薄膜进行非晶态碳网络结构自由驰豫,在热力学作用下碳结构向稳定相---弯曲石墨烯片层结构转变,并埋置于非晶碳网络中,形成透明类石墨烯结构。也就是说,射频电场、变化的脉冲电场相互结合作用,使得所述DLC膜能够快速、稳定地沉积于基体的表面。参考图7,是根据本发明的上述实施例的类金刚石薄膜的透射电镜图,所述DLC膜由非晶和纳米晶结构组成。
进一步,所述DLC制备装置在制备所述DLC膜时,所述等离子体源气体、所述反应气体原料和所述辅助气体被分阶段地加入所述DLC制备装置中,相应地,所述射频电场和所述脉冲电场被选择性地分阶段施加于被反应气体原料。
举例地但不限于,在一个实施例中,当所述等离子体源气体被加入所述DLC制备装置中时,也可以称为处于第一阶段时,施加射频电场和脉冲电场。在该阶段中,所述等离子体源气体在射频电场和脉冲电场的作用下形成部分等离子体,以及通过气体分子之间的相互作用,比如相互撞击作用,进一步促进产生部分等离子体。优选地,在打开所述射频电场和脉冲电场时,先打开所述射频电场,而后打开所述脉冲电场,这种方式中更容易启辉,从而使得离化作用更好;当所述反应气体原料和所述辅助气体原料被加入时,也可以称为第二阶段,同时施加所述射频电场和所述脉冲电场,也就是保持所述射频电源和脉冲电源的打开。在该阶段中,部分所述反应气体原料在所述射频电场和所述脉冲电场的作用下产生等离子体,部分所述反应气体在所述等离子体源气体产生的等离子体的激发作用下产生等离子体,部分所述辅助气体在所述射频电场和所述脉冲电场的作用下产生等离子体,部分所述辅助气体在其它等离子体的作用被激发产生等离子体,由此所述DLC制备装置中的等离子体浓度不断升高,由此激活等离子体的沉积反应 过程,使得所述DLC膜能够快速、有效地沉积于所述基体表面。本领域技术人员可以理解的是,等离子体增强化学气相沉积过程是一个非常复杂的反应过程,其进行离化沉积过程发生的反应不限于上述内容。
当所述等离子体源气体被加入所述DLC制备装置时,也可以称为处于第一阶段时,仅施加所述脉冲电场。在该阶段中,所述等离子体源气体在脉冲电场的作用下形成至少部分等离子体,以及气体分子之间的相互作用,比如相互撞击作用,进一步促进产生等离子体。当所述反应气体原料和所述辅助气体原料被加入时,也可以称为第二阶段,同时施加所述射频电场和所述脉冲电场。在该阶段中,部分所述反应气体原料在所述射频电场和所述脉冲电场的作用下产生等离子体,部分所述反应气体在所述等离子体源气体产生的等离子体的激发作用下产生等离子体,部分所述辅助气体在所述射频电场和所述脉冲电场的作用下产生等离子体,部分所述辅助气体在其它等离子体作用被激发产生等离子体,由此所述DLC制备装置中的等离子体浓度不断升高,由此激活等离子体的沉积反应过程,使得所述DLC膜能够快速、有效地沉积于所述基体表面。
在一个实施例中,所述射频电源和所述高压脉冲电源可以同时施加,也可以先后施加。在一个实施例中,在加入所述等离子体源气体时,先施加所述高压脉冲电源,在加入所述反应气体原料时,再施加所述射频电源,由此使得两个电场先后配合工作。在一个实施例中,在加入所述等离子体源气体时,施加所述射频电源,在加入所述反应气体原料时,再施加所述高压脉冲电源,由此使得两个电场先后配合工作。
值得一提的是,射频电场和脉冲电场的选择影响沉积形成的所述DLC膜的性能,而对于不同的装置结构,其优选的方式存在差异,在本发明的射频电场和脉冲电场内外布置的这种装置结构中,在第一阶段和第二阶段脉冲电场和射频电场同时施加成膜的效果要优于单独施加脉冲电场或者射频电场,且在打开顺序上,先打开射频电场,后打开脉冲电场要优于同时打开射频电场和脉冲电场以及先打开脉冲电场,后打开射频电场的方式,先打开射频电场,再打开脉冲电场的方式,气体更容易启辉而产生等离子体。值得一提的是,在一些实施例中,在第一阶段中加入的所述等离子体源气体只产生部分等离子体,但是由于其基本性质,比如惰性气体,其不会沉积于所述基体的表面,或者说其并不构成所述类金刚石膜的组成成分。在所述等离子体源形成等离子体时,等离子体作用于所述基体的表面, 对所述基体的表面产生蚀刻作用,即清除所述基体表面的残留物,并且为所述反应气体原料的沉积准备基础。所述等离子体源对所述基体的表面蚀刻作用,使得所述DLC膜更加牢固地沉积于所述基体的表面。在一些实施例中,在所述第一阶段加入的所述等离子体源气体只产生部分等离子体,其不仅会对所述基体产生蚀刻作用,且会沉积于所述基体的表面,比如和第二阶段的所述反应原料气体共同进行沉积反应。比如氮气和氟碳气体,其和第二阶段的所述反应气体原料碳氢气体共同进行沉积反应,可以调节所述DLC膜中的C-H键、C-N键、N-H键的比例含量,由此改变所述DLC膜的性能。
在所述第二阶段,所述反应源气体和所述辅助气体共同气相沉积于所述基体的表面形成所述DLC膜。
值得一提的是,射频和高压脉冲的共同作用增强了沉积效率,使得在所述基体表面能够有效沉积形成保护膜,也就是说,在较短时间内化学沉积反应形成所述DLC膜,由此提高了生产效率,使得所述DLC膜能够被批量化的工业生产。
进一步,在所述DLC制备装置在制备所述DLC膜时,控制进入装置的气体流量,以控制所述DLC膜的沉积速率,以及沉积厚度。举例地,控制所述等离子体源气体、所述反应气体原料和所述辅助气体的气体流量。在所述DLC制备装置在制备所述DLC膜时,控制反应腔体内的压强大小、射频功率大小、脉冲电压、占空比以及镀膜时间等工艺参数,由此获得预期的所述DLC膜。也就是说,通过调节、控制气体流量、反应腔体内的压强大小、射频功率大小、脉冲电压、占空比以及镀膜时间等工艺参数能够控制获得的所述DLC膜的性能,包括厚度、硬度、透明性等。
进一步,在所述DLC制备装置在制备所述DLC膜时,控制所述制备装置中的反应温度,比如通过温度检测模块来检测基体周围的温度,并且反馈调节其它工艺参数,使得温度控制在预定范围,制备装置内的温度范围为25℃~100℃。优选地,温度范围为25℃~50℃。
图2是根据本发明的一个实施例的DLC制备装置框图。图3是根据本发明的上述实施例的DLC制备装置简图。图4A-4B是根据本发明的上述实施例的DLC制备装置的一种实施方式立体图。图5A是根据本发明的上述实施例的DLC制备装置的一种实施例方式的分解示意图。
参考图2和图3,本发明提供一所述DLC制备装置,所述DLC制备装置用 于制备所述DLC膜,进一步,所述DLC装置用于通入反应气体进行PEDVD沉积,在基体表面形成所述DLC膜。
所述DLC制备装置包括一主体10,并且具有一反应腔室100,所述反应腔室100供容纳所述基体,以及供通入的气体进行沉积反应,所述主体100形成所述反应腔室100。
优选地,所述反应腔室100是一密闭腔室,也就是说,所述反应腔室100不会在非控制状态下气体流通。
进一步,所述多个气体供给部20包括一等离子体源供给部21、一反应气体原料供给部22和一辅助气体供给部23。所述等离子体源供部21被可控制地连通所述反应腔室100,所述等离子体源供给部21用于向所述反应腔室100供给所述等离子体源气体。所述等离子体源气体举例地但不限于惰性气体、氮气、氟碳气体,其中惰性气体举例地但不限于He、Ar,氟碳气体举例地但不限于四氟化碳。所述等离子体源气体可以是单一气体,也可以是两种或者两种以上的气体的混合物。
所述反应气体原料供给部22可控制地连通所述反应腔室100,所述反应气体原料供给部22用于向所述反应腔室100供给所述反应气体原料。所述反应气体原料是碳氢气体C
xH
y,C
xH
y中x为1-10的整数,y为1-20的整数。所述反应气体原料可以是单一气体,也可以是两种或者两种以上的气体混合物;优选地,所述碳氢气体选自常压下为气态的甲烷、乙烷、丙烷、丁烷、乙烯、乙炔、丙烯、丙炔,也可以是经过减压或者加热蒸发形成的蒸气,比如苯蒸气、甲苯蒸气。
所述辅助气体供给部23被可控制地连通所述反应腔室100,所述辅助气体供给部23用于向所述反应腔室100供给所述辅助气体。辅助气体举例地但不限于氢气、氮气、氟碳气体。
根据本发明的实施例,所述等离子体源供给部21包括多个供给管路26,分别用于供给不同的所述等离子体源气体。更具体地,所述等离子体源供给部21的供给管路26的数量或者说连通数量由需要通入的所述等离子体源气体决定。也就是说,当需要通入的所述等离子体源的气体种类为1时,所述等离子体源供给部21的供给管路26数量为1,当需要通入的所述等离子体源气体种类数量为2时,所述等离子体源供给部21的供给管路26的数量为2,依次类推。优选地,所述等离子体源供给部21的每个供给管路26供给单一的气体,也就是说,一个 供给管路26只通过一种气体,而不是多种气体或者混合气体,通过的方式,可以防止气体之间的预先反应,以及方便控制通入的气体量的多少。可选地,在一些实施例中,所述管路中可以通入多种气体,或者在多个管路中通入同一种气体。
在本发明的一个实施例中,所述等离子体源供给部21的多个供给管路26包括一个供给管路26,所述供给管路26用于向所述反应腔体通入所述等离子体源气体。举例地,在一个实施例中,所述等离子体源供给部21的供给管路26用于供给氩气。
所述反应气体原料供给部22包括多个供给管路26,分别用于供给不同的所述反应气体原料。更具体地,所述反应气体原料供给部22的供给管路26的数量或者说连通数量由需要通入的所述反应气体原料决定。也就是说,当需要通入的所述反应气体原料的气体种类为1时,所述反应气体原料供给部22的供给管路26数量为1,当需要通入的所述反应气体原料的气体种类数量为2时,所述反应气体原料供给部22的供给管路26的数量为2,依次类推。优选地,所述反应气体原料供给部22的每个供给管路26供给单一的气体,也就是说,一个供给管路26只通过一种气体,而不是多种气体或者混合气体,通过这样的方式,可以防止气体之间的预先反应,以及方便控制通入的气体量的多少。可选地,在一些实施例中,所述管路中可以通入多种气体,或者在多个管路中通入同一种气体。
在本发明的一个实施例中,所述反应气体原料供给部22的包括两个供给管路26,分别用于通入两种不同的气体,举例地但限于,其中一个所述管路供给甲烷,另一个所述管路用于供给乙炔。
所述辅助气体供给部23包括多个供给管路26,分别用于供给不同的所述辅助气体。更具体地,所述辅助气体供给部23的供给管路26的数量或者说连通数量由需要通入的所述辅助气体决定。也就是说,当需要通入的所述辅助气体的气体种类为1时,所述辅助气体供给部23的供给管路26数量为1,当需要通入的所述辅助气体的气体种类数量为2时,所述辅助气体供给部23的供给管路26的数量为2,依次类推。优选地,所述辅助气体供给部23的每个供给管路26供给单一的气体,也就是说,一个供给管路26只通过一种气体,而不是多种气体或者混合气体,通过的方式,可以防止气体之间的预先反应,以及方便控制通入的气体量的多少。可选地,在一些实施例中,所述管路中可以通入多种气体,或者在多个管路中通入同一种气体。
在本发明的一个实施例中,所述辅助气体供给部23的包括一个供给管路26,所述供给管路26用于向所述反应腔体通入所述辅助气体。举例地,在一个实施例中,所述辅助气体供给部23的供给管路26用于供给氢气。
根据本发明的一个实施例,所述类金刚石薄膜制备装置包括一汇合区25,所述汇合区25连通所述反应腔室100,所述汇合区25用于将各所述气体供给部20的气体汇合。也就是说,所述汇合部连通所述等离子体源供给部21、所述反应气体原料供给部22以及所述辅助气体供给部23。在本发明的一个实施例中,通入的气体经过所述汇合区汇合后送入所述反应腔室100。当然,在本发明的其它实施例中,各所述供给部也可以独立将气体送入所述反应腔室100。
所述气体供给部20包括一控制阀24,所述控制阀24用于控制气体的通断。更进一步,所述气体供给部20包括多个控制阀24,分别被设置于所述等离子体源供给部21、所述反应气体原料供给部22以及所述辅助气体原料供给部的供给管路26,以分别控制各管路中的气体流通。
所述类金刚石薄膜制备装置包括一射频电源30和一脉冲电源40,所述射频电源30用于向所述反应腔室100提供射频电场,所述脉冲电源40用于向所述反应腔室100提供脉冲电场。
图4A-4B是根据本发明的上述实施例的DLC制备装置的一种实施方式立体图。图4C是根据本发明的上述实施例的DLC制备装置的另一种实施方式立体图。图5A是根据本发明的上述实施例的DLC制备装置的一种实施例方式的分解示意图。图5B是进气框的变形实施例。图6是根据本发明的上述实施例的DLC制备装置的变形实施方式简图。
所述DLC制备装置包括一等离子体源单元50,所述等离子体源单元50电连接于所述射频电源30,以便于从所述射频电源30获取电能而产生射频电场。
所述等离子体源单元50被设置于所述主体10的外部,举例地但不限于,所述等离子体源单元50被设置于所述主体10的至少一侧。举例地,当所述主体10是方形结构时,所述等离子体源单元可以被设置于所述主体10的六个侧面的其中任一或者多个侧面,当所述主体10是柱体结构时,所述等离子体源单元能够被设置于所述主体10的环形侧面和/或者两底面。
参考图4A-5A,在本发明的这个实施例中,所述主体10进一步包括一箱体11和一控制门12,所述控制门12用于控制所述箱体11的打开或者关闭。所述 主体10设有一抽气口101,所述抽气口101被设置于所述箱体11的一侧面。在本发明的一个实施例中,所述抽气口101被设置于所述箱体11的背侧,即所述控制门12相对的一面。
在本发明的另一个实施例中,参考附图4C,所述抽气口101被设置于所述箱体11的顶侧,即,与所述控制门12相邻的顶侧面。在安装使用时,所述控制门12可以是朝向外侧方向,即朝向操作者一方,所述等离子体源单元50位于相邻的一侧面,所述抽气口101位于上侧面,即所述DLC制备装置的顶侧。
优选地,所述等离子体源单元50是一种射频感应耦合等离子体源(Radio Frequency Inductively Coupled Plasma Source,RF-ICP),用于向所述反应腔室100提供感应耦合电场,以产生等离子体。
所述等离子体源单元50包括一进气框51、一隔离板52和一感应线圈53,所述进气框51被密封地连接于所述主体10,更具体地,所述进气框51被贴靠于所述主体10的一侧面。所述隔离板52被设置于所述进气框51和所述感应线圈53之间。
参考图5A,所述进气框51具有至少一连通通道5100,所述连通通道5100用于连通所述主体和所述气体供给部,以便于通过所述气体供给部向所述主体的所述反应腔室通入气体原料。所述主体10具有一窗口1001,所述窗口1001连通所述反应腔室100和外部。所述连通通道5100连通所述窗口1001。也就是说,在工作时,所述气体供给部20供给气体,气体进入所述进气框51,通过所述进气框51的所述连通通道5100以及所述窗口1001进入所述反应腔室100。
进一步,所述进气框51具有至少一连通孔5101和一主通道5102,所述连通孔5101连通所述主通道5102形成一个所述连通通道5100。更具体地,所述连通孔5101被设置于所述进气框51的横向,也就是说,所述连通孔5101所在的平面与所述主体10的外侧面大致平行。所述主通道5102被设置于所述进气框51的纵向,也就是说,所述主通道5102的方向垂直于所述主体10的外侧面。换句话说,气体进入所述进气框51的方向和气体进入所述反应腔室100的方向不同,更具体地,气体进入所述进气框51的方向和气体进入所述反应腔室100的方向相互垂直。
值得一提的是,所述气体供给部20需要通过管路连通至所述进气框51,而所述隔离板52和所述感应线圈53被直接安装于所述进气框51的外侧,也就是 说,所述进气框51为所述隔离板52和所述感应线圈53提供安装位置,而进入的气体通过所述感应线圈53产生的感应耦合电场的作用而形成等离子体,因此,将气体进入的通道,即所述连通孔5101设置在横向,而将所述主通道5102,气体进入所述反应腔室100的通道,设置在纵向,更加高效地利用所述主体10的外部空间,使得所述DLC制备装置的主要体积不会太大,减少放置空间的占用。
所述主通道5102的尺寸大于所述连通孔5101的直径尺寸,或者说,所述主通道5102的容量大于所述连通孔5101的容量,值得一提的是,所述连通孔5101是气体进入的通道,通过较小的尺寸可以更加精确地控制气体流速。所述进气通道,是经过所述感应线圈53的作用形成等离子体的通道,更大的空间使得感应电场的作用面积更大,并且更多的气体分子或者离子之间的相互作用更强。
进一步,所述连通孔5101可以是直线延伸的形状,也可以是曲线或者其它不规则形状,也就是说,所述连通孔5101内部可以沿所述进气框51侧边直线延伸,也可以是曲线贯穿所述进气框51的侧边。所述连通孔5101的数量可以是一个或多个,在本发明的一个实施例中,分别在所述进气框51的四个侧边设置一个所述连通孔5101,分别连通所述主通道5102,从而使得所述进气框51的侧边空间都可以被利用。
所述进气框51具有多个安装孔5105,所述安装孔5105用于通过固定元件将所述进气框安装于所述主体10,举例地但不限于,通过螺钉穿过所述安装孔5105将所述进气框固定于所述主体10。
参考图5B,是根据发明的所述进气框51的另一变形实施例,在这个实施例中,所述进气框51进一步具有一内连通道5103,所述内连通道5103被设置于所述进气框51的内部,在内部连通相邻的两个所述连通孔5101。所述进气框51的内侧具有至少一内布气孔5104,所述内布气孔5104连通所述内连通道5103和所述主进气通道5102。也就是说,在本发明的这个实施例中,所述连通孔5101并不是直接连通所述主通道5102,而是通过所述内连通道5103以及所述内布气孔5104连通所述主通道5102。优选地,多个所述内布气孔5104分别被布置于所述进气框51内侧的不同位置,举例地但不限于,所述进气框51的四个边框内侧,由此更加均匀地进入所述主通道5102。
在发明的一个实施中,所述进气框51具有多个所述内连通道5103,分别相同连通,形成一内环形通道5200,由此使得通过任意一个所述连通孔5101都可 以将气体送入,而通过另一侧的任一所述布气孔5104将气体输送至所述主通道5102。
进一步,不同的气体可以在所述内连通道5103或者形成的所述内环形通道5200中进行于预先的汇合,使得气体混合更加充分,并且可以初步的反应,形成更多的等离子体。
进一步,所述布气孔5104的数量可以多于所述连通孔5101的数量,由此可以更加快速或者气量较多地进入所述主通道5102,在所述主通道形成更多等离子体,并且进入所述反应腔室100。
在本发明的一个实施例中,所述进气框51可以具有一个所述连通孔5101,用于进气,也就是说,当有多种气体需要输送时,可以先汇合通过所述连通孔5101进入,或者可以先后通过同一个所述连通孔5101进入所述内连通道5103,进而通过所述内布气孔5104分散至所述主通道5102的各个位置。
所述隔离板52封堵所述主通道5102的其中一端口,隔离所述进气框51的所述主通道5102和所述感应线圈53,也就是说,气体由所述连通孔5101进入,通过所述主通道5102进入所述反应腔室100,而不会流动到所述感应线圈53一侧。进一步,所述隔离板52密封、隔离气体但是不隔离电场,也就是说,所述主通道5102内的气体或者所述反应腔室100内气体能够接收到所述感应线圈53的感应电场作用。优选地,所述隔离板52是陶瓷密封板,从而减少对所述感应线圈53的感应电场馈入所述主通道5102和所述反应腔室100的影响。
所述等离子体源单元50进一步包括一外盖板54,所述外盖板54被设置于所述感应线圈53的外侧,换句话说,所述感应线圈53被夹持于所述隔离板52和所述外盖板54之间。
所述进气框51包括一主框体511和一插接组件512,所述主框体511被密封地设置于所述主体10的外侧,所述插接组件512被设置于所述主框体511的外侧,所述隔离板52、所述感应线圈53和所述外盖板54依次被插接于所述插接组件512,从而通过所述插接组件512将所述隔离板52、所述感应线圈53和所述外盖板54可拆卸地固定于所述主框体511。
所述DLC制备装置包括一置物极板60,所述置物极板60电连接所述脉冲电源40,以便于从所述脉冲电源40获取电能而产生脉冲电场。所述置物极板60被设置于所述反应腔室100内,以便于向所述反应腔室100提供脉冲电场。所述 置物极板是平面板状结构,适于放置所述基体。也就是说,待沉积的样品被放置于所述置物极板60上进行沉积作用。值得一提的是,所述置物极板60一方面用于放置所述基体,另一方面用于提供脉冲电场,也就是说,在所述基体的放置位置提供脉冲电场作用,即从所述基体的底部以及周围提供脉冲电场作用,电场作用更加直接。
根据本发明的实施例,所述类金刚石薄膜制备装置采用射频电场和高压脉冲电场的共同作用来辅助完成等离子体增强化学沉积过程。优选地,射频和高压脉冲同时作用于PECVD沉积过程。在射频和高压脉冲共同作用的过程中,利用低功率射频放电维持等离子体环境,抑制高压放电过程的弧光放电由此提高化学沉积效率。弧光放电是辉光放电进一步加强的放电形式,其瞬间电流可以达到几十甚至几百安培以上,这些高电流经过产品表面损坏产品,由于对于电子产品,其危害更大,而低频率射频放电维持低温等离子体环境,由此抑制脉冲高压放电过程的弧光放电,射频电场和脉冲电场相互配合来优化沉积过程,减少对待沉积的基体的损伤。
所述等离子体源单元50可通过对等离子体源气体、反应气体原料的放电使整个镀膜过程处于等离子体环境,反应气体原料处于高能量状态;所述脉冲电源40和所述置物极板60的脉冲高电压的作用是脉冲电源40在放电过程中产生强电场,处于高能状态的活性粒子受到强电场作用加速沉积于基体表面,形成非晶态碳网络结构。所述脉冲电源40和所述置物极板60处于不放电的状态时,利于沉积在基体表面的DLC薄膜进行非晶态碳网络结构自由驰豫,在热力学作用下碳结构向稳定相---弯曲石墨烯片层结构转变,并埋置于非晶碳网络中,形成透明类石墨烯结构。也就是说,射频电场、变化的脉冲电场相互结合作用,使得所述DLC薄膜能够快速、稳定地沉积于基体的表面。
值得一提的是,射频电场和高压脉冲电场的共同作用增强了沉积效率,使得在电子设备屏幕表面能够有效沉积形成保护膜,也就是说,在较短时间内化学沉积反应形成所述DLC膜,由此提高了生产效率,使得所述DLC膜能够被批量化地工业生产。
还值得一提的是,在现有技术中,通常采用磁控溅射镀膜的方式来形成类金刚石薄膜DLC,磁控溅射工艺是PVD工艺的一种,其以块状石墨靶材作为碳源,其离化效率和沉积效率都较低,因此在一些场合应用上会受限。而在本发明的实 施例中,PECVD碳源为气体,通过外加的直流脉冲电源40和射频电源30进行电离作用,离化程度和沉积效率提高,能够形成高硬度的DLC膜层,同时成本更低。另一方面,在PVD工艺中,以石墨作为碳源靶材,在制备过程中,需要对其预先加热,且反应速率慢,因此在整个过程中的热量积累较多,反应温度较高。而在本发明的PECVD反应过程中,碳源是气体,其不需要加热过程,沉积的薄膜较薄,沉积时间较短,因此在整个过程中的热量积累较少,反应温度较低,可以控制在25℃~100℃,适于一些电子设备的镀膜。
还值得一提的是,在实际的工业生产中,生产效率是其中一个重要因素,以手机屏幕为例,其只是手机众多部件中的其中一个,如果单纯为了提高屏幕的一些性能而耗费大量的时间,这个对于实际生产应用是不可行的,比如,在现有的一些DLC膜中,虽然其能够通过较长的反应时间达到改善性能的效果,但是其并不适于批量的生产应用,这也是限制一些膜被实际应用的一个因素之一,而在本发明的实施例中,通过所述DLC制备装置,在其反应腔室100中进行PECVD化学沉积,通过射频和高压脉冲的共同作用,其能够通过相对简单的工艺过程,并且使得沉积速率有效提高,由此使得类金刚石薄膜能够被广泛应用于批量化的工业生产中。
根据本发明的一个实施例,所述置物极板60具有一气孔,连通所述置物极板60两侧。所述气孔用于进入所述反应腔室100的气体穿过而对其产生放电作用。更进一步,当所述汇合部的通入的气体沿所述感应耦合等离子体源(ICP)的所述进气通道进入所述反应腔室100时,在所述置物极板60周围对所述气体产生放电作用,促使所述气体被离化而产生等离子体。
更进一步,所述置物极板60设置多个所述气孔,阵列地排布于所述置物极板60,以使得气流能够均匀地进入到达位于下方的所述置物极板60上方,并对气流产生相对一致的电场作用。
所述气孔可以是直线贯通的孔,也可以是曲线或者折线的方式连通所述置物极板60两侧的孔。所述气孔的横截面形状可以是圆形、方形、多边形或者其它曲线形状。
多个所述置物极板60被间隔地平行布置。相邻两所述置物极板60之间的间距为预定距离,相邻两所述置物极板60之间距离的选择,一方面需要考虑相邻两所述置物极板60上的基体施加的电场条件,另一方面需要考虑所述空间利用 率,即一次能够沉积的样品的和数量,比如,距离太大,脉冲电场作用较差,影响离化效率以及沉积效率,且空间利用率低,距离太小,脉冲电场作用太强,会影响基体比如电子设备的性能,且不利于样品的取放,工作效率底,因此需要平衡不同因素的影响。举例地,相邻两所述置物极板60之间的间距为10-200mm。优选地,相邻两所述置物极板60之间的间距为20mm-150mm。可选地,相邻两所述置物极板60之间的间距为20mm-30mm、30mm-40mm、40mm-50mm、50mm-60mm、60mm-70mm、70mm-80mm、80mm-90mm、90mm-100mm、100mm-110mm、110mm-120mm、120mm-130mm、130mm-140mm或140mm-150mm。
所述等离子体源单元50的在所述主体10外部的设置位置和设置数量可以根据需要调整,在本发明的一个实施例中,所述等离子体源单元50的数量为1个,被设置于所述主体10的一个侧面,更进一步,所述等离子体源单元50被设置于所述主体10的与所述置物极板60相互垂直的一个侧面,参考图3。在本发明的另一个实施例中,参考图6,两个所述等离子体源单元50分别对称地被设置于所述主体10的两个侧面,更进一步,两个所述等离子体源单元50分别被设置于所述主体10的与所述置物极板60相互垂直的两个侧面。
参考图3,所述DLC制备装置包括一泵系统70,所述泵系统70连接至所述反应腔室100,以调节所述反应腔室100内的气体压力大小。所述泵系统70包括一压力调节阀71,所述压力调节阀71用于调节所述反应腔室100内的压力。所述泵系统70能够用于抽取所述反应腔室100中的气体,使其压力减小或者趋向预定压强范围,所述泵系统70能够用于向所述反应腔室100内输送气体,以提供气体反应原料。
所述DLC制备装置包括一温度检测模块80,所述温度检测模块80用于检测所述反应腔室100内的温度,以反馈控制所述类金刚石薄膜制备装置的其它工艺参数。举例地但不限于,所述温度检测模块80是热电偶。
优选地,所述温度检测模块80被设置于所述基体放置位置的等效位置,以便于检测所述基体的实时反应温度。比如,所述温度检测模块80被设置于所述置物板60的放置样品位置的正下方,或者所述温度检测模块80被设置与所述置物板60上放置样品位置的周围,或者所述温度检测模块80被设置于所述置物板60上放置样品的正上方,或者所述温度检测模块80被设置于所述置物板60的 放置样品的位置,如所述基体下方的气孔中。
所述DLC制备装置的反应腔室100内的反应温度控制范围为25℃~100℃。优选地,温度范围为25℃~50℃。在上述温度范围对所述基体的影响较小,适于不耐高温的产品,比如适于电子产品。
值得一提的是,主流电子产品所用材料为高分子材料,其耐热变形能力较差,一般耐温都在100℃以下,作为制造工艺的终端工艺,镀膜处理需要确保改变原材料的性能,所以低温工艺是电子产品加工的硬需求。在制备所述类金刚石薄膜时,通过与产品摆放等效位置的热电偶来实时检测反应温度,控制反应温度,使其不会影响电子设备。在形成所述类金刚石薄膜时,可以在产品的单独部件上形成,比如在未组装的电子屏上形成,也可以在组装的产品上形成,比如在组装成电子设备的屏幕上形成,工艺条件更加灵活。
所述DLC制备装置包括一控制部90,所述控制部90控制所述制备装置中反应条件,举例地但不限于,所述控制部90控制所述等离子源供给部的气体供给、所述反应气体原料的气体供给、所述辅助体的气体供给、所述泵系统70的工作、所述温度检测模块80、所述脉冲电源40以及所述射频电源30的工作。所述控制部90能够通过控制射频和高压脉冲的放电特性、反应气体的流量以及镀膜时间等工艺参数,来获得目标性的所述类金刚石薄膜。
进一步,所述控制部90能够控制所述脉冲电源40、射频电源30的电极放电特性,能够控制各所述气体供给部20的气体流量、镀膜时间等工艺参数,以方便地获得目标性的DLC薄膜。
值得一提的是,现有技术中的离子交换增强玻璃制备过程繁琐,需要利用高温加热硝酸钾等离子盐形成离子浴,且离子交换时间长,成本较高。而本发明的实施例中,所述DLC制备装置利用PECVD方法直接在玻璃等基材表面沉积类金刚石薄膜,常温下即可完成,所需时间短,利于成本控制;另一方面,本发明的实施例中的所述DLC制备装置通过射频与高压脉冲辅助等离子体化学气相沉积,利用低功率射频放电维持等离子体环境,抑制高压放电过程的弧光放电,与现有技术中的磁控溅射等物理气相沉积法相比整个沉积过程中基体温度低,可应用于一些不耐高温的电子器件的镀膜。当对手机玻璃屏幕进行强化处理时,可以先将手机玻璃组装完成再进行DLC气相沉积镀膜,也就是说,在电子设备制造完成之后再设置所述DLC膜,工艺灵活性高;另一方面,所述控制部90控制多 个参数的协同作用,制备过程工艺可控性好。
参考图1,根据本发明的实施例,提供一DLC膜的制备方法,其包括如下步骤:
(A)向一装载了基体的反应腔室100通入一等离子体源气体;
(B)打开射频电源30和脉冲电源40,激活所述等离子体源气体产生等离子体;
(C)将包括有碳氢气体的反应气体原料与辅助气体的气体混合物流入到反应腔室100中,在脉冲电场和射频电场的共同作用下沉积DLC薄膜;和
(D)通入空气或者惰性气体取出基体。
具体地,所述DLC薄膜的制备方法可以包括如下过程:
步骤(1)样品表面清洗与活化:将在酒精、丙酮中超声处理后的基体置于样品室后抽真空至1.5×10
-3Pa以下,通入等离子体源气体中的高纯氦气基体进行刻蚀清洗。打开射频电源30和高压脉冲电源40,等离子体源气体辉光放电产生等离子体,对基体进行10分钟的刻蚀清洗、活化。即,步骤(A)-步骤(B)的一种实施方式。
步骤(2)沉积DLC膜:清洗完毕后,利用射频与高压脉冲共同辅助等离子体化学气相沉积的方法制备透明硬质含氢类金刚石碳膜:通入碳氢气源作为反应气源,打开射频电源30和高压脉冲电源40,或者说保持步骤(1)中电源处于打开状态,进行沉积作用,待沉积薄膜后关闭,释放真空取出样品。即,步骤(C)-步骤(D)的一种实施方式。
值得一提的是,所述类金刚石薄膜制备装置是包括多层电极组,因此可以一次放置多个或者说较多数量的所述基体以及适于大面积的镀膜需求,由此进行批量化镀膜过程。
在步骤(1)中,样品表面清洗与活化阶段,通入氩气的流量50sccm-200sccm,控制所述反应腔室100的压强范围至30mtorr以下,高压脉冲电源40电压-1000V、占空比10%、清洗时间10min。
在一个实施例中的步骤(1)中,需要射频电场和高压脉冲电场的作用来对所述基体的表面进行预处理,即步骤(B)的实施过程,只打开所述脉冲电源40,使得所述电极板60能够放电。举例地,在步骤(1)中,所述等离子体源气体,如氩气或者氦气,在高压脉冲电场和射频电场的作用下产生等离子体,并且在基 体表面进行等离子体气相沉积过程,其对基体的表面进行微量蚀刻,即剥离微量的表层,但是由于其惰性作用,其并不能沉积停留于所述基体的表面。也就是说,在该过程中,主要是对表面的部分清除,而没有形成沉积层。步骤(1)为所述反应气体原料的沉积准备离化条件,并且使得基体的表面被微量的蚀刻,清洗表面,使得后续沉积的类金刚石薄膜更加牢固地结合于基体的表面。
值得一提的是,加入所述反应腔室100的气体流量对应相应的压力大小,过高或者过低的压力都会影响离化效果。过低的压力达不到清洗效果,过高的压力会存在损坏基体的风险。清洗时间长短影响清洗效果,清洗时间太短达不到清洗效果,时间过程,会有过度蚀刻的风险,且会使得整个工艺周期增长,提高工艺成本。根据本发明的实施例,在通入所述等离子体源的阶段,通入氩气或者氦气的流量50sccm-200sccm,控制反应腔中的压力为50-150mtorr,高压脉冲电源40电压-200V~-5000V、占空比10%~60%、清洗时间5~15min,在这些范围,可以较好地调节上述各种因素,使其有利于整个所述DLC膜的沉积过程。
在步骤(2)中,采用射频和高压脉冲电压辅助等离子体化学气相沉积的方法制备透明硬质含氢类金刚石碳膜。该方法可以通过射频维持整个镀膜阶段的等离子体环境,通过施加在样品基底的脉冲高电压,脉冲电源40在放电过程中,活性粒子可以在强电场作用下沉积于基体表面,形成非晶态碳网络结构。而不放电的过程中是非晶态碳网络结构自由驰豫的过程,碳结构在热力学作用下向稳定相---纳米晶石墨烯片层结构转变,并埋置于非晶碳网络中,形成透明非晶/纳米晶石墨烯片层复合结构。例如作为成膜气体使用99.999%的甲烷、氩气、氢气和99.5%的乙炔(碳源由甲烷或乙炔提供,可掺杂氩气或氢气,碳源和掺杂气体比例可以由5:1至1:5之间调节),通入30~500SCCM反应气体由气体供给部20供给,将腔室压力设为0.5~10Pa。此外对感应耦合等离子体源(ICP)50施加100~700W,在反应腔室100内产生感应振荡电磁场,电离通过的气体形成等离子体。对阴极电极板上施加-600~-1200V偏压,加速牵引感应耦合等离子体源(ICP)形成的等离子体,如此在基材上形成透明硬质纳米复合膜。
含氢类金刚石碳膜镀膜阶段参数设置CH
4气体流量40-100sccm、C
2H
2气体流量50-200sccm、Ar的气体流量40-100sccm、H
2的气体流量40-100sccm、所述反应腔室100内的压强控制范围50-150mTorr、射频电源30功率范围50-300W,偏压脉冲电源40电压-200V—-5000V、占空比10%-80%、镀膜时间5-30min, 最终得到5-1000nm的透明硬质含氢类金刚石碳膜。
在所述反应气体原料沉积的阶段,通入的不同气体流量比影响所述DLC膜的原子比例,影响膜层的性能,根据本发明的实施例,当CH
4气体流量40-100sccm、C
2H
2气体流量50-200sccm、Ar的气体流量40-100sccm、H
2的气体流量40-100sccm时,所述DLC膜的刚性较好,且可以通过氢气调节所述DLC膜的柔韧性,并且保持预定的沉积反应速率。
在所述反应气体原料沉积的阶段,射频电源30的功率电场和脉冲电场的电源电压大小影响电离过程的升温、离化率和沉积速率等相关参数,根据本发明的实施例,当射频电源30功率范围50-300W,偏压脉冲电源40电压-200V—-5000V、占空比10%-80%,在这些参数范围时,可以使得温升不会过快,也不会过度延长工艺时间,使得离化率较高并且保持较好的沉积速率。
负偏压值的大小直接关系到气体离化情况和到达产品表面时的迁移能力。高电压意味着更高的能量,可以获得高硬度涂层。但需要注意的是,高的离子能量会对基体产品产生很强的轰击效应,所以在微观尺度上会在表面产生轰击坑,同时高能量轰击会加快温度提升,可能导致温度过高而损坏产品,因此需要在偏压值、反应温度以及反应速率之间平衡。
优选地,在一些实施例中,射频的频率使用20~300KHz,较高的脉冲频率,可以避免绝缘产品表面的电荷持续积累,抑制大电弧现象和增加涂层沉积厚度极限。
在所述反应气体原料沉积的阶段,镀膜时间过短形成的膜层较薄,硬度表现差,而镀膜时间过长,厚度增大,但是影响透明性。根据本发明的实施例,当镀膜时间为5-30min时,能够在厚度、硬度以及透明性之间平衡,最终得到5-1000nm的透明硬质含氢类金刚石碳膜。
进一步,在步骤(2),所述反应腔室100内的温度控制范围为25℃~100℃。优选地,温度范围为25℃~50℃。
下面结合实施例对本发明作进一步阐明,但本发明的内容不仅仅局限于下面的实施例。
产品主要性能指标如下表1所示
表1
实施例
以下,作为本发明实施例的各种镀膜条件中,进行DLC覆膜的成膜,以上述实施方式中说明的规定的条件下的成膜作为实施例、该条件之外的条件下的成膜作为比较例,分别测定各情况下的DLC覆膜的膜特性。需要说明的是,实施例、比较例中作为成膜装置,均使用参照图1的上述实施方式中说明的构成的装置。另外,作为基材选用6.5英寸石英玻璃屏。作为前提条件,玻璃屏需要用无水乙醇、丙酮分别超声清洗20min,随即用氮气吹干,装夹在真空腔室内,通过抽空系统将腔室内气压抽至1.5×10
-3Pa以下,通入100SCCM高纯氩气,打开偏压电源(直流脉冲)和射频电源,腔室压力控制在25mtorr、偏压电源电压500-900V、占空比10%、频率80kHz,对基材进行10分钟的清洁。接着,镀膜于基材之上,如以下说明的各实施例和比较例所示,通过ICP加强CVD方式进行DLC镀膜。
第一组实施例:甲烷氩气组合
首先,作为实施例1~3和比较例1、2,镀膜气体为纯度99.999%的CH
4和Ar组合。实施例1~3和比较例1、2的镀膜条件(气体压力、气体流量、电源条件、镀膜时间)如以下表2所示。另外,表2也记载了不同镀膜条件膜层的特性(膜厚、硬度、透光率)。
表2
本系列实施例腔室的压力都保持在25mtorr,实施例通过设置不同偏压值来展开实验的。作为对比例的实施例分别选择单独使用偏压电源和射频电源。
从表中数据可以看出使用本发明的镀膜装置,使用不同偏压值都可以获得性能优异的膜层,且成膜速度也适合工业化生产,但偏压值偏低会导致等离子体获得的能量不够,而过高的偏压对基体有溅射效应,会导致沉积效率低,内应力上升。从实施例2可以得出,适当的工艺参数可以获得高的表面硬度(莫氏硬度7H)和高的透过率,从而非常适合应用在柔性屏上。
比较实施例2和对比例1、对比例2可以发现,不加偏压只通过ICP来沉积的膜层成膜速度慢且硬度表现较差,而只接偏压不使用ICP技术获得的各项膜层性能质量指标都比实施例1差。这是由于综合利用ICP和偏压电极技术可以获得一种非晶碳和纳米晶石墨烯的复合结构(如图7所示)。
第二组实施例:乙炔氩气组合
首先,实施例4~6和比较例3、4选用气体纯度为99.9%的C
2H
2和99.999% 的Ar组合作为反应气体。实施例4~6和比较例3、4的镀膜条件(气体压力、气体流量、电源条件、镀膜时间)如以下表3所示。另外,表3也记载了不同镀膜条件膜层的特性(膜厚、硬度、透光率)。
表3
本系列实施例腔室的压力都保持在25mtorr,偏压电源电压值设为900V,实施例通过设置不同射频功率来展开实验的。作为对比例选择单独使用偏压电源和射频电源,比较对比例1、2,对比不同碳源下,不同的电源组合对其膜层质量的影响。
从表中数据可以看出使用本发明的镀膜装置,合理设置参数,可以获得性能优异的膜层,增加射频功率可以提高离子浓度,从而增加镀膜效率,但过快的沉积效率会影响膜层质量。从实施例5可以得出,适当的工艺参数可以获得高透光率和高硬度涂层。
比较实施例5和对比例1~4可以发现,不加偏压只通过ICP来沉积的膜层成膜速度慢且硬度表现较差,而只接偏压不适用ICP获得的各项膜层性能质量指 标都比各实施例差,且在不同的气体组合下该现象保持一致。
第三组实施例:乙炔氢气组合
首先,作为实施例7~9和比较例5、6,镀膜气体为纯度99.999%的C
2H
2和H
2组合。实施例7~9和比较例5、6的镀膜条件(气体压力、气体流量、电源条件、镀膜时间)如以下表4所示。另外,表4也记载了不同镀膜条件膜层的特性(膜厚、硬度、透光率)。
表4
本系列实施例、对比例偏压值设为900V,射频功率300W,通过设置不同腔室压力来展开实验。
从表中数据可以看出使用本发明的镀膜装置在一定的腔体气压范围内,合理设置其他参数,可以获得性能合格的膜层,腔室压力大小直接关系到辉光现象,从而影响成膜速率和膜层质量。气压过低粒子碰撞几率低,从而离化率低,气压过高粒子碰撞几率高,带电粒子能量损失过多,获得的膜层质量会下降。从实施 例7可以得出,适当的工艺参数可以获得高透光率和高硬度涂层。
比较实施例5和对比例1~4可以发现,其他参数一定的情况下,气压过高、过低都会导致无法起辉,所以合理设定腔室压力很重要。
本领域的技术人员应理解,上述描述及附图中所示的本发明的实施例只作为举例而并不限制本发明。本发明的目的已经完整并有效地实现。本发明的功能及结构原理已在实施例中展示和说明,在没有背离所述原理下,本发明的实施方式可以有任何变形或修改。
Claims (37)
- 一DLC制备装置,其特征在于,包括:一主体,所述主体具有一反应腔室,所述反应腔室用于放置一基体;一等离子体源单元;和至少一气体供给部,所述气体供给部用于向所述反应腔室提供反应气体,所述等离子体源单元被设置于所述主体外部,向所述反应腔室提供射频电场,以促进产生等离子体,使得所述反应气体通过PECVD方式沉积于所述基体的表面形成一DLC膜。
- 根据权利要求1所述的DLC制备装置,其包括一射频电源,所述射频电源电连接所述等离子体源单元,为所述等离子体源单元提供电源。
- 根据权利要求1所述的DLC制备装置,其中所述等离子体源单元包括一进气框、一隔离板和一感应线圈,所述进气框被密封地设置于所述主体外部,所述隔离板位于所述进气框和所述感应线圈之间。
- 根据权利要求3所述的DLC制备装置,其中所述进气框具有一连通通道,连通所述主体的所述反应腔室和所述气体供给部。
- 根据权利要求4所述的DLC制备装置,其中所述进气框具有至少一连通孔和一主通道,所述主体具有一窗口,所述窗口连通所述反应腔室,所述主体的所述窗口和所述进气框的所述连通孔以及所述主通道连通形成所述连通通道。
- 根据权利要求5所述的DLC制备装置,其中所述连通口和所述主通道位于相互垂直的方向。
- 根据权利要求4所述的DLC制备装置,其中所述进气框具有至少一连通孔、一内连通道、一布气孔和一主通道,所述连通孔连通外部,用于输入气体,所述布气孔被设置于所述进气框内侧并且连通所述主通道,所述内连通道连通所述连通孔和所述布气孔,所述主体的所述窗口、所述进气框的所述连通孔、所述内连通道、所述布气孔和所述主通道连通形成所述连通通道。
- 根据权利要求7所述的DLC制备装置,其中多个所述内连通道相互连通形成一内环形通道。
- 根据权利要求3所述的DLC制备装置,其中所述等离子体源单元进一步包括一外盖板,所述感应线圈被夹持于所述隔离板和所述外盖板之间。
- 根据权利要求9所述的DLC制备装置,其中所述进气框包括一主框体和一插接组件,所述主框体被密封地设置于所述主体的外部,所述插接组件被设置于所述主框体的外部,所述隔离板、所述感应线圈和所述外盖板被插接于所述插接组件。
- 根据权利要求3所述的DLC制备装置,其中所述隔离板是陶瓷密封板。
- 根据权利要求1所述的DLC制备装置,其中所述等离子体源单元是一种射频感应耦合等离子体源,提供感应耦合电场。
- 根据权利要求1-12任一所述的DLC制备装置,其中所述DLC制备装置包括一置物极板和一脉冲电源,所述置物极板被容纳于所述反应腔室内,所述置物极板电连接所述脉冲电源,用于向所述反应腔室提供脉冲电场,所述基体适于被放置于所述置物极板。
- 根据权利要求13所述的DLC制备装置,其中所述置物极板具有一气孔,连通所述置物极板的两侧。
- 根据权利要求13所述的DLC制备装置,其包括多个置物极板,多个所述置物极板平行间隔地布置。
- 根据权利要求13所述的DLC制备装置,其中所述脉冲电源电压控制范围为-200V—-5000V。
- 根据权利要求1-12任一所述的DLC制备装置,其中所述气体供给部包括一等离子体源供给部,所述等离子体源供给部用于向所述反应腔室提供一等离子体源气体,以激活PECVD沉积反应。
- 根据权利要求17所述的DLC制备装置,其中所述等离子体源气体选自组合:惰性气体、氮气、氟碳气体中的一种或多种。
- 根据权利要求1-12任一所述的DLC制备装置,其中所述气体供给部包括一反应气体原料供给部,所述反应气体原料供给部用于向所述反应腔室提供一碳氢气体C xH y,所述碳氢气体C xH y通过PECVD方式沉积于所述基体表面,以形成所述类金刚石薄膜。
- 根据权利要求1-12任一所述的DLC制备装置,其中所述气体供给部包括一辅助气体供给部,所述辅助气体供给部用于向所述反应腔室提供一辅助气体,所述辅助气体用于调节所述类金刚石薄膜中的C-H含量,与所述碳氢气体C xH y反应沉积于所述基体的表面形成所述类金刚石薄膜。
- 根据权利要求20所述的DLC制备装置,其中所述辅助气体选自组合:氮气、氢气、氟碳气体中的一种或多种。
- 根据权利要求1-12任一所述的类金刚石薄膜制备装置,其包括一温度检测模块,所述温度检测模块被设置于所述基体放置位置的等效位置。
- 一DLC膜制备方法,其特征在于,向一反应腔室提供一反应气体,在一射频电场和一脉冲电场的作用下,促使反应气体通过PECVD方式沉积于所述反应腔室内的一基体的表面形成一DLC膜。
- 根据权利要求23所述的DLC膜制备方法,其中在控制过程中,先打开射频电场,后打开脉冲电场。
- 根据权利要求23所述的DLC膜制备方法,其中所述射频电场被设置于所述脉冲电场外部。
- 根据权利要求23所述的DLC膜制备方法,其中所述射频电场是感应耦合电场。
- 根据权利要求23-26任一所述的DLC膜制备方法,其中包括步骤:向所述反应腔室提供一等离子体源气体,以激活PECVD沉积反应,所述射频电场和所述脉冲电场同时作用于所述等离子体源气体。
- 根据权利要求23-26任一所述的DLC膜制备方法,其中包括步骤:向所述反应腔室提供一辅助气体,所述辅助气体用于调节所述类金刚石薄膜中的C-H含量,与所述碳氢气体C xH y反应沉积于所述基体的表面形成所述DLC膜。
- 根据权利要求23-26任一所述的DLC膜制备方法,其中在所述反应腔室内设置一置物极板,所述置物极板电连接一脉冲电源,以在所述反应腔室内提供所述脉冲电场。
- 根据权利要求23-26任一所述的DLC膜制备方法,其中包括步骤:检测所述基体等效位置的温度,以反馈控制。
- 一DLC膜制备方法,其特征在于,包括步骤:a)向一装载了基体的反应腔室通入一等离子体源气体;b)打开脉冲电源和射频电源,分别提供射频电场和脉冲电场,激活所述等离子体源气体产生等离子体;和c)向所述反应腔室中通入一碳氢气体C xH y,在所述基体表面沉积DLC膜。
- 根据权利要求31所述的DLC膜制备方法,其中在所述步骤b)中,先 打开射频电源,后打开脉冲电源。
- 根据权利要求31所述的DLC膜制备方法,其中包括步骤:在脉冲电场外部设置射频电场。
- 根据权利要求31所述的DLC膜制备方法,其中所述射频电场是感应耦合电场。
- 根据权利要求31-34任一所述的DLC膜制备方法,其中步骤c)包括步骤:向所述反应腔室提供一辅助气体,所述辅助气体用于调节所述类金刚石薄膜中的C-H含量,与所述碳氢气体C xH y反应沉积于所述基体的表面形成所述类金刚石薄膜。
- 根据权利要求35所述的类金刚石薄膜制备方法,其中包括步骤:抽取所述反应腔室中的气体,调节所述反应腔室中的气体压强大小。
- 根据权利要求35所述的类金刚石薄膜制备方法,其中包括步骤:检测所述基体等效位置的温度,以反馈控制。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6572935B1 (en) * | 1999-03-13 | 2003-06-03 | The Regents Of The University Of California | Optically transparent, scratch-resistant, diamond-like carbon coatings |
CN101768011A (zh) * | 2008-12-29 | 2010-07-07 | 中国科学院兰州化学物理研究所 | 抗腐蚀类金刚石薄膜的制备方法 |
CN102453859A (zh) * | 2010-10-29 | 2012-05-16 | 中国科学院兰州化学物理研究所 | 含氢类金刚石碳薄膜材料的制备方法 |
CN107641788A (zh) * | 2016-07-22 | 2018-01-30 | 北京华石联合能源科技发展有限公司 | 一种抗结焦的类金刚石膜的制备方法 |
CN207183207U (zh) * | 2017-06-02 | 2018-04-03 | 北京北方华创微电子装备有限公司 | 用于处理工件的等离子体反应装置 |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4645977A (en) * | 1984-08-31 | 1987-02-24 | Matsushita Electric Industrial Co., Ltd. | Plasma CVD apparatus and method for forming a diamond like carbon film |
JPS61130487A (ja) * | 1984-11-29 | 1986-06-18 | Matsushita Electric Ind Co Ltd | プラズマ・インジエクシヨン・cvd装置 |
JP3119172B2 (ja) * | 1995-09-13 | 2000-12-18 | 日新電機株式会社 | プラズマcvd法及び装置 |
US6321680B2 (en) * | 1997-08-11 | 2001-11-27 | Torrex Equipment Corporation | Vertical plasma enhanced process apparatus and method |
JP4044218B2 (ja) * | 1998-08-28 | 2008-02-06 | 松下電器産業株式会社 | プラズマ処理装置 |
JP4849705B2 (ja) * | 2000-03-24 | 2012-01-11 | 東京エレクトロン株式会社 | プラズマ処理装置、プラズマ生成導入部材及び誘電体 |
KR20050110503A (ko) * | 2004-05-19 | 2005-11-23 | 삼성에스디아이 주식회사 | 가스분사노즐 시스템 및 이를 이용한 유도결합 플라즈마화학기상증착 장치 |
JP4534619B2 (ja) * | 2004-06-21 | 2010-09-01 | 株式会社Sumco | 半導体シリコン基板用熱処理治具 |
DE102006032568A1 (de) * | 2006-07-12 | 2008-01-17 | Stein, Ralf | Verfahren zur plasmagestützten chemischen Gasphasenabscheidung an der Innenwand eines Hohlkörpers |
US20090029067A1 (en) * | 2007-06-28 | 2009-01-29 | Sciamanna Steven F | Method for producing amorphous carbon coatings on external surfaces using diamondoid precursors |
JP2009224420A (ja) * | 2008-03-14 | 2009-10-01 | Sumitomo Precision Prod Co Ltd | プラズマ処理装置 |
JP5800547B2 (ja) * | 2011-03-29 | 2015-10-28 | 東京エレクトロン株式会社 | プラズマ処理装置及びプラズマ処理方法 |
KR101215511B1 (ko) * | 2012-06-27 | 2012-12-26 | (주)이노시티 | 프로세스 챔버 및 기판 처리 장치 |
DE102012024340A1 (de) * | 2012-12-13 | 2014-06-18 | Oerlikon Trading Ag, Trübbach | Plasmaquelle |
WO2014164300A1 (en) * | 2013-03-13 | 2014-10-09 | Applied Materials, Inc | Pulsed pc plasma etching process and apparatus |
KR101439878B1 (ko) * | 2013-12-17 | 2014-09-12 | (주) 일하하이텍 | 리모트 플라즈마 발생장치 |
JP6246685B2 (ja) * | 2014-09-12 | 2017-12-13 | 株式会社東芝 | 静電チャック機構、基板処理方法及び半導体基板処理装置 |
US11008655B2 (en) * | 2016-03-03 | 2021-05-18 | Lam Research Corporation | Components such as edge rings including chemical vapor deposition (CVD) diamond coating with high purity SP3 bonds for plasma processing systems |
JP6807775B2 (ja) * | 2017-02-28 | 2021-01-06 | 東京エレクトロン株式会社 | 成膜方法及びプラズマ処理装置 |
KR102563925B1 (ko) * | 2018-08-31 | 2023-08-04 | 삼성전자 주식회사 | 반도체 제조 장치 |
JP7169910B2 (ja) * | 2019-03-11 | 2022-11-11 | 東京エレクトロン株式会社 | 半導体装置の製造方法 |
CN110747447A (zh) * | 2019-09-11 | 2020-02-04 | 江苏菲沃泰纳米科技有限公司 | 电子设备外盖增强纳米膜及其制备方法和应用 |
CN110760814A (zh) * | 2019-09-11 | 2020-02-07 | 江苏菲沃泰纳米科技有限公司 | 电子设备及其钢化加强膜和制备方法及应用 |
-
2019
- 2019-12-04 CN CN201911227596.8A patent/CN112899662A/zh active Pending
-
2020
- 2020-11-17 TW TW109140162A patent/TWI772969B/zh active
- 2020-12-04 WO PCT/CN2020/133768 patent/WO2021110111A1/zh unknown
- 2020-12-04 US US17/782,166 patent/US20220380902A1/en active Pending
- 2020-12-04 EP EP20895449.5A patent/EP4071270A4/en active Pending
- 2020-12-04 JP JP2022532851A patent/JP2023504812A/ja active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6572935B1 (en) * | 1999-03-13 | 2003-06-03 | The Regents Of The University Of California | Optically transparent, scratch-resistant, diamond-like carbon coatings |
CN101768011A (zh) * | 2008-12-29 | 2010-07-07 | 中国科学院兰州化学物理研究所 | 抗腐蚀类金刚石薄膜的制备方法 |
CN102453859A (zh) * | 2010-10-29 | 2012-05-16 | 中国科学院兰州化学物理研究所 | 含氢类金刚石碳薄膜材料的制备方法 |
CN107641788A (zh) * | 2016-07-22 | 2018-01-30 | 北京华石联合能源科技发展有限公司 | 一种抗结焦的类金刚石膜的制备方法 |
CN207183207U (zh) * | 2017-06-02 | 2018-04-03 | 北京北方华创微电子装备有限公司 | 用于处理工件的等离子体反应装置 |
Non-Patent Citations (3)
Title |
---|
JI LI, HONGXUAN LI, FEI ZHA, WEILONG QUAN, JIANMIN CHEN, HUIDI ZHOU: "Preparation of Diamond-Like Carbon Films by Inductively Coupled Radio Frequency Plasma-Enhanced Chemical Vapor Deposition: Pulse Bias Voltage Effect", PROCEEDINGS OF THE 7TH NATIONAL SURFACE ENGINEERING CONFERENCE AND THE 2ND YOUTH ACADEMIC FORUM ON SURFACE ENGINEERING, VOL. 1, 1 October 2008 (2008-10-01), pages 353 - 356, XP055819141 * |
OHTSU Y., H. NODA, C. NAKAMURA, T. MISAWA, H. FUJITA, M. AKIYAMA, C. DIPLASU: "Effect of negative pulsed high-voltage-bias on diamond-like carbon thin film preparation using capacitively coupled radio-frequency plasma chemical vapor deposition", SURFACE & COATINGS TECHNOLOGY, vol. 201, 27 October 2006 (2006-10-27), pages 6674 - 6677, XP055819144, DOI: 10.1016/j.surfcoat.2006.09.057 * |
See also references of EP4071270A4 * |
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EP4071270A1 (en) | 2022-10-12 |
TWI772969B (zh) | 2022-08-01 |
CN112899662A (zh) | 2021-06-04 |
US20220380902A1 (en) | 2022-12-01 |
JP2023504812A (ja) | 2023-02-07 |
TW202122619A (zh) | 2021-06-16 |
EP4071270A4 (en) | 2024-03-13 |
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