DLC manufacturing device and manufacturing method

Abstract

The DLC manufacturing apparatus and manufacturing method are provided. The DLC manufacturing apparatus comprises a main body (10) having a reaction chamber (100) for placing a substrate, a plasma source unit (50), and at least one gas supply unit (20) for supplying a reactive gas to the reaction chamber (100). The plasma source unit (50) is installed outside the main body (10) and applies a radio frequency electric field to the reaction chamber (100) to promote the generation of plasma, and the reactive gas is deposited on the surface of the substrate by a PECVD method to form a DLC film.

Description

[Technical field]

[0001] The present invention relates to the field of diamond-like carbon film manufacturing, and further to an apparatus and method for manufacturing transparent and hard DLC, which is suitable for depositing on the surfaces of electronic devices and their accessories for protection. [Background technology]

[0002] Diamond-like carbon (DLC) films are metastable materials containing sp3 and sp2 carbon bonds, and combine the excellent properties of diamond and graphite, with high hardness, high resistivity, good optical properties, and excellent tribological properties. Diamond-like carbon films come in a variety of different structural forms, and carbon nanomaterials with special structures (fullerene-like carbon, nano-amorphous carbon, graphene) have attracted much attention from the scientific and industrial communities as high-performance solid lubricant materials due to their extremely low friction coefficient, high hardness, good elastic recovery, and excellent wear resistance.

[0003] One of the conventional methods for producing diamond-like carbon films is a physical vapor deposition method, for example, by magnetron sputtering to form a coating film, thereby obtaining a DLC film. The other is a chemical vapor deposition method, for example, by plasma-enhanced chemical vapor deposition (PECVD), in which a DLC film is deposited using a hydrocarbon gas such as methane, ethane, acetylene, benzene, or butane as a carbon source, and a DLC film containing a predetermined amount of hydrogen is produced through a complex process of activating, dissociating, and depositing the hydrocarbon gas by plasma.

[0004] Meanwhile, the manufacturing process of DLC involves a complex reaction process, and the properties of the formed DLC film are related to various factors such as the composition ratio of raw materials and the control of specific process conditions. Among them, the control of the same raw material process conditions also has a significant effect on the properties of the formed DLC film, and the influence method is relatively complex. Meanwhile, the performance of the DLC film required for different coating products is also different. In the field of electronic devices, for example, when applied to the screen of a smartphone, it is not only required to improve the surface rigidity, but also to have good light transmittance without affecting the visual effect of the screen of the electronic device. Summary of the Invention [Problem to be solved by the invention]

[0005] One advantage of the present invention is to provide a DLC manufacturing apparatus and method that uses the synergistic action of an internal and external radio frequency electric field and a high voltage pulse electric field to perform plasma enhanced chemical vapor deposition (PECVD) to form a DLC film.

[0006] Another advantage of the present invention is to provide a DLC manufacturing apparatus and method in which a radio frequency electric field and a high voltage pulse electric field formed by inductive coupling cooperate to provide plasma enhanced chemical deposition reaction conditions under which a DLC film is manufactured from a reactant gas.

[0007] Another advantage of the present invention is to provide a DLC manufacturing apparatus and method in which a synergistic effect of a radio frequency electric field and a high voltage pulse electric field in different directions is used to perform a plasma enhanced chemical deposition reaction to form the DLC film.

[0008] Another advantage of the present invention is that it provides a DLC manufacturing apparatus and method that maintains a plasma environment with a low power radio frequency discharge and suppresses arcing during high voltage discharge, thereby improving chemical deposition efficiency.

[0009] Another advantage of the present invention is to provide a DLC manufacturing apparatus and method that can control the performance of the DLC film by controlling the bias voltage value, maintain high deposition efficiency, and obtain a DLC film with high surface hardness and high transmittance.

[0010] Another advantage of the present invention is to provide a DLC manufacturing apparatus and method that controls radio frequency power to vary ion concentration, thereby improving coating efficiency.

[0011] Another advantage of the present invention is to provide a DLC manufacturing apparatus and method that adjusts the glow phenomenon by controlling the pressure inside the chamber, thereby adjusting the deposition rate and film layer quality. Another advantage of the present invention is to provide a DLC manufacturing apparatus and method that can obtain a target DLC by controlling process parameters such as the discharge characteristics of the radio frequency and high voltage pulse, the flow rate of the reactive gas, and the coating time.

[0012] Another advantage of the present invention is to provide a DLC manufacturing apparatus and method, in which, in one embodiment, the directions of the radio frequency electric field and the high voltage pulse electric field are perpendicular to each other.

[0013] Another advantage of the present invention is to provide an apparatus and method for producing DLC ​​that is suitable for deposition on the surfaces of electronic devices and their accessories and can maintain good optical transparency.

[0014] Another advantage of the present invention is that it provides a DLC manufacturing apparatus and method that is suitable for mass production applications due to the short reaction time and high deposition efficiency of the PECVD deposition process, resulting in high overall production efficiency. [Means for solving the problem]

[0015] In one aspect, the present invention provides a method for producing a composition comprising: a body having a reaction chamber for disposing a substrate; A plasma source unit; at least one gas supply for supplying a reaction gas to the reaction chamber; Equipped with The plasma source unit is provided outside the main body, and supplies a radio frequency electric field to the reaction chamber to promote the generation of plasma, and the reaction gas is deposited on the surface of the substrate by a PECVD method to form a DLC film, thereby providing a DLC manufacturing apparatus.

[0016] A DLC manufacturing apparatus according to an embodiment of the present invention includes a radio frequency power source electrically connected to the plasma source unit and supplying power to the plasma source unit.

[0017] According to one embodiment of the DLC manufacturing apparatus, the plasma source unit includes a gas inlet frame airtightly installed outside the main body, an induction coil, and a shielding plate installed between the gas inlet frame and the induction coil.

[0018] In the DLC manufacturing apparatus according to one embodiment, the gas inlet frame has a communication path that communicates the reaction chamber of the main body with the gas supply unit.

[0019] According to one embodiment of a DLC manufacturing apparatus, the gas inlet frame has at least one communication hole and a main path, the main body has a window portion communicating with the reaction chamber, and the window portion of the main body communicates with the communication hole of the gas inlet frame and the main path to form the communication path.

[0020] In the DLC manufacturing apparatus according to one embodiment, the communication port and the main path are provided perpendicular to each other.

[0021] According to one embodiment of the DLC manufacturing apparatus, the gas introduction frame has at least one communication hole communicating with the outside for injecting gas, an air distribution hole provided inside the gas introduction frame and communicating with the main path, an inner communication path that connects the communication hole with the air distribution hole, and a main path, and the communication path is formed by connecting the window portion of the main body, the communication hole of the gas introduction frame, the inner communication path, the air distribution hole, and the main path.

[0022] In the DLC manufacturing apparatus according to one embodiment, the inner communication paths are connected to each other to form an inner annular path.

[0023] In one embodiment of the DLC manufacturing apparatus, the plasma source unit further includes an outer cover plate, and the induction coil is sandwiched between the shield plate and the outer cover plate.

[0024] According to one embodiment of the DLC manufacturing apparatus, the gas introduction frame includes a main frame body that is airtightly installed outside the main body, and an insertion member that is arranged outside the main frame body and into which the shielding plate, the induction coil, and the external cover plate are inserted.

[0025] In one embodiment of the DLC manufacturing apparatus, the blocking plate is a ceramic sealing plate.

[0026] In one embodiment of the DLC manufacturing apparatus, the plasma source unit is a radio frequency inductively coupled plasma source that applies an inductively coupled electric field.

[0027] According to one embodiment of the DLC manufacturing apparatus, the DLC manufacturing apparatus comprises a mounting plate and a panel power supply, the mounting plate is housed in the reaction chamber and is electrically connected to the pulse power supply to apply a pulse electric field to the reaction chamber, and the substrate is suitably disposed on the mounting plate.

[0028] In the DLC manufacturing apparatus according to one embodiment, the stationary electrode plate has air holes that communicate both sides of the stationary electrode plate.

[0029] A DLC manufacturing apparatus according to one embodiment includes a plurality of mounting electrodes arranged in parallel with gaps therebetween.

[0030] In the DLC manufacturing apparatus according to one embodiment, the voltage control range of the pulse power supply is -200V to -5000V.

[0031] In one embodiment of the DLC manufacturing apparatus, the gas supply unit includes a plasma source supply unit, which supplies a plasma source gas to the reaction chamber and activates a deposition reaction by a PECVD method.

[0032] In the DLC manufacturing apparatus according to one embodiment, the plasma source gas is at least one selected from the group consisting of an inert gas, a nitrogen gas, and a fluorocarbon gas.

[0033] In one embodiment of the DLC manufacturing apparatus, the gas supply unit includes a reactive gas raw material supply unit for supplying a hydrocarbon gas CxHy to the reaction chamber, and the hydrocarbon gas CxHy is deposited on the surface of the substrate by a PECVD method to form the diamond-like carbon film.

[0034] In one embodiment of the DLC manufacturing apparatus, the gas supply unit includes an auxiliary gas supply unit for supplying an auxiliary gas to the reaction chamber, and the auxiliary gas adjusts the CH content in the diamond-like carbon film and reacts with the hydrocarbon gas CxHy to deposit on the surface of the substrate, thereby forming the diamond-like carbon film.

[0035] In the DLC manufacturing apparatus according to one embodiment, the auxiliary gas is at least one selected from the group consisting of nitrogen gas, hydrogen gas, and fluorocarbon gas.

[0036] The diamond-like carbon film manufacturing apparatus according to one embodiment includes a temperature detection module provided at a position equivalent to the position at which the substrate is disposed.

[0037] In another aspect, the present invention provides a method for producing a DLC film, comprising: supplying a reactive gas to a reaction chamber; and urging the reactive gas to deposit on a surface of a substrate in the reaction chamber by a PECVD method using a radio frequency electric field and a pulsed electric field to form a DLC film.

[0038] In one embodiment of the method for manufacturing a DLC film, in the control process, a radio frequency electric field is applied, and then a pulse electric field is applied.

[0039] In one embodiment of the method for manufacturing a DLC film, the radio frequency electric field is provided outside the pulse electric field.

[0040] In one embodiment of the method for manufacturing a DLC film, the radio frequency electric field is an inductively coupled electric field.

[0041] According to one embodiment of the method for producing a DLC film, the method includes the steps of supplying a plasma source gas to the reaction chamber, activating a deposition reaction by a PECVD method, and simultaneously applying the radio frequency electric field and the pulse electric field to the plasma source gas.

[0042] According to one embodiment of the method for manufacturing a DLC film, the method includes a step of supplying an auxiliary gas to the reaction chamber, the auxiliary gas adjusting a CH content in the diamond-like carbon film and reacting with the hydrocarbon gas CxHy to deposit the DLC film on a surface of the substrate.

[0043] In one embodiment of the method for producing a DLC film, a mounting plate that is electrically connected to a pulsed power supply and supplies the pulsed electric field in the reaction chamber is disposed in the reaction chamber.

[0044] A method for producing a DLC film according to one embodiment includes a step of detecting the temperature at an equivalent position on the substrate and performing feedback control.

[0045] In another aspect, the present invention provides a method for producing a composition comprising: (a) introducing a plasma source gas into a reaction chamber in which a substrate is disposed; (b) turning on a pulsed power source and a radio frequency power source to apply a radio frequency electric field and a pulsed electric field, respectively, to activate the plasma source gas to generate plasma; and (c) introducing a hydrocarbon gas CxHy into the reaction chamber and depositing a DLC film on the surface of the substrate.

[0046] According to one embodiment of the method for producing a DLC film, in step (b), the radio frequency power supply is turned on, and then the pulse power supply is turned on.

[0047] According to one embodiment, a method for manufacturing a DLC film includes applying a radio frequency electric field outside the pulsed electric field.

[0048] In one embodiment of the method for manufacturing a DLC film, the radio frequency electric field is an inductively coupled electric field.

[0049] According to one embodiment of the method for manufacturing a DLC film, step (c) includes a step of supplying an auxiliary gas to the reaction chamber, the auxiliary gas adjusts the CH content in the diamond-like carbon film and reacts with the hydrocarbon gas CxHy to deposit the diamond-like carbon film on the surface of the substrate, thereby forming the diamond-like carbon film.

[0050] A method for manufacturing a diamond-like carbon film according to an embodiment of the present invention includes the steps of extracting gas from within the reaction chamber and adjusting the air pressure within the reaction chamber.

[0051] A method for manufacturing a diamond-like carbon film according to one embodiment includes a step of detecting the temperature at an equivalent position on the substrate and performing feedback control. [Brief description of the drawings]

[0052] [Figure 1] 1 is a flowchart of a method for manufacturing DLC ​​according to an embodiment of the present invention. [Diagram 2] FIG. 2 is a block diagram of a DLC manufacturing apparatus according to the embodiment of the present invention. [Diagram 3] FIG. 2 is a schematic diagram of a DLC manufacturing apparatus according to the embodiment of the present invention. [Figure 4A] FIG. 2 is a perspective view of one embodiment of a DLC manufacturing apparatus according to the embodiment of the present invention. [Figure 4B] FIG. 2 is a perspective view of one embodiment of a DLC manufacturing apparatus according to the embodiment of the present invention. [Figure 4C] FIG. 2 is a perspective view of another embodiment of the DLC manufacturing apparatus according to the embodiment of the present invention. [Figure 5A] FIG. 2 is an exploded schematic view of one embodiment of the DLC manufacturing apparatus according to the embodiment of the present invention. [Figure 5B] FIG. 4 is a schematic diagram of a modified embodiment of the gas inlet frame of the DLC manufacturing apparatus according to the embodiment of the present invention. [Figure 6] FIG. 4 is a schematic diagram of a modified embodiment of the DLC manufacturing apparatus according to the embodiment of the present invention. [Figure 7] 4 is a transmission electron microscope image of the diamond-like carbon film according to the embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0053] The following description discloses the present invention to enable those skilled in the art to practice the present invention. The following preferred embodiments are given by way of example only, and other obvious modifications may occur to those skilled in the art. The basic principles of the present invention defined in the following description may be applied to other embodiments, modifications, improvements, equivalents, and other technical solutions that do not depart from the spirit and scope of the present invention.

[0054] In the present disclosure, the terms "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside" and the like are used with respect to the orientation or positional relationship shown in the drawings, and are only for the purpose of explaining or simplifying the present invention, and do not necessarily indicate or imply that such devices or elements must have a specific orientation and a specific oriented structure and operation, as should be understood by those skilled in the art. Thus, the terms should not be construed as limiting the present invention.

[0055] It should also be understood that the term "a" should be interpreted as "at least one" or "one or more." That is, in one embodiment, the number of an element may be one, but in another embodiment, the number of the element may be multiple. The term "a" should not be interpreted as limiting the number.

[0056] References to "one embodiment," "an embodiment," "an exemplary embodiment," "various embodiments," "some embodiments," and the like indicate that the embodiment of the invention so described may include a particular feature, structure, or characteristic, but not all embodiments necessarily include that feature, structure, or characteristic. Furthermore, some embodiments may have some, all, or none of the features described with respect to other embodiments.

[0057] Fig. 1 is a flow chart of a method for producing DLC ​​according to an embodiment of the present invention. Fig. 2 is a block diagram of a DLC production apparatus according to the embodiment of the present invention. Fig. 3 is a schematic diagram of a DLC production apparatus according to the embodiment of the present invention.

[0058] 1 to 5A, the present invention provides a DLC manufacturing apparatus. The DLC manufacturing apparatus is used for performing a PECVD reaction to manufacture a DLC film suitable for depositing on a surface of a substrate to improve the surface performance of the substrate. Furthermore, the DLC manufacturing apparatus chemically deposits and forms the DLC film on the surface of the substrate by a plasma-enhanced chemical vapor deposition (PECVD) method. In other words, the substrate is placed in a reaction chamber of the DLC manufacturing apparatus to perform plasma-enhanced chemical deposition, and the DLC film is formed on the surface of the substrate.

[0059] "Substrate" refers to a small or large area object to be coated or a surface to be improved by the method of the present invention. The substrate referred to herein can be glass, plastic, inorganic material, or any other material having a surface to be coated or modified. The substrate can be an electronic device and its accessories, such as, but not limited to, a smartphone, a tablet computer, an e-reader, a wearable device, a television, a computer display panel, a glass screen, a flexible screen.

[0060] "Plasma" refers to a state in which electrons, positive and negative ions, excited atoms, molecules, and free radicals are mixed together.

[0061] Furthermore, according to one embodiment of the present invention, the DLC manufacturing apparatus uses a hydrocarbon gas C as a reaction gas raw material. x H y The DLC film is obtained by plasma enhanced chemical vapor deposition using the above-mentioned.

[0062] The DLC film can increase the surface rigidity of the substrate, such as Mohs hardness, and can further improve the drop resistance and abrasion resistance of the substrate. The DLC is a nanofilm having a relatively small thickness, and the thickness range is, but is not limited to, 10 to 2000 nm.

[0063] The DLC manufacturing device deposits C on the surface of the substrate in a PECVD process.x H y The gaseous reactive raw material is vapor-phase deposited, and the thickness of the DLC film can be thinned, for example to nanometer size, by a plasma chemical deposition reaction process, and the target DLC film can be obtained by controlling the process parameters in the deposition process by PECVD, for example, to obtain the DLC film having a predetermined thickness. That is, the DLC film having a predetermined thickness can be obtained under different predetermined reaction conditions, rather than being selected at any value.

[0064] C x H y In the formula, x is an integer from 1 to 10, and y is an integer from 1 to 20. The reaction gas raw material can be a single gas or a mixture of two or more gases; the hydrocarbon gas is preferably selected from the group consisting of methane, ethane, propane, butane, ethylene, acetylene, propylene, and propyne, which are in a gaseous state under normal pressure, and may also be vapor formed by evaporation under reduced pressure or heat, such as benzene vapor or toluene vapor.

[0065] Compared with other existing deposition processes, the plasma-enhanced chemical vapor deposition (PECVD) process has many advantages. (1) No need to use organic solvents during dry deposition. (2) The etching action of plasma on the substrate surface improves adhesion between the deposited thin film and the substrate. (3) Thin films can be uniformly deposited on the surface of irregular substrates, resulting in very high gas-phase permeability. (4) The designability of the coating layer is good, and compared with liquid-phase methods that control precision at the micron level, the chemical vapor deposition method can control the thickness of the coating layer at the nanoscale. (5) The structure of the coating layer is easily designed. The chemical vapor deposition method is activated by plasma, and there is no need to design and initiate a specific initiator for a composite coating layer of different materials. Various raw materials can be combined by simply adjusting the input energy. (6) Excellent density. In the chemical vapor deposition method, multiple active sites are often activated in the process of initiating plasma, and similar to solution reactions, one molecule has multiple functional groups, and a cross-linked structure is formed between molecular chains via multiple functional groups. (7) As a coating processing technology, it has excellent versatility and can be used in a wide range of applications, including as coating objects and raw materials.

[0066] The plasma-enhanced chemical vapor deposition (PECVD) process generates plasma by glow discharge, which can be achieved by microwave, radio frequency, ultraviolet, or electric spark discharge.

[0067] Further, according to an embodiment of the present invention, when the DLC film is manufactured by the DLC manufacturing apparatus, a plasma source gas for activating the chemical deposition reaction of the reactive gas raw material is introduced into the DLC manufacturing apparatus. The plasma source gas includes, but is not limited to, an inert gas, nitrogen gas, and a fluorocarbon gas. Among them, the inert gas includes, but is not limited to, He and Ar, and the fluorocarbon gas includes, but is not limited to, carbon tetrafluoride. The plasma source gas may be a single gas or a mixture of two or more gases. The plasma source gas may be introduced simultaneously with the reactive gas raw material or may be introduced sequentially. Preferably, the reactive gas raw material is introduced after the plasma source gas is introduced. Of course, in one embodiment of the present invention, the plasma source gas may not be necessary, that is, the reactive gas raw material may be directly deposited on the surface of the substrate, in which case the amount of the reactive gas raw material required may increase or the reaction rate may be affected to a certain extent.

[0068] Furthermore, according to one embodiment of the present invention, when the DLC film is manufactured by the DLC manufacturing apparatus, an auxiliary gas is introduced into the DLC manufacturing apparatus. The auxiliary gas is combined with a reactant gas source to form the DLC film, that is, to become a constituent part of the diamond-like carbon film. The auxiliary gas is a non-hydrocarbon gas, i.e., C x H y It is a gas other than C and H, and contains elements other than C and H. The auxiliary gas adjusts the performance of the DLC film, for example, adjusts the rigidity and improves the flexibility. By adding the auxiliary gas, the CC content and / or the CH and other bond content in the DLC film formed by a pure hydrocarbon gas can be adjusted, and the performance of the DLC film can be adjusted in conjunction with the properties of the auxiliary gas itself.

[0069] The auxiliary gas includes, but is not limited to, nitrogen gas, hydrogen gas, and fluorocarbon gas. The auxiliary gas can be introduced simultaneously with the reaction gas raw material or can be introduced sequentially. Preferably, the auxiliary gas is introduced simultaneously with the reaction gas raw material. In other words, this allows the production of hydrogen-containing diamond-like carbon films, nitrogen-containing diamond-like carbon films, fluorine-containing diamond-like carbon films, etc., with different hydrogen contents. The auxiliary gas can adjust the content ratio of CH bonds, CN bonds, and NH bonds in the DLC film, thereby changing the performance of the DLC.

[0070] It is worth mentioning that the addition of the auxiliary gas can adjust and improve the performance of the DLC film, but it may weaken the rigidity and original performance of the DLC film, so the amount of the auxiliary gas added must be balanced. The inventors have found that the addition of the auxiliary gas can improve certain properties of the DLC film, but when the amount of the auxiliary gas added is increased to a certain extent, the hardness of the DLC film is significantly reduced. For example, when the auxiliary gas is hydrogen gas, the role of the auxiliary gas is to adjust the proportion of hydrocarbons in the DLC film, for example, by increasing the content of CH bonds, thereby improving the flexibility of the DLC film. It is worth mentioning that when the content of the hydrogen gas exceeds a certain range, the auxiliary gas impairs the rigidity of the DLC film, so the amount of the auxiliary gas added must be controlled. When the content of the hydrogen gas exceeds 40%, the rigidity is significantly reduced. DLC films with a high hydrogen content have higher lubricity and transparency than DLC films with a low hydrogen content, and a certain amount of hydrogen contributes to the formation of SP3 bonds, which can increase hardness to a certain extent. However, as the hydrogen content continues to increase, the hardness of the diamond-like carbon film gradually decreases.

[0071] Furthermore, it is worth mentioning that the addition of the auxiliary gas can not only adjust the performance of the DLC film, but also increase the ionization concentration of the PECVD reaction process, making the reaction proceed more quickly.

[0072] Further, according to one embodiment of the present invention, when the DLC film is manufactured by the DLC manufacturing apparatus, the synergistic action of the radio frequency electric field and the pulse electric field is used to support the implementation of a plasma enhanced chemical deposition process. Preferably, the radio frequency and the high voltage pulse are applied simultaneously in the PECVD deposition process. In the synergistic action of the radio frequency and the high voltage pulse, a low power wireless high frequency discharge is used to maintain a plasma environment and suppress arcing during the high voltage discharge process, thereby improving the chemical deposition efficiency.

[0073] The radio frequency can be discharged into the inert gas and the reactive gas raw material, so that the whole coating process can be carried out in a plasma environment, and the reactive gas raw material can be brought into a high-energy state. The role of the pulse high voltage is to generate a strong electric field during the discharge process of the pulse power source, and the active particles in a high-energy state can be rapidly deposited on the surface of the substrate by the action of the strong electric field to form an amorphous carbon network structure. When the pulse electric field is in a non-discharge state, the DLC film deposited on the surface of the substrate can freely relax the amorphous carbon network structure, and the carbon structure can be transformed into a stable phase-curved graphene sheet layer structure by the thermodynamic action, and embedded in the amorphous carbon network to contribute to the formation of a transparent graphene-like structure. That is, the radio frequency electric field and the changing pulse electric field can be synergistically acted on each other to rapidly and stably deposit the DLC film on the surface of the substrate. Referring to FIG. 7, a transmission electron microscope image of the diamond-like carbon film according to the embodiment of the present invention is shown, and the DLC film is composed of an amorphous structure and a nanocrystalline structure.

[0074] Furthermore, when the DLC film is manufactured by the DLC manufacturing apparatus, the plasma source gas, the reactive gas raw material, and the auxiliary gas are supplied to the DLC manufacturing apparatus in stages, and accordingly, the radio frequency electric field and the pulse electric field are applied to the reactive gas raw material in stages and selectively.

[0075] In one embodiment, when the plasma source gas is supplied to the DLC manufacturing apparatus (also called the first stage), a radio frequency electric field and a pulse electric field are applied, but are not limited thereto. In this stage, the plasma source gas forms a part of plasma by the radio frequency electric field and the pulse electric field, and further promotes the generation of a part of plasma by interaction between gas molecules such as mutual impact. When the radio frequency electric field and the pulse electric field are applied, it is preferable to apply the radio frequency electric field and then the pulse electric field, and this form makes it easier to start glowing, so that ionization is more effective. In addition, when the reactive gas raw material and the auxiliary gas raw material are supplied (also called the second stage), the radio frequency electric field and the pulse electric field are applied simultaneously, that is, the radio frequency power supply and the pulse power supply are kept on. In this stage, a part of the reactive gas raw material generates plasma by the radio frequency electric field and the pulse electric field, and a part of the reactive gas generates plasma by excitation of the plasma generated by the plasma source gas. In addition, some of the auxiliary gases generate plasma by the radio frequency electric field and the pulse electric field, and some of the auxiliary gases are excited by other plasmas to generate plasma. This continuously increases the plasma concentration in the DLC manufacturing apparatus, activating the plasma deposition reaction process, so that the DLC film is rapidly and effectively deposited on the surface of the substrate. It should be understood by those skilled in the art that the plasma-excited chemical vapor deposition process is a very complicated reaction process, and the reactions occurring during the ionization deposition process are not limited to the above.

[0076] When the plasma source gas is supplied to the DLC manufacturing apparatus (also called the first stage), only the pulse electric field is applied. In this stage, the plasma source gas forms at least a part of plasma by the pulse electric field, and further promotes plasma generation by interaction between gas molecules such as mutual impact. When the reactive gas raw material and the auxiliary gas raw material are supplied (also called the second stage), the radio frequency electric field and the pulse electric field are applied simultaneously. In this stage, a part of the reactive gas raw material generates plasma by the radio frequency electric field and the pulse electric field, and a part of the reactive gas generates plasma by the excitation action of the plasma generated by the plasma source gas. In addition, a part of the auxiliary gas generates plasma by the radio frequency electric field and the pulse electric field, and a part of the auxiliary gas generates plasma by being excited by other plasma. As a result, the plasma concentration in the DLC manufacturing apparatus is continuously increased, so that the deposition reaction process of plasma is activated, and as a result, the DLC film is rapidly and effectively deposited on the surface of the substrate.

[0077] In one embodiment, the radio frequency power supply and the high voltage pulse power supply can be applied simultaneously or sequentially. In one embodiment, the high voltage pulse power supply is applied first when the plasma source gas is supplied, and the radio frequency power supply is applied when the reactive gas raw material is supplied, so that the two electric fields operate in a back-and-forth manner. In one embodiment, the radio frequency power supply is applied when the plasma source gas is supplied, and the high voltage pulse power supply is applied when the reactive gas raw material is supplied, so that the two electric fields operate in a back-and-forth manner.

[0078] It is worth mentioning that the selection of radio frequency field and pulsed field affects the performance of the deposited DLC film, but there are different preferred forms for different device structures, and in the device structure of the present invention in which radio frequency field and pulsed field are arranged inside and outside, the effect of simultaneously applying pulsed field and radio frequency field in the first and second stages is better than that of applying pulsed field or radio frequency field alone, and the effect of applying radio frequency field and then pulsed field is better than that of simultaneously applying radio frequency field and pulsed field or that of applying pulsed field and then radio frequency field, and the effect of applying radio frequency field and then pulsed field is better, and the gas is more likely to glow start and generate plasma when applying radio frequency field and then pulsed field. It is also worth mentioning that in some embodiments, the plasma source gas added in the first stage generates only a part of plasma, but due to its basic characteristics, for example, inert gas is not deposited on the surface of the substrate or does not become a part of the diamond-like carbon film. When the plasma is generated from the plasma source, the plasma acts on the surface of the substrate to etch the surface of the substrate, i.e., removes residues on the surface of the substrate while preparing the reactive gas precursor for deposition. The etching action of the plasma source on the substrate surface causes the DLC film to be more firmly deposited on the substrate surface. In some embodiments, the plasma source gas added in the first stage generates only a portion of the plasma, which not only etches the substrate but also deposits on the substrate surface, and may cause a deposition reaction together with the reactive gas precursor in the second stage. For example, nitrogen gas and fluorocarbon gas may cause a deposition reaction together with the hydrocarbon gas, which is the reactive gas precursor in the second stage, to adjust the content ratio of CH bonds, CN bonds, and NH bonds in the DLC film, thereby changing the performance of the DLC film.

[0079] In the second stage, the reactant gas and the auxiliary gas are deposited together on the surface of the substrate to form the DLC film.

[0080] It is worth mentioning that the synergistic effect of radio frequency and high voltage pulse improves the deposition efficiency, and the protective film can be effectively deposited and formed on the surface of the substrate, that is, the DLC film can be formed by chemical deposition reaction within a short time, thereby improving the production efficiency and enabling industrial mass production of the DLC film.

[0081] Furthermore, when the DLC film is manufactured by the DLC manufacturing apparatus, the deposition rate and the deposition film thickness of the DLC film can be controlled by controlling the gas flow rate introduced into the apparatus. An example is controlling the gas flow rate of the plasma source gas, the reactant gas raw material, and the auxiliary gas. When the DLC film is manufactured by the DLC manufacturing apparatus, the desired DLC film can be obtained by controlling process parameters such as the pressure in the reaction chamber, the radio frequency power, the pulse voltage, the duty ratio, and the coating time. In other words, the performance including the thickness, hardness, and transparency of the obtained DLC film can be controlled by adjusting or controlling process parameters such as the gas flow rate, the pressure in the reaction chamber, the radio frequency power, the pulse voltage, the duty ratio, and the coating time.

[0082] Furthermore, when the DLC film is manufactured by the DLC manufacturing apparatus, the reaction temperature in the manufacturing apparatus can be controlled, for example, by detecting the ambient temperature of the substrate by a temperature detection module and feedback-adjusting other process parameters, thereby controlling the temperature within a predetermined range. The temperature range in the manufacturing apparatus is 25°C to 100°C. Preferably, the temperature range is 25°C to 50°C.

[0083] Fig. 2 is a block diagram of a DLC manufacturing apparatus according to one embodiment of the present invention. Fig. 3 is a schematic diagram of a DLC manufacturing apparatus according to the embodiment of the present invention. Figs. 4A-4B are perspective views of an embodiment of a DLC manufacturing apparatus according to the embodiment of the present invention. Fig. 5A is an exploded schematic view of an embodiment of a DLC manufacturing apparatus according to the embodiment of the present invention.

[0084] 2 and 3, the present invention provides a DLC manufacturing apparatus for manufacturing the DLC film. Furthermore, the DLC apparatus introduces a reaction gas to perform deposition by PECVD to form the DLC film on a surface of a substrate.

[0085] The DLC manufacturing apparatus includes a main body 10 and a reaction chamber 100. The reaction chamber 100 is used to accommodate the substrate and to cause an introduced gas to carry out a deposition reaction, and the main body 100 forms the reaction chamber 100.

[0086] Preferably, the reaction chamber 100 is a sealed chamber, i.e., the reaction chamber 100 does not allow for uncontrolled gas flow therethrough.

[0087] Further, the plurality of gas supply units 20 includes a plasma source supply unit 21, a reactive gas raw material supply unit 22, and an auxiliary gas supply unit 23. The plasma source supply unit 21 is controllably connected to the reaction chamber 100, and the plasma source supply unit 21 is used to supply the plasma source gas to the reaction chamber 100. The plasma source gas includes, but is not limited to, an inert gas, a nitrogen gas, and a fluorocarbon gas. Among them, the inert gas includes, but is not limited to, He, Ar, and the fluorocarbon gas includes, but is not limited to, carbon tetrafluoride. The plasma source gas can be a single gas or a mixture of two or more gases.

[0088] The reaction gas source supply unit 22 is controllably connected to the reaction chamber 100, and is used to supply the reaction gas source to the reaction chamber 100. The reaction gas source is a hydrocarbon gas C x H y and C x H yIn the formula, x is an integer from 1 to 10, and y is an integer from 1 to 20. The reaction gas raw material may be a single gas or a mixture of two or more gases. The hydrocarbon gas is preferably selected from the group consisting of methane, ethane, propane, butane, ethylene, acetylene, propylene, and propyne, which are in a gaseous state under normal pressure, and may also be vapor formed by evaporation under reduced pressure or heat, such as benzene vapor or toluene vapor.

[0089] The auxiliary gas supply 23 is controllably connected to the reaction chamber 100, and is used to supply the auxiliary gas to the reaction chamber 100. Examples of auxiliary gases include, but are not limited to, hydrogen gas, nitrogen gas, and fluorocarbon gas.

[0090] According to an embodiment of the present invention, the plasma source supply unit 21 includes a plurality of supply lines 26 each used to supply a different plasma source gas. More specifically, the number or number of connections of the supply lines 26 of the plasma source supply unit 21 is determined by the plasma source gas to be introduced. That is, when one type of the plasma source gas is to be introduced, the number of the supply lines 26 of the plasma source supply unit 21 is one, whereas when two types of the plasma source gas are to be introduced, the number of the supply lines 26 of the plasma source supply unit 21 is two, and the following is inferred from this. Preferably, a single gas is supplied from each supply line 26 of the plasma source supply unit 21. That is, only one type of gas is passed through each supply line 26, not multiple gases or mixed gases. In this way, it is easy to control the amount of gas introduced while preventing pre-reaction between gases. Optionally, in some embodiments, multiple types of gases can be introduced into the lines, or the same gas can be introduced into multiple lines.

[0091] In one embodiment of the present invention, the supply lines 26 of the plasma source supply unit 21 include one supply line 26 for supplying the plasma source gas to the reaction chamber. For example, in one embodiment, the supply line 26 of the plasma source supply unit 21 is used to supply argon gas.

[0092] The reaction gas raw material supply unit 22 includes a plurality of supply lines 26 for respectively supplying different reaction gas raw materials. More specifically, the number or number of connections of the supply lines 26 of the reaction gas raw material supply unit 22 is determined by the reaction gas raw materials to be introduced. That is, when one type of reaction gas raw material is to be introduced, the number of supply lines 26 of the reaction gas raw material supply unit 22 is one, whereas when two types of reaction gas raw materials are to be introduced, the number of supply lines 26 of the reaction gas raw material supply unit 22 is two, and the following is inferred from this. Preferably, a single gas is supplied from each supply line 26 of the reaction gas raw material supply unit 22. That is, only one type of gas is passed through each supply line 26, not multiple gases or mixed gases. In this way, it is easy to control the amount of gas introduced while preventing pre-reaction between gases. Optionally, in some embodiments, multiple types of gases can be introduced into the lines, or the same gas can be introduced into multiple lines.

[0093] In one embodiment of the present invention, the reaction gas raw material supply unit 22 includes two supply lines 26 for introducing two different gases, respectively. For example, one of the lines supplies methane and the other line supplies acetylene, but this is not limiting.

[0094] The auxiliary gas supply unit 23 includes a plurality of supply lines 26 each used to supply a different auxiliary gas. More specifically, the number or number of connections of the supply lines 26 of the auxiliary gas supply unit 23 is determined by the auxiliary gas to be introduced. That is, when one type of the auxiliary gas is to be introduced, the number of the supply lines 26 of the auxiliary gas supply unit 23 is one, whereas when two types of the auxiliary gas are to be introduced, the number of the supply lines 26 of the auxiliary gas supply unit 23 is two, and the following is inferred from this. Preferably, a single gas is supplied from each supply line 26 of the auxiliary gas supply unit 23. That is, only one type of gas is passed through each supply line 26, not multiple gases or mixed gases. In this way, it is easy to control the amount of gas introduced while preventing pre-reaction between gases. Optionally, in some embodiments, multiple types of gases can be introduced into the lines, or the same gas can be introduced into multiple lines.

[0095] In one embodiment of the present invention, the auxiliary gas supply 23 comprises one supply line 26 for supplying the auxiliary gas to the reaction chamber. For example, in one embodiment, the supply line 26 of the auxiliary gas supply 23 is used to supply hydrogen gas.

[0096] According to one embodiment of the present invention, the diamond-like carbon film manufacturing apparatus includes a confluence region 25, which is connected to the reaction chamber 100 and connects the gases of the respective gas supply units 20. That is, the confluence region connects the plasma source supply unit 21, the reaction gas raw material supply unit 22, and the auxiliary gas supply unit 23. In one embodiment of the present invention, the introduced gases are connected in the confluence region and then supplied to the reaction chamber 100. Of course, in other embodiments of the present invention, each of the supply units can supply gases to the reaction chamber 100 individually.

[0097] The gas supply unit 20 includes a control valve 24 for controlling the introduction and shutoff of gas. The gas supply unit 20 further includes a plurality of control valves 24 provided in the supply pipes 26 of the plasma source supply unit 21, the reactive gas raw material supply unit 22, and the auxiliary gas raw material supply unit, respectively, for separately controlling the flow of gas in each pipe.

[0098] The diamond-like carbon film manufacturing apparatus includes a radio frequency power supply 30 and a pulse power supply 40. The radio frequency power supply 30 is used to apply a radio frequency electric field to the reaction chamber 100, and the pulse power supply 40 is used to supply a pulse electric field to the reaction chamber 100.

[0099] 4A-4B are perspective views of one embodiment of the DLC manufacturing apparatus according to the embodiment of the present invention. FIG. 4C is a perspective view of another embodiment of the DLC manufacturing apparatus according to the embodiment of the present invention. FIG. 5A is an exploded schematic view of one embodiment of the DLC manufacturing apparatus according to the embodiment of the present invention. FIG. 5B is a modified embodiment of the gas inlet frame. FIG. 6 is a schematic view of a modified embodiment of the DLC manufacturing apparatus according to the embodiment of the present invention.

[0100] The DLC manufacturing apparatus includes a plasma source unit 50, which is electrically connected to the radio frequency power source 30 so as to obtain electrical energy from the radio frequency power source 30 and generate a radio frequency electric field.

[0101] The plasma source unit 50 is disposed outside the main body 10. For example, the plasma source unit 50 is disposed on at least one side of the main body 10, but is not limited thereto. For example, when the main body 10 has a rectangular structure, the plasma source unit can be disposed on any one or more of six sides of the main body 10, and when the main body 10 has a columnar structure, the plasma source unit can be disposed on an annular side and / or both bottoms of the main body 10.

[0102] 4A to 5A, in this embodiment of the present invention, the main body 10 further includes a housing 11 and a control door 12. The control door 12 is used to control opening and closing of the housing 11. The main body 10 is provided with a gas extraction port 101, which is disposed on one side surface of the housing 11. In one embodiment of the present invention, the gas extraction port 101 is disposed on the back side of the housing 11, i.e., on one surface facing the control door 12.

[0103] In another embodiment of the present invention, referring to Fig. 4C, the gas extraction port 101 is located on the top side of the housing 11, i.e., on the top side adjacent to the control door 12. In installed use, the control door 12 can be designed to face outward, i.e., toward an operator. The plasma source unit 50 is located on one adjacent side, and the gas extraction port 101 is provided on the upper side, i.e., on the top side of the DLC manufacturing apparatus.

[0104] Preferably, the plasma source unit 50 is a Radio Frequency Inductively Coupled Plasma Source (RF-ICP) for applying an inductively coupled electric field to the reaction chamber 100 to generate plasma.

[0105] The plasma source unit 50 includes a gas inlet frame 51, a shield plate 52, and an induction coil 53, and the gas inlet frame 51 is airtightly connected to the main body 10. More specifically, the gas inlet frame 51 is attached to one side surface of the main body 10. The shield plate 52 is provided between the gas inlet frame 51 and the induction coil 53.

[0106] 5A, the gas inlet frame 51 has at least one communication path 5100, which communicates the main body with the gas supply unit, thereby allowing gas raw material to be introduced from the gas supply unit to the reaction chamber of the main body. The main body 10 has a window 1001, which communicates the reaction chamber 100 with the outside. The communication path 5100 communicates with the window 1001. That is, during operation, the gas supply unit 20 supplies gas, which enters the gas inlet frame 51 and is introduced into the reaction chamber 100 through the communication path 5100 and the window 1001 of the gas inlet frame 51.

[0107] Further, the gas inlet frame 51 has at least one communication hole 5101 and a main path 5102, and the communication hole 5101 communicates with the main path 5102 to form the communication path 5100. More specifically, the communication hole 5101 is arranged in the horizontal direction of the gas inlet frame 51. That is, a plane including the communication hole 5101 is arranged substantially parallel to the outer surface of the main body 10. The main path 5102 is arranged in the vertical direction of the gas inlet frame 51. That is, the direction of the main path 5102 is perpendicular to the outer surface of the main body 10. In other words, the direction in which the gas is made to enter the gas inlet frame 51 is different from the direction in which the gas is made to enter the reaction chamber 100, and more specifically, the direction in which the gas is made to enter the gas inlet frame 51 and the direction in which the gas is made to enter the reaction chamber 100 are perpendicular to each other.

[0108] It is worth mentioning that the gas supply unit 20 needs to communicate with the gas inlet frame 51 through a pipeline, but the baffle plate 52 and the induction coil 53 are directly attached to the outside of the gas inlet frame 51, that is, the gas inlet frame 51 provides a place for attaching the baffle plate 52 and the induction coil 53, but the introduced gas generates plasma through the inductively coupled electric field generated by the induction coil 53, so that the communication hole 5101, which is the path for the gas to enter, is arranged horizontally, and the main path 5102, which is the path for the gas to enter the reaction chamber 100, is arranged vertically, so that the external space of the main body 10 can be used more effectively, and the main volume of the DLC manufacturing apparatus does not become too large, and waste of the installation space can be reduced.

[0109] The size of the main passage 5102 is larger than the diameter of the communication hole 5101, in other words, the capacity of the main passage 5102 is larger than the capacity of the communication hole 5101. It is worth mentioning that the communication hole 5101 is a passage for introducing gas, and its small size allows the gas flow rate to be more precisely controlled. The gas supply passage is a passage for generating plasma by the action of the induction coil 53, and it is considered that the larger the space, the larger the area of ​​action of the induction electric field, and the stronger the interaction between more gas molecules or ions.

[0110] Furthermore, the communication hole 5101 may be in a shape extending linearly, or may be in a curved or other irregular shape. That is, the inside of the communication hole 5101 may be arranged to extend linearly along the side of the gas inlet frame 51, or to penetrate the side of the gas inlet frame 51 in a curved shape. The number of the communication holes 5101 may be one or more. In one embodiment of the present invention, the four sides of the gas inlet frame 51 are provided with one communication hole 5101 each to communicate with the main passage 5102, so that the side space of the gas inlet frame 51 can also be utilized.

[0111] The gas inlet frame 51 has a plurality of mounting holes 5105, and the mounting holes 5105 are used to mount the gas inlet frame to the main body 10 via a fixing member. As an example, the gas inlet frame may be fixed to the main body 10 by passing a screw through the mounting holes 5105, but is not limited thereto.

[0112] 5B, there is shown another modified embodiment of the gas inlet frame 51 according to the present invention. In this embodiment, the gas inlet frame 51 has an inner communication path 5103, which is provided inside the gas inlet frame 51 and connects two adjacent communication holes 5101 inside. At least one air distribution hole 5104 is provided inside the gas inlet frame 51 to connect the inner communication path 5103 and the main inlet passage 5102. That is, in this embodiment of the present invention, the communication hole 5101 does not directly communicate with the main path 5102, but communicates with the main path 5102 via the inner communication path 5103 and the air distribution hole 5104. Preferably, the multiple air distribution holes 5104 are each arranged at a different position inside the gas inlet frame 51, for example, inside the four frames of the gas inlet frame 51, but are not limited to this, which allows the air to penetrate more uniformly into the main path 5102.

[0113] In one embodiment of the present invention, the gas inlet frame 51 has multiple inner connecting paths 5103 which are connected to each other to form an inner annular path 5200, thereby allowing gas to be introduced from any of the connecting holes 5101, while gas can also be sent to the main path 5102 from any of the air distribution holes 5104 on the other side.

[0114] Furthermore, different gases can be pre-merged in the inner communication passage 5103 or the formed inner annular passage 5200, so that the gases can be mixed more thoroughly and more plasma can be generated in the preliminary reaction.

[0115] Furthermore, the number of the air distribution holes 5104 can be set to be greater than the number of the communication holes 5101, so that gas can be introduced into the main passage 5102 more quickly or in greater quantities, allowing more plasma to be generated in the main passage and enter the reaction chamber 100.

[0116] In one embodiment of the present invention, the gas inlet frame 51 can have one communication hole 5101 for taking in air. That is, when it is necessary to transport a plurality of kinds of gases, they can be merged and then enter from the communication hole 5101, or they can be sequentially entered into the inner communication path 5103 through the same communication hole 5101, and then dispersed to each position of the main path 5102 through the inner air distribution hole 5104.

[0117] The blocking plate 52 functions to seal one port of the main path 5102 and isolate the main path 5102 of the gas inlet frame 51 from the induction coil 53. That is, the gas is introduced from the communication hole 5101, passes through the main path 5102, and enters the reaction chamber 100, but does not flow into the induction coil 53. Furthermore, the blocking plate 52 isolates the gas, but seals it so as not to isolate the electric field. That is, the gas in the main path 5102 or the gas in the reaction chamber 100 can be affected by the induced electric field caused by the induction coil 53. Preferably, the blocking plate 52 is a ceramic seal plate to reduce the effect of the induced electric field of the induction coil 53 being fed to the main path 5102 and the reaction chamber 100.

[0118] The plasma source unit 50 further includes an outer cover plate 54. The outer cover plate 54 is disposed outside the induction coil 53, in other words, the induction coil 53 is sandwiched between the shield plate 52 and the outer cover plate 54.

[0119] The gas inlet frame 51 includes a main frame 511 and an insert member 512. The main frame 511 is hermetically disposed outside the main body 10, the insert member 512 is disposed outside the main frame 511, and the blocking plate 52, the induction coil 53, and the external cover plate 54 are sequentially inserted into the insert member 512, so that the blocking plate 52, the induction coil 53, and the external cover plate 54 are removably fixed to the main frame 511 by the insert member 512.

[0120] The DLC manufacturing apparatus includes a mounting plate 60, which is electrically connected to the pulsed power supply 40 so as to obtain electrical energy from the pulsed power supply 40 and generate a pulsed electric field. The mounting plate 60 is accommodated in the reaction chamber 100 and applies a pulsed electric field to the reaction chamber 100. The mounting plate has a flat structure and is suitable for mounting the substrate. That is, the sample to be deposited is placed on the mounting plate 60 for deposition. It is worth mentioning that the mounting plate 60 is used not only to position the substrate, but also to apply a pulsed electric field, that is, to provide a pulsed electric field effect at the position where the substrate is placed. That is, the pulsed electric field effect is provided from the bottom and the periphery of the substrate, so that the electric field effect is more direct.

[0121] According to an embodiment of the present invention, the diamond-like carbon film manufacturing apparatus supports the implementation of a plasma-enhanced chemical deposition process by the synergistic action of a radio frequency electric field and a high-voltage pulse electric field. Preferably, the radio frequency and the high-voltage pulse are applied simultaneously in the PECVD deposition process. In the synergistic action of the radio frequency and the high-voltage pulse, the chemical deposition efficiency is improved by maintaining a plasma environment by a low-power radio frequency discharge and suppressing arc discharge during the high-voltage discharge process. Arc discharge is a type of discharge method in which glow discharge is further strengthened, and its instantaneous current can reach tens or hundreds of amperes. If these large currents flow to the surface of a product, they may damage the product, which is more harmful to electronic products. However, it is expected that the low-power radio frequency discharge maintains a low-temperature plasma environment and suppresses arc discharge during the pulse high-voltage discharge process, and the synergistic action of the radio frequency electric field and the pulse electric field optimizes the deposition process and reduces damage to the substrate to be deposited.

[0122] The plasma source unit 50 can perform the entire coating process in a plasma environment by discharging the plasma source gas and the reactive gas raw material, and the reactive gas raw material can be in a high-energy state; the role of the pulsed high voltage by the pulsed power source 40 and the above-mentioned electrode plate 60 is to generate a strong electric field during the discharge process of the pulsed power source 40, and the active particles in the high-energy state are rapidly deposited on the surface of the substrate under the action of the strong electric field to form an amorphous carbon network structure. When the pulsed power source 40 and the above-mentioned electrode plate 60 are in a non-discharging state, the DLC film deposited on the surface of the substrate undergoes free relaxation of the amorphous carbon network structure, and the carbon structure is transformed into a stable phase-curved graphene sheet layer structure under the thermodynamic action, which is embedded in the amorphous carbon network and contributes to forming a transparent graphene-like structure. In other words, the radio frequency electric field and the changing pulsed electric field act synergistically with each other, so that the DLC film can be rapidly and stably deposited on the surface of the substrate.

[0123] It is worth mentioning that the combined action of radio frequency and high voltage pulse improves the deposition efficiency, so that the protective film can be effectively deposited and formed on the surface of the electronic device screen; that is, the DLC film can be formed by chemical deposition reaction within a short time, so that the production efficiency is improved and the DLC film can be mass-produced industrially.

[0124] It is also worth mentioning that in the prior art, diamond-like carbon (DLC) films are usually formed by magnetron sputtering coating, and the magnetron sputtering process is a kind of PVD process, which uses a block graphite target as the carbon source, and its ionization efficiency and deposition efficiency are low, so that its application in some cases is limited. Meanwhile, in the embodiment of the present invention, the carbon source in PECVD is gas, and the ionization action is performed by the external DC pulse power supply 40 and the radio frequency power supply 30, so that the ionization degree and deposition efficiency are improved, and thus a high hardness DLC film layer can be formed, and the cost is further reduced. Meanwhile, in the PVD process, graphite is used as the carbon source target, and it needs to be preheated during the manufacturing process, and the reaction rate is slow, so that the heat accumulation in the entire process is large and the reaction temperature is high. In contrast, in the PECVD reaction process of the present invention, the carbon source is gas, there is no need to heat it, the deposited thin film is thin, and the deposition time is short, so that the heat accumulation in the entire process is small, and the reaction temperature is low, which can be controlled to 25°C to 100°C, which is suitable for coating some electronic devices.

[0125] It is also worth mentioning that in actual industrial production, production efficiency is one of the important factors. For example, the screen of a mobile phone is only one of many parts of a mobile phone. If it takes a lot of time to simply improve some of the performance of the screen, it is not feasible in actual production and application. For example, some existing DLC ​​films can achieve the effect of improving performance with a longer reaction time, but it is not suitable for mass production, which is one of the reasons that restricts the practical application of some thin films. On the other hand, in the embodiment of the present invention, the DLC manufacturing apparatus performs PECVD chemical deposition in its reaction chamber 100, and the synergistic effect of radio frequency and high voltage pulse can effectively increase the deposition rate with a simpler process, so that diamond-like carbon films can be widely used in mass industrial production.

[0126] According to an embodiment of the present invention, the positron plate 60 has air holes communicating both sides of the positron plate 60. The air holes are used to pass the gas entering the reaction chamber 100 and apply a discharge effect. Furthermore, when the gas introduced into the junction enters the reaction chamber 100 along the gas introduction path of the inductively coupled plasma source (ICP), a discharge effect is generated on the gas around the positron plate 60, whereby the gas is ionized to generate plasma.

[0127] Furthermore, the base plate 60 is provided with a plurality of air holes arranged in an array on the base plate 60 so as to allow the air flow to flow uniformly to above the base plate 60 located below and to generate a relatively consistent electric field action on the air flow.

[0128] The air hole may be a straight hole penetrating the electrode plate 60, or a curved or broken line hole communicating with both sides of the electrode plate 60. The cross-sectional shape of the air hole may be circular, rectangular, polygonal or other curved shape.

[0129] A plurality of the above-mentioned placement electrode plates 60 are arranged in parallel with a gap therebetween. The distance between two adjacent placement electrode plates 60 is a predetermined distance, and when selecting the distance between two adjacent placement electrode plates 60, it is necessary to consider the electric field conditions applied to the substrate on the two adjacent placement electrode plates 60 while also considering the space utilization rate, i.e., the number of samples that can be deposited at one time. For example, if the distance is too large, the effect of the pulse electric field is weak, affecting the ionization efficiency and deposition efficiency, and the space utilization rate is low, while if the distance is too small, the effect of the pulse electric field is too strong, affecting the performance of the substrate such as an electronic device, making it inconvenient to insert and remove samples, and poor work efficiency, so it is necessary to balance the effects of various factors. For example, the distance between two adjacent placement electrode plates 60 is 10 mm to 200 mm. Preferably, the distance between two adjacent placement electrode plates 60 is 20 mm to 150 mm. Optionally, the distance between two adjacent stationary electrodes 60 is 20mm to 30mm, 30mm to 40mm, 40mm to 50mm, 50mm to 60mm, 60mm to 70mm, 70mm to 80mm, 80mm to 90mm, 90mm to 100mm, 100mm to 110mm, 110mm to 120mm, 120mm to 130mm, 130mm to 140mm, or 140mm to 150mm.

[0130] The position and number of the plasma source units 50 arranged outside the main body 10 can be adjusted as required. In one embodiment of the present invention, the number of the plasma source units 50 is one, and the plasma source unit 50 is arranged on one side of the main body 10. Moreover, the plasma source unit 50 is arranged on one side of the main body 10 perpendicular to the electrode plate 60, as shown in FIG. 3. In another embodiment of the present invention, two plasma source units 50 are arranged symmetrically on two sides of the main body 10, and further, the two plasma source units 50 are respectively arranged on two sides of the main body 10 perpendicular to the electrode plate 60.

[0131] 3, the DLC manufacturing apparatus includes a pump system 70 connected to the reaction chamber 100 to adjust the air pressure in the reaction chamber 100. The pump system 70 includes a pressure regulating valve 71 for adjusting the pressure in the reaction chamber 100. The pump system 70 can be used to extract gas from the reaction chamber 100 to lower the pressure or to bring the pressure closer to a predetermined pressure range, and can be used to deliver gas into the reaction chamber 100 to provide a gaseous reaction source.

[0132] The DLC manufacturing apparatus includes a temperature detection module 80 for detecting the temperature in the reaction chamber 100 and feedback-controlling other process parameters of the diamond-like carbon film manufacturing apparatus. Here, the temperature detection module 80 is exemplified by, but not limited to, a thermocouple.

[0133] Preferably, the temperature detection module 80 is disposed at a position equivalent to the position where the substrate is disposed so as to detect the real-time reaction temperature of the substrate. For example, the temperature detection module 80 is disposed directly below the position where the sample is disposed on the mounting plate 60, or the temperature detection module 80 is disposed around the position where the sample is disposed on the mounting plate 60, or the temperature detection module 80 is disposed directly above the position where the sample is disposed on the mounting plate 60, or the temperature detection module 80 is disposed at the position where the sample is disposed on the mounting plate 60, for example, at an air hole below the substrate.

[0134] The reaction temperature range in the reaction chamber 100 of the DLC manufacturing apparatus is controlled to 25° C. to 100° C. Preferably, the temperature range is 25° C. to 50° C. The above temperature range has little effect on the substrate and is suitable for products that cannot withstand high temperatures, such as electronic products.

[0135] The materials used in typical electronic products are polymeric materials, which are prone to deterioration in their resistance to thermal deformation and generally have a high temperature resistance of less than 100°C. As the final process in the manufacturing process, the coating process needs to ensure the performance change of the raw materials, so low-temperature processes are essential for processing electronic products. When manufacturing such diamond-like carbon films, the reaction temperature is detected in real time by a thermocouple installed at the same position as the product, and the reaction temperature is controlled so as not to affect the electronic device. When forming the diamond-like carbon film, it can be formed on a single component such as an unassembled electronic screen, or on an assembled product such as the screen of an assembled electronic device, making the process conditions more flexible.

[0136] The DLC manufacturing apparatus includes a control unit 90. The control unit 90 controls the reaction conditions in the manufacturing apparatus, and examples of the control unit 90 include, but are not limited to, controlling the gas supply of the plasma source supply unit, the gas supply of the reactive gas raw material, the gas supply of the auxiliary gas, the operation of the pump system 70, the temperature detection module 80, the pulse power supply 40, and the radio frequency power supply 30. The control unit 90 controls process parameters such as the discharge characteristics of the radio frequency and high voltage pulses, the flow rate of the reactive gas, and the coating time, thereby obtaining a target diamond-like carbon film.

[0137] Furthermore, in order to easily obtain the target DLC film, the 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 process parameters such as the gas flow rate and coating time of each of the gas supply units 20.

[0138] It is worth mentioning that the manufacturing process of ion-exchanged tempered glass in the prior art is complicated, and potassium nitrate plasma salt needs to be heated at high temperature to form an ion bath, and the ion exchange time is long and the cost is high. Meanwhile, in the embodiment of the present invention, the DLC manufacturing apparatus directly deposits diamond-like carbon film on the surface of a substrate such as glass by PECVD method, which can be completed at room temperature, the time required is short, and the cost is easy to control. Meanwhile, the DLC manufacturing apparatus in the embodiment of the present invention assists in carrying out plasma chemical vapor deposition by radio frequency and high voltage pulse, and uses low-power radio frequency discharge to maintain a plasma environment and suppress arc discharge in the high voltage discharge process, and compared with the conventional physical vapor deposition method such as magnetron sputtering, the substrate temperature during the entire deposition process is low, so it can be applied to the coating of some electronic devices that cannot withstand high temperatures. If a tempering treatment is to be performed on the glass screen of a mobile phone, the vapor deposition coating of DLC can be performed after the assembly of the mobile phone glass is completed. That is, the DLC film can be installed after the manufacturing of the electronic device is completed, so the process flexibility is high; and the control unit 90 can control the synergistic effect of multiple parameters, so the controllability of the manufacturing process is good.

[0139] Referring to FIG. 1, according to an embodiment of the present invention, there is provided a method for manufacturing a DLC film, which includes the following steps. (A) introducing a plasma source gas into a reaction chamber 100 in which a substrate is placed; (B) turning on the radio frequency power source 30 and the pulse power source 40 to activate the plasma source gas to generate plasma; (C) A gas mixture of a reactive gas source containing a hydrocarbon gas and an auxiliary gas is flowed into the reaction chamber 100, and a DLC film is deposited by the combined action of a pulsed electric field and a radio frequency electric field; (D) Air or an inert gas is introduced and the substrate is removed.

[0140] Specifically, the method for producing the DLC film may include the following steps.

[0141] Step (1) Cleaning and activation of the sample surface: After placing the substrate sonicated in alcohol and acetone in the sample chamber, 1.5 × 10 -3 The vacuum is drawn to a pressure of 0.1 Pa or less, and high-purity helium gas in the plasma source gas is introduced to etch and clean the substrate. Then, the radio frequency power supply 30 and the high-voltage pulse power supply 40 are turned on to generate plasma by glow discharge of the plasma source gas, and the substrate is etched and activated for 10 minutes. In other words, this is one embodiment of step (A)-step (B).

[0142] Step (2) Deposition of DLC film: After cleaning, use radio frequency and high voltage pulses to support the production of transparent, hard, hydrogen-containing diamond-like carbon films by plasma enhanced chemical vapor deposition; introduce a hydrocarbon gas source as a reactive gas, turn on the radio frequency power supply 30 and the high voltage pulse power supply 40, or carry out the deposition action with the power supplies on in step (1), turn them off after depositing a thin film, release the vacuum, and take out the sample. That is, this is one embodiment of step (C)-step (D).

[0143] It is worth mentioning that the diamond-like carbon film manufacturing apparatus includes a multi-layer electrode group, so that multiple or a relatively large number of the substrates can be arranged at once, and the coating requirements for a large area can be met, and the coating process can be carried out in one go.

[0144] In step (1), during cleaning and activation of the sample surface, the flow rate of the introduced argon gas is 50sccm to 200sccm, the pressure range of the reaction chamber 100 is 30mtorr or less, the high voltage pulse power supply is 40 to -1000V, the duty ratio is 10%, and the cleaning time is 10min.

[0145] In one embodiment, step (1) requires pre-treating the surface of the substrate by the action of a radio frequency electric field and a high voltage pulse electric field, i.e., in the process of carrying out step (B), only the pulse power supply 40 is turned on so that the electrode plate 60 can discharge. For example, in step (1), the plasma source gas, such as argon gas or helium gas, generates plasma by 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 the surface of the substrate, i.e., peeling off a small amount of the surface layer, but due to its inert action, it cannot be deposited and left on the surface of the substrate. That is, in this process, the surface is mainly partially removed, but no deposition layer is formed. Step (1) prepares the ionization conditions for depositing the reactive gas raw material, micro-etches the surface of the substrate, and cleans the surface, so that the diamond-like carbon film to be deposited subsequently can be more firmly bonded to the surface of the substrate.

[0146] It is worth mentioning that the flow rate of the gas introduced into the reaction chamber 100 corresponds to the magnitude of the corresponding pressure, and if the pressure is too high or too low, it will affect the ionization effect. If the pressure is too low, the cleaning effect will not be obtained, and if the pressure is too high, the substrate may be damaged. In addition, the length of the cleaning time may affect the cleaning effect. If the cleaning time is too short, the cleaning effect will not be obtained, and if the time is too long, there is a risk of over-etching, which will lengthen the overall process period and increase the process cost. According to an embodiment of the present invention, in the step of introducing the plasma source, the flow rate of the introduced argon gas or helium gas is 50sccm to 200sccm, the pressure range of the reaction chamber is 50 to 150mtorr, the high voltage pulse power supply 40 is -200V to -5000V, the duty ratio is 10% to 60%, and the cleaning time is 5 to 15min. In these ranges, each of the above factors can be appropriately adjusted to contribute to the overall deposition process of the DLC film.

[0147] In step (2), radio frequency and high-voltage pulse voltage are used to support the fabrication of a transparent, hard, hydrogen-containing diamond-like carbon film by plasma enhanced chemical vapor deposition. In this method, radio frequency can maintain a plasma environment throughout the coating stage, and the pulse high voltage applied to the sample substrate can deposit active particles on the substrate surface under the action of a strong electric field in the discharge process of the pulse power source 40 to form an amorphous carbon network structure. The non-discharge process is a process of free relaxation of the amorphous carbon network structure, in which the carbon structure is transformed into a stable phase-curved graphene sheet layer structure under the thermodynamic action, and is embedded in the amorphous carbon network to form a transparent amorphous / nanocrystalline graphene sheet layer composite structure. For example, 99.999% methane, argon, hydrogen, and 99.5% acetylene are used as the deposition gas (carbon source can be provided from methane or acetylene, and argon gas or hydrogen gas can be doped, and the ratio of carbon source to doping gas can be adjusted between 5:1 and 1:5), 30 to 500 SCCM of reaction gas is supplied by the gas supply unit 20, and the chamber pressure is set to 0.5 to 10 Pa. Furthermore, 100 to 700 W is applied to the inductively coupled plasma source (ICP) 50, which generates an induced oscillating electromagnetic field in the reaction chamber 100, and the passing gas is ionized to generate plasma. A bias voltage of -600 to 1200 V is applied to the cathode electrode plate, which accelerates and draws in the plasma formed by the inductively coupled plasma source (ICP), thus forming a transparent and hard nanocomposite film on the substrate.

[0148] The parameters for the hydrogen-containing diamond-like carbon coating process are CH 4 Gas flow rate: 40 to 100 sccm, C 2 H 2 The gas flow rate of H is 50 to 200 sccm, the gas flow rate of Ar is 40 to 100 sccm, 2The gas flow rate is set to 40 to 100 sccm, the pressure range in the reaction chamber 100 is set to 50 to 150 mTorr, the power range of the radio frequency power supply 30 is set to 50 to 300 W, the voltage of the bias pulse power supply 40 is set to -200 V to -5000 V, the duty ratio is set to 10% to 80%, and the coating time is set to 5 to 30 minutes, thereby finally obtaining a transparent and hard hydrogen-containing diamond-like carbon film of 5 to 1000 nm.

[0149] During the deposition of the reactive gas source, the ratio of different gas flow rates introduced affects the atomic ratio of the DLC film and thus the performance of the film layer. 4 The gas flow rate is 40 to 100 sccm, C 2 H 2 The gas flow rate of H is 50 to 200 sccm, the gas flow rate of Ar is 40 to 100 sccm, 2 When the gas flow rate is set to 40 to 100 sccm, the rigidity of the DLC film is good, the flexibility of the DLC film can be adjusted by the hydrogen gas, and a predetermined deposition reaction rate can be maintained.

[0150] In the deposition step of the reactive gas raw material, the magnitude of the power voltage of the power field and the pulse field of the radio frequency power source 30 affects related parameters such as the temperature rise, ionization rate, and deposition rate in the ionization process. According to an embodiment of the present invention, when the power range of the radio frequency power source 30 is 50 to 300 W, the voltage of the bias pulse power source 40 is -200 V to -5000 V, and the duty ratio is 10% to 80%, within these parameter ranges, the temperature rise is not too fast, the process time is not excessively extended, and a good deposition rate can be maintained while the ionization rate is increased.

[0151] The magnitude of the negative bias voltage directly relates to the ionization of the gas and its mobility when it reaches the surface of the product. High voltage means higher energy, which can result in a hard coating layer. However, high ion energy has a strong impact effect on the substrate product, which can cause micro-scale impact craters on the surface, while high energy impacts can accelerate the temperature rise, which can cause the product to be damaged due to excessive temperature. Therefore, it is necessary to balance the bias voltage, reaction temperature and reaction speed.

[0152] Preferably, in some embodiments, the radio frequency is between 20 and 300 KHz. The relatively high pulse frequency avoids the continuous accumulation of charge on the surface of the insulating product, suppresses large arcing, and increases the limit of the deposition thickness of the coating layer.

[0153] In the deposition step of the reactive gas raw material, if the coating time is too short, the formed film layer becomes thin and the hardness is poor, while if the coating time is too long, the thickness increases but the transparency is affected. According to the embodiment of the present invention, when the coating time is set to 5-30 min, the thickness, hardness and transparency can be balanced, and finally, a transparent and hard hydrogen-containing diamond-like carbon film of 5-1000 nm can be obtained.

[0154] Furthermore, in step (2), the temperature range in the reaction chamber 100 is controlled to 25°C to 100°C. Preferably, the temperature range is 25°C to 50°C.

[0155] The present invention will be further described below in conjunction with examples, but the contents of the present invention are not limited to the following examples. The main performance indicators of the product are as shown in Table 1 below. TIFF0007621358000001.tif92170

[0156] Working Example Among the various coating conditions in the examples of the present invention, the film formation under the specified conditions described in the above embodiment as the DLC coating film formation is set as an example, and the film formation under conditions other than these conditions is set as a comparative example, and the characteristics of the DLC coating film under each situation are measured. In the examples and comparative examples, the film formation device used was the device having the structure shown in the above embodiment in FIG. 1. Also, a 6.5-inch quartz glass screen was used as the substrate. As a prerequisite, the glass screen was ultrasonically cleaned with absolute ethanol and acetone for 20 minutes each, then dried by spraying nitrogen gas, and clamped in a vacuum chamber, and the air pressure in the chamber was set to 1.5×10 -3 It is necessary to vacuum the substrate for 10 minutes by using an air extraction system to obtain a vacuum of 0.1 Pa or less, introducing 100 SCCM of high-purity argon gas, turning on the bias power supply (DC pulse) and radio frequency power supply, controlling the chamber pressure to 25 mtorr, bias power supply voltage to 500-900 V, duty ratio to 10%, and frequency to 80 kHz. Next, a film is coated on the substrate, and DLC coating is performed by the ICP-enhanced CVD method as shown in each of the examples and comparative examples described below.

[0157] First set of examples: Combination of methane and argon gases First, in Examples 1 to 3 and Comparative Examples 1 and 2, the coating gas was CH 4 and Ar. The coating conditions (atmospheric pressure, gas flow rate, power supply conditions, coating time) in Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 2 below. Furthermore, Table 2 shows the film layer properties (film thickness, hardness, light transmittance) under various coating conditions. TIFF0007621358000002.tif146170

[0158] In this set of examples, the chamber pressure is all kept at 25 mtorr, and in the examples, tests are performed by setting different bias voltage values. In a comparative example, the bias power supply and the radio frequency power supply are each used separately.

[0159] As is clear from the data shown in the above table, the coating apparatus of the present invention can obtain thin films with excellent performance even when using different bias voltage values, and the deposition rate is also suitable for industrial production, but if the bias voltage value is too low, the energy obtained by the plasma will be insufficient, while if the bias voltage is too high, a sputtering effect will occur on the substrate, the deposition efficiency will decrease, and the internal stress will increase. From Example 2, it can be concluded that by properly setting the process parameters, high surface hardness (Mohs hardness 7H) and high transmittance can be obtained, which can be very suitable for use in flexible screens.

[0160] As can be seen by comparing Example 2 with Comparative Examples 1 and 2, the film layer deposited only by ICP without bias voltage has a slow deposition rate and poor hardness performance, while the performance and quality indexes of the film layer obtained only by bias voltage without using ICP technology are all worse than those of Example 1. This is because the combined use of ICP and bias electrode technology resulted in a composite structure of amorphous carbon and nanocrystalline graphene (see Figure 7).

[0161] Second set of examples: Combination of acetylene and argon gas First, in Examples 4 to 6 and Comparative Examples 3 and 4, a C gas having a gas purity of 99.9% was used as the reaction gas. 2 H 2 A combination of 10 ... TIFF0007621358000003.tif144170

[0162] In this series of examples, the chamber pressure is all kept at 25 mtorr, and the voltage value of the bias power supply is set at 900 V. In the examples, the test is carried out by setting different radio frequency power. As a comparative example, the bias power supply and the radio frequency power supply are used alone, and compared with Comparative Examples 1 and 2, the effect of different power supply combinations with different carbon sources on the thin film quality is compared.

[0163] As can be seen from the data shown in the above table, the coating apparatus of the present invention can obtain coatings with excellent performance by setting the parameters reasonably, and increasing the radio frequency power can increase the ion concentration and therefore improve the coating efficiency. However, if the deposition efficiency is too fast, it may affect the quality of the film layer. From Example 5, it can be concluded that if the process parameters are properly set, a coating layer with high light transmittance and high hardness can be obtained.

[0164] As can be seen by comparing Example 5 with Comparative Examples 1 to 4, the film layer deposited only by ICP without bias voltage has a slow film formation rate and reduced hardness performance, while the performance and quality indexes of the film layer obtained only by bias voltage without using ICP are all worse than those of the other Examples, and this phenomenon is consistent across different gas combinations.

[0165] Third set of examples: Combination of acetylene and hydrogen gas First, in Examples 7 to 9 and Comparative Examples 5 and 6, the coating gas was C 2 H 2 and H 2 The coating conditions (atmospheric pressure, gas flow rate, power supply conditions, coating time) in Examples 7 to 9 and Comparative Examples 5 and 6 are shown in Table 4 below. Furthermore, Table 4 shows the film layer properties (film thickness, hardness, light transmittance) under various coating conditions. TIFF0007621358000004.tif141170

[0166] In this series of examples and comparative examples, the bias voltage value is set to 900V, the radio frequency power is set to 300W, and the tests are carried out by setting different chamber pressures.

[0167] As can be seen from the data shown in the above table, the coating apparatus of the present invention can be used within a certain chamber pressure range and other parameters can be reasonably set to obtain a film layer with acceptable performance. The magnitude of the chamber pressure can directly affect the glow phenomenon, which in turn can affect the film deposition rate and the quality of the film layer. If the air pressure is too low, the probability of particle collision will be low, resulting in a low ionization rate, while if the air pressure is too high, the probability of particle collision will be high, resulting in a large energy loss of charged particles, resulting in a poor quality of the obtained film layer. From Example 7, it can be concluded that if the process parameters are properly set, a coating layer with high light transmittance and high hardness can be obtained.

[0168] As can be seen by comparing Example 5 with Comparative Examples 1 to 4, if the air pressure is too high or too low and other parameters are kept constant, the gray phenomenon does not occur, so it is very important to set the chamber pressure appropriately.

[0169] It should be understood by those skilled in the art that the embodiments of the present invention described above and illustrated in the accompanying drawings are given by way of example only, and are not intended to limit the present invention. The objects of the present invention have been fully and effectively achieved. The functional and structural principles of the present invention have been shown and explained in the examples. Various modifications and alterations can be made to the embodiments of the present invention without departing from the principles.

Claims

1. a body having a reaction chamber for disposing a substrate; A plasma source unit; at least one gas supply for supplying a reaction gas to the reaction chamber; Equipped with The plasma source unit is provided outside the body, and applies a radio frequency electric field to the reaction chamber to generate plasma, and deposits the reaction gas on the surface of the substrate by a PECVD method to form a DLC film; a pulsed power source and a radio frequency power source for applying a pulsed electric field and the radio frequency electric field, respectively, to activate the reactive gas and generate plasma; the plasma source unit includes a gas inlet frame airtightly provided outside the main body, an induction coil, and a shield plate provided between the gas inlet frame and the induction coil; the gas inlet frame has a communication path that communicates the reaction chamber of the main body with the gas supply unit, the gas inlet frame has at least one communication hole and a main passage on an outer surface of the body, the body has a window portion communicating with the reaction chamber, the window portion of the body communicates with the communication hole of the gas inlet frame and the main passage to form the communication passage; The communication hole and the main passage are arranged in a direction perpendicular to each other, the communication hole is parallel to the outer surface of the body, and the main passage is perpendicular to the outer surface of the body; The plasma source unit further includes an outer cover plate, and the induction coil is sandwiched between the shield plate and the outer cover plate; the gas introduction frame comprises a main frame body airtightly provided outside the main body, and an insertion member disposed outside the main frame body and into which the blocking plate, the induction coil and the external cover plate are inserted.

2. The DLC manufacturing apparatus of claim 1 , wherein the radio frequency power source is electrically connected to the plasma source unit and supplies power to the plasma source unit.

3. 2. The DLC manufacturing apparatus according to claim 1, wherein the at least one communication hole communicates with the outside to inject gas, the gas inlet frame further has an air distribution hole provided inside the gas inlet frame and communicating with the main path, and an inner communication path that communicates the communication hole and the air distribution hole, and the communication path is formed by communicating the window portion of the main body, the communication hole of the gas inlet frame, the inner communication path, the air distribution hole, and the main path.

4. The DLC manufacturing apparatus according to claim 3 , wherein a plurality of the inner communication paths are connected to each other to form an inner annular path.

5. 2. The DLC manufacturing apparatus according to claim 1, wherein the blocking plate is a ceramic sealing plate.

6. 2. The DLC manufacturing apparatus of claim 1, wherein the plasma source unit is a radio frequency inductively coupled plasma source that applies an inductively coupled electric field.

7. The DLC manufacturing apparatus according to any one of claims 1 to 6, further comprising a mounting electrode plate, the mounting electrode plate being accommodated in the reaction chamber and electrically connected to the pulsed power supply to apply the pulsed electric field to the reaction chamber, and the substrate being suitably disposed on the mounting electrode plate.

8. 8. The DLC manufacturing apparatus according to claim 7, wherein the mounting electrode plate has air holes that connect both sides of the mounting electrode plate.

9. 8. The DLC manufacturing apparatus according to claim 7, comprising a plurality of mounting plates arranged in parallel with a gap therebetween.

10. 8. The DLC manufacturing apparatus according to claim 7, wherein the voltage control range of the pulse power supply is −200V to −5000V.

11. The DLC manufacturing apparatus according to any one of claims 1 to 6, wherein the gas supply unit includes a plasma source supply unit that supplies a plasma source gas to the reaction chamber and activates a deposition reaction by a PECVD method.

12. 12. The DLC manufacturing apparatus according to claim 11, wherein the plasma source gas is at least one selected from the group consisting of an inert gas, a nitrogen gas, and a fluorocarbon gas.

13. 7. The DLC manufacturing apparatus according to claim 1, wherein the gas supply unit includes a reactive gas raw material supply unit for supplying a hydrocarbon gas CxHy to the reaction chamber, and the hydrocarbon gas CxHy is deposited on a surface of the substrate by a PECVD method to form the DLC film.

14. 7. The DLC manufacturing apparatus according to claim 1, wherein the gas supply unit includes an auxiliary gas supply unit for supplying an auxiliary gas to the reaction chamber, the auxiliary gas adjusts a C—H content in the DLC film and reacts with a hydrocarbon gas CxHy to deposit on the surface of the substrate, thereby forming the DLC film.

15. 15. The DLC manufacturing apparatus according to claim 14, wherein the auxiliary gas is at least one selected from the group consisting of nitrogen gas, hydrogen gas, and fluorocarbon gas.

16. The DLC manufacturing apparatus according to any one of claims 1 to 6, further comprising a temperature detection module provided at a position around the substrate.

17. Supplying a reactive gas to a reaction chamber of the body via at least one gas supply, and urging the reactive gas to be deposited on a surface of a substrate in the reaction chamber by a PECVD method using a radio frequency electric field and a pulsed electric field to form a DLC film; a plasma source unit electrically connected to a radio frequency power source to receive electrical energy from the radio frequency power source and generate the radio frequency electric field; the plasma source unit includes a gas inlet frame airtightly provided outside the main body, an induction coil, and a shield plate provided between the gas inlet frame and the induction coil; the gas inlet frame has a communication path that communicates the reaction chamber of the main body with the gas supply unit, the gas inlet frame has at least one communication hole and a main passage on an outer surface of the body, the body has a window portion communicating with the reaction chamber, the window portion of the body communicates with the communication hole of the gas inlet frame and the main passage to form the communication passage; The communication hole and the main passage are arranged in a direction perpendicular to each other, the communication hole is parallel to the outer surface of the body, and the main passage is perpendicular to the outer surface of the body; The plasma source unit further includes an outer cover plate, and the induction coil is sandwiched between the shield plate and the outer cover plate; the gas introduction frame comprises a main frame body airtightly provided outside the main body, and an insertion member disposed outside the main frame body and into which the blocking plate, the induction coil and the external cover plate are inserted.

18. 20. The method of claim 17, wherein the controlling step applies a radio frequency electric field followed by a pulsed electric field.

19. The method of claim 17, wherein the radio frequency electric field is an inductively coupled electric field.

20. The method for producing a DLC film according to any one of claims 17 to 19, comprising the steps of supplying a plasma source gas to the reaction chamber, activating a deposition reaction by a PECVD method, and simultaneously applying the radio frequency electric field and the pulse electric field to the plasma source gas.

21. 20. The method for producing a DLC film according to any one of claims 17 to 19, further comprising the step of: supplying an auxiliary gas to the reaction chamber, the auxiliary gas adjusting a C-H content in the DLC film, reacting with a hydrocarbon gas CxHy, and depositing the DLC film on the surface of the substrate.

22. The method for producing a DLC film according to any one of claims 17 to 19, further comprising disposing a mounting plate in the reaction chamber, the mounting plate being electrically connected to a pulsed power supply and applying the pulsed electric field in the reaction chamber.

23. The method for producing a DLC film according to any one of claims 17 to 19, further comprising a step of detecting a temperature at a position around the substrate and performing feedback control.

24. (a) introducing a plasma source gas via at least one gas supply into a reaction chamber of a body in which a substrate is disposed; (b) turning on a pulsed power source and a radio frequency power source to apply a radio frequency electric field and a pulsed electric field, respectively, to activate the plasma source gas to generate plasma; (c) introducing a hydrocarbon gas CxHy into the reaction chamber to deposit a DLC film on the surface of the substrate; a plasma source unit electrically connected to the radio frequency power source to obtain electrical energy from the radio frequency power source and generate the radio frequency electric field; the plasma source unit includes a gas inlet frame airtightly provided outside the main body, an induction coil, and a shield plate provided between the gas inlet frame and the induction coil; the gas inlet frame has a communication path that communicates the reaction chamber of the main body with the gas supply unit, the gas inlet frame has at least one communication hole and a main passage on an outer surface of the body, the body has a window portion communicating with the reaction chamber, the window portion of the body communicates with the communication hole of the gas inlet frame and the main passage to form the communication passage; The communication hole and the main passage are arranged in a direction perpendicular to each other, the communication hole is parallel to the outer surface of the body, and the main passage is perpendicular to the outer surface of the body; The plasma source unit further includes an outer cover plate, and the induction coil is sandwiched between the shield plate and the outer cover plate; the gas introduction frame comprises a main frame body airtightly provided outside the main body, and an insertion member disposed outside the main frame body and into which the blocking plate, the induction coil and the external cover plate are inserted.

25. The method for producing a DLC film according to claim 24, wherein in step (b), the radio frequency power source is turned on before the pulse power source is turned on.

26. The method of claim 24, wherein the radio frequency electric field is an inductively coupled electric field.

27. The method for producing a DLC film according to any one of claims 24 to 26, wherein step (c) includes a step of supplying an auxiliary gas to the reaction chamber, the auxiliary gas adjusting a C-H content in the DLC film and reacting with the hydrocarbon gas CxHy to deposit on the surface of the substrate to form the DLC film.

28. 28. The method of claim 27, further comprising the step of extracting gas from the reaction chamber and adjusting the air pressure in the reaction chamber.

29. The method for producing a DLC film according to claim 27, further comprising the step of detecting a temperature at a position around the substrate and performing feedback control.

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