JP6693099B2 - Film forming method, film forming apparatus, and film forming program - Google Patents

Description

  The present invention relates to a plasma processing apparatus that uses plasma to form a film on the surface of a material to be processed having conductivity such as steel.

Conventionally, various film forming apparatuses have been proposed for forming a film on the surface of a material to be processed having conductivity, such as steel, using plasma.
For example, a technique for forming a diamond-like carbon (DLC) film on the surface of the material to be processed is known from Patent Document 1 and the like.

  In the film forming apparatus disclosed in Patent Document 1, the duty ratio of the material to be processed varies from "initial microwave pulse duty ratio", for example, 60% to "intermediate layer final duty ratio", for example, 72%. A microwave pulse of "500 Hz" with a microwave pulse duty ratio is supplied. Further, a predetermined voltage of "negative bias voltage pulse duty ratio", for example, "500 Hz" at 90%, for example, a negative bias voltage pulse of -200 V is applied to the material to be processed.

Here, the intermediate layer film formation time is set to, for example, 15 seconds. Further, the inert gas Ar and the source gases CH ₄ , C ₂ H ₂ and TMS (tetramethylsilane) are supplied from the gas supply unit. As a result, in the portion of the intermediate layer film near the surface of the material to be processed in the film thickness direction, the added metal element Si of the DLC film is relatively large, and a DLC film having good adhesion to the material to be processed is formed. .. In addition, in the intermediate layer film, as the distance from the surface of the material to be processed is increased in the film thickness direction, the added metal element Si of the DLC film becomes relatively small, and a DLC film having good adhesion with the DLC layer film laminated on the upper side is formed. Be filmed.

JP, 2014-189898, A

  However, in the film forming apparatus disclosed in Patent Document 1 described above, in order to form a DLC film having good adhesion to the material to be processed, the intermediate layer film forming time becomes long, and There is a problem that it is difficult to shorten. It is possible to increase the voltage of the negative bias voltage pulse or increase the power of the microwave pulse in order to increase the film formation speed of the intermediate layer film formation process, but the number of occurrences of abnormal discharge increases. , The surface defects of the DLC film increase, and there is a risk of affecting the wear characteristics after the DLC film is formed. Further, although the film formation rate can be increased to some extent by increasing the negative applied voltage of the negative bias voltage pulse, if the negative applied voltage of the negative bias voltage pulse is increased to a predetermined voltage value, it is further increased. There is a concern that the film formation speed will not increase even if the temperature is increased.

  Therefore, the present invention has been made to solve the above-described problems, and it is possible to significantly reduce the film formation time for forming a DLC film having good adhesion to a material to be processed. An object is to provide a film forming method, a film forming apparatus, and a film forming program.

  In order to achieve the above object, the film forming method according to claim 1 is a processing container in which a conductive material to be processed can be placed, and a gas supply unit for supplying a raw material gas and an inert gas to the processing container. A microwave supply unit for supplying a pulsed microwave pulse for generating plasma along the processed surface of the material to be processed, and a pulsed shape for expanding the sheath layer along the processed surface of the material to be processed. A negative voltage application unit for applying a negative bias voltage pulse to the material to be processed, and a microwave pulse supplied from the microwave supply unit via the microwave introduction surface, and the treatment on the microwave introduction surface. A film forming apparatus including a microwave supply port for propagating as a surface wave to the enlarged sheath layer along the processed surface of the material to be processed arranged so as to project into the container, and a control unit. A microwave for supplying a microwave pulse for generating plasma along the processing surface of the material to be processed via the microwave supply unit, which is performed by the control unit. Supplying step, negative voltage applying step of applying a negative bias voltage pulse to the processed surface of the material to be processed through the negative voltage applying section, and control for controlling the microwave supplying section and the negative voltage applying section The control unit controls the control unit so that a period for supplying a microwave pulse having a pulse frequency of 6 kHz or more is provided via the microwave supply unit in the control process, and the negative voltage is applied. If a plurality of negative bias voltage pulses are applied during the supply stop time during which the microwave is not supplied within one cycle of the microwave pulse via the applying unit, In addition, the application time of the negative bias voltage in one cycle of the negative bias voltage pulse is controlled to be longer than the microwave supply time in one cycle of the microwave pulse. ..

  The film forming method according to claim 2 is the film forming method according to claim 1, wherein in the control step, a negative bias voltage pulse of 75 kHz or more is applied through the negative voltage applying section. Is controlled so as to apply.

  Further, the film forming method according to claim 3 is the film forming method according to claim 2, wherein the control section includes a cycle of the negative bias voltage pulse via the negative voltage applying section in the control step. The first duty ratio, which is the ratio of the application time of one pulse of the negative bias voltage to the above, is controlled to be 63% or more to 93% or less, and the negative bias voltage within one cycle of the negative bias voltage pulse is controlled. Is controlled so as to be 3.6 microseconds or more.

  Further, a film forming method according to a fourth aspect is the film forming method according to any one of the first to third aspects, wherein the source gas contains a hydrocarbon-based gas.

  Further, a film forming method according to a fifth aspect is the film forming method according to any one of the first to fourth aspects, wherein in the control step, the control unit includes the microwave supply unit via the microwave supply unit. The second duty ratio, which is the ratio of the supply time of one pulse of the microwave to the cycle of the microwave pulse, is controlled to be 24% or less.

  Further, a film forming method according to claim 6 is the film forming method according to any one of claims 1 to 5, wherein the control unit includes 40 kHz through the microwave supply unit in the control step. It is characterized by controlling so as to supply a microwave pulse of less than.

  Further, a film forming method according to claim 7 is the film forming method according to any one of claims 1 to 6, wherein the control unit includes a first layer on a surface of the material to be processed in the control step. After forming the first film of the eye to a predetermined thickness, when forming the second film of the second layer, one pulse of the microwave with respect to the cycle of the microwave pulse is passed through the microwave supply unit. The second duty ratio, which is the ratio of the supply time, is controlled to be larger than that during the formation of the first coating.

  Further, the film forming method according to claim 8 is the film forming method according to claim 7, wherein the control unit has a thickness of the first film of the first layer of 10 nm or more in the control step. It is characterized in that the thickness is controlled so that

  Further, the film forming method according to claim 9 is the film forming method according to claim 1, wherein in the control step, the control unit applies the negative voltage of −600 V and the negative voltage of 200 kHz through the negative voltage applying unit. Of the bias voltage pulse is applied to the material to be processed, and the first duty ratio, which is the ratio of the application time of one pulse of the negative bias voltage to the period of the negative bias voltage pulse, is 80%. Control so as to supply the microwave pulse of 1 kW and 30 kHz through the microwave supply unit, and is the ratio of the supply time of one pulse of the microwave to the cycle of the microwave pulse. It is characterized in that the second duty ratio is controlled to be 8%.

  A film forming apparatus according to a tenth aspect of the invention is a processing container in which a conductive material to be processed can be placed, a gas supply unit for supplying a source gas and an inert gas to the processing container, and the processing target material. A microwave supply unit for supplying a pulsed microwave pulse for generating plasma along the processed surface of the processing material, and a pulsed negative bias voltage for expanding the sheath layer along the processed surface of the processing material. A negative voltage application unit for applying a pulse to the material to be processed, and a microwave pulse supplied from the microwave supply unit is projected through the microwave introduction surface into the processing container with respect to the microwave introduction surface. A microwave supply port that propagates as a surface wave to the expanded sheath layer along the processed surface of the material to be processed, the microwave supply part, and the negative voltage application part. And a control unit for controlling the supply of a microwave pulse having a pulse frequency of at least 6 kHz via the microwave supply unit, and applying the negative voltage. A plurality of negative bias voltage pulses during a supply stop time during which no microwave is supplied within one cycle of the microwave pulse, and a negative bias voltage pulse within one cycle of the negative bias voltage pulse. The bias voltage application time is controlled to be longer than the microwave supply time within one cycle of the microwave pulse.

  Furthermore, the film forming program according to claim 11 is a processing container in which a material to be processed having conductivity can be arranged, a gas supply unit for supplying a source gas and an inert gas to the processing container, A microwave supply unit for supplying a pulsed microwave pulse for generating plasma along the processed surface of the processed material having conductivity for generating plasma along the processed surface of the processed material; Negative voltage applying unit for applying a pulsed negative bias voltage pulse for enlarging the sheath layer along the processing surface of the processing material to the processing target material, and microwave introduction of the microwave pulse supplied from the microwave supply unit Surface wave to the expanded sheath layer along the processing surface of the material to be processed which is arranged so as to project into the processing container with respect to the microwave introduction surface through the surface. To a computer for controlling a film forming apparatus provided with a microwave supply port for propagating a microwave pulse for generating plasma along the processed surface of the material to be processed through the microwave supply unit. A microwave supplying step, a negative voltage applying step of applying a negative bias voltage pulse to the processed surface of the material to be processed through the negative voltage applying section, the microwave supplying section and the negative voltage applying section And a control step for controlling the step of controlling the control circuit so that a period during which at least a microwave pulse having a pulse frequency of 6 kHz or higher is supplied through the microwave supply part is provided in the control step. Through the applying unit, a plurality of negative bias voltage pulses are generated within the supply stop time during which the microwave is not supplied within one cycle of the microwave pulse. And the application time of the negative bias voltage in one cycle of the negative bias voltage pulse is controlled to be longer than the supply time of the microwave in one cycle of the microwave pulse. It is characterized by being executed.

  In the film forming method according to claim 1, the film forming apparatus according to claim 10, and the film forming program according to claim 11, a DLC film having good adhesion to the material to be processed is formed on the surface of the material to be processed in a short time. It becomes possible to form a film with a predetermined thickness. Therefore, it becomes possible to significantly shorten the film formation time for forming the DLC film having good adhesion to the material to be processed.

  Further, in the film forming method according to the second aspect, by applying a negative bias voltage pulse of 75 kHz or more, a plurality of negative bias voltage pulses within one cycle of the microwave pulse during which the microwave is not supplied are supplied. The bias voltage pulse can be surely applied. Further, it is possible to easily control the application time of the negative bias voltage within one cycle of the negative bias voltage pulse so as to be longer than the supply time of the microwave within one cycle of the microwave pulse. .. As a result, it becomes possible to further shorten the film formation time for forming the DLC film having high adhesion on the surface of the material to be processed.

  Further, in the film forming method according to the third aspect, it is possible to prolong the application time of the negative bias voltage within one cycle of the negative bias voltage pulse, and the DLC film having high adhesion to the surface of the material to be processed. It is possible to further shorten the film forming time for forming the film.

  Further, in the film forming method according to the fourth aspect, since the raw material gas contains a hydrocarbon-based gas, it becomes possible to reliably form a DLC film having high adhesion on the surface of the material to be processed.

  In the film forming method according to claim 5, the material to be processed is controlled by controlling the second duty ratio, which is the ratio of the supply time of one pulse of the microwave to the cycle of the microwave pulse, to be 24% or less. It is possible to improve the film formation rate for forming a DLC film having high adhesion on the surface of the.

  Further, in the film forming method according to claim 6, by controlling so as to supply a microwave pulse of less than 40 kHz, a DLC film having high adhesion is stably formed on the surface of the material to be processed while suppressing abnormal discharge. Then, it becomes possible to form a film.

  Further, in the film forming method according to the seventh aspect, the film forming speed for forming the second film of the second layer can be made higher than the film forming speed for forming the first film of the first layer. .. As a result, the first coating of the first layer is formed on the surface of the material to be processed and the adhesion is secured, and even if the deposition rate of the second coating of the second layer is increased, the DLC for the material to be processed is increased. The adhesiveness as a film is maintained. As a result, it is possible to shorten the entire film formation processing time for forming a DLC film having a predetermined thickness on the surface of the material to be processed.

  Further, in the film forming method according to claim 8, by controlling the thickness of the first coating of the first layer to be 10 nm or more, high adhesion to the surface of the material to be processed can be obtained. It is possible to further shorten the film formation time for forming the DLC film. Further, it becomes possible to maintain the adhesiveness between the first coating of the first layer and the second coating of the second layer.

  Further, in the film forming method according to the ninth aspect, it becomes possible to form a DLC film having high adhesion on the surface of the material to be processed to a predetermined thickness in a short time. Therefore, it becomes possible to significantly shorten the film formation time for forming the DLC film having good adhesion to the material to be processed.

It is explanatory drawing which shows schematic structure of the film-forming apparatus which concerns on this embodiment. It is a block diagram which shows the electric constitution of the film-forming apparatus. It is a schematic diagram of the waveform of a microwave pulse and the waveform of a negative bias voltage pulse. It is a schematic diagram which shows an example of the DLC film formed into the surface of the to-be-processed material. It is a figure which shows an example of the cleaning data table stored in ROM or HDD of a control part. It is a figure which shows an example of the intermediate layer film-forming data table stored in ROM or HDD of a control part. It is a figure which shows an example of the DLC layer film-forming data table stored in ROM or HDD of a control part. It is a flow chart which shows "basic film formation processing" which CPU of a control part performs. 6 is a first adhesion measurement result table showing an example of the relationship between the positive voltage application time per pulse and the adhesion of each DLC film formed at each frequency of the negative bias voltage pulse. 9 is a negative voltage application time table showing an example of a relationship between a positive voltage application time and a negative voltage application time per pulse at each frequency of a negative bias voltage pulse. A first example showing the relationship between the positive voltage application time per pulse and the first duty ratio, which is the ratio of the negative voltage application time per pulse of the negative bias voltage pulse, at each frequency of the negative bias voltage pulse It is a duty ratio table. An example of the relationship between the second duty ratio, which is the ratio of the supply time of a microwave pulse having a pulse frequency of 30 kHz per pulse, at each frequency of the negative bias voltage pulse, and the deposition rate of each DLC film deposited It is a film-forming rate table shown. An example of the relationship between the second duty ratio, which is the ratio of the supply time of a microwave pulse having a pulse frequency of 30 kHz per pulse, and the adhesiveness of each DLC film formed at each frequency of the negative bias voltage pulse is shown. It is a 2nd adhesiveness measurement result table. 7 is an abnormal discharge frequency table showing an example of the relationship between the frequency of a microwave pulse and the abnormal discharge frequency in a negative bias voltage pulse having a pulse frequency of 200 kHz. It is a 3rd adhesiveness measurement result table which shows an example of the relationship between the frequency of a microwave pulse, and the adhesiveness of each DLC film formed into a negative bias voltage pulse of pulse frequency 200kHz. 9 is a surface defect number table showing an example of the relationship between the negative bias voltage and the number of surface defects of each DLC film formed in a negative bias voltage pulse having a pulse frequency of 200 kHz. 11 is a fourth adhesion measurement result table showing an example of the relationship between the negative bias voltage and the adhesion of each DLC film formed in the case of a negative bias voltage pulse having a pulse frequency of 200 kHz. Fifth adhesion measurement result showing an example of the relationship between the thickness of the intermediate layer film formed on the surface of the material to be processed and the adhesion of each DLC film formed at each frequency of the negative bias voltage pulse It's a table. 9 is an intermediate layer film formation condition table showing an example of film formation conditions capable of forming an intermediate layer film whose adhesion test is HF1 to HF4 by the basic film formation process shown in FIG. 8. It is a flowchart which shows the "2nd film-forming process" which CPU of the control part of the film-forming apparatus which concerns on another 1st Embodiment performs. It is a 6th adhesion measurement result table which shows an example of the relationship between the film-forming process which provided the exhaust process, and the adhesiveness of each DLC film formed in each frequency of a negative bias voltage pulse.

  Hereinafter, a film forming apparatus according to the present invention will be described in detail with reference to the drawings based on an embodiment embodied. First, a schematic configuration of the film forming apparatus 1 according to the present embodiment will be described based on FIGS. 1 and 2.

  As shown in FIGS. 1 and 2, the film forming apparatus 1 according to this embodiment includes a processing container 2, a vacuum pump 3, a gas supply unit 5, a control unit 6, and the like. The processing container 2 is made of metal such as stainless steel and has a hermetic structure. The vacuum pump 3 is a pump that can evacuate the inside of the processing container 2 via the pressure control valve 7. Inside the processing container 2, a material 8 to be processed, which is an object of film formation, having conductivity is held by a holder 9 having conductivity, which is made of stainless steel or the like.

  The material of the material to be processed 8 is not particularly limited as long as the surface has conductivity, but in the present embodiment, it is low temperature tempered steel. Here, the low temperature tempered steel is a material such as JIS G4051 (carbon steel steel for machine structure), G4401 (carbon tool steel), G44-4 (steel for alloy tool), or maraging steel. In addition to the low temperature tempered steel, the material to be processed may be ceramic or resin in which a conductive material is coated. Moreover, you may use the to-be-processed material in which the metal film was formed into the surface by the sputtering method etc.

The gas supply unit 5 supplies a raw material gas for film formation and an inert gas into the processing container 2. Specifically, an inert gas such as He, Ne, Ar, Kr, or Xe and a hydrocarbon-based source gas such as CH ₄ , C ₂ H ₂ , or TMS (tetramethylsilane) are supplied. In the present embodiment, description will be made on the assumption that the material to be processed 8 is subjected to the DLC film formation process by the source gases of C ₂ H ₂ , CH ₄ , and TMS.

The flow rates and pressures of the raw material gas and the inert gas supplied from the gas supply unit 5 may be controlled by the CPU 31 described later, or may be controlled by the operator. The raw material gas may be a gas containing a compound having a CH bond such as an alkyne, alkene, alkane, or aromatic compound, or a compound containing carbon. H ₂ may be included in the source gas.

  Plasma is generated for performing the DLC film formation process on the material 8 to be processed held inside the processing container 2. This plasma is generated by the microwave pulse control unit 11, the microwave oscillator 12, the microwave power supply 13 (see FIG. 2), the negative voltage power supply 15, and the negative voltage pulse generation unit 16. In the present embodiment, it is assumed that the surface wave excited plasma is generated by the method disclosed in Japanese Patent Laid-Open No. 2004-47207 (hereinafter, referred to as “MVP method (Microwave sheet-Voltage combination Plasma method)”). In the following description, the MVP method will be described.

  The microwave pulse control unit 11 oscillates a pulse signal having a pulse frequency of 39 kHz or less at a predetermined duty ratio as described later according to an instruction from the control unit 6 (see FIG. 15 and the like), and outputs the oscillated pulse signal to the microwave oscillator 12. Supply. The microwave oscillator 12 generates a microwave pulse according to the pulse signal from the microwave pulse control unit 11. The microwave power supply 13 supplies power to the microwave oscillator 12 that oscillates the microwave of 2.45 GHz with the instructed output according to the instruction of the control unit 6. That is, the microwave oscillator 12 supplies the microwave of 2.45 GHz to the isolator 17 described later in the form of pulsed microwave pulse according to the pulse signal from the microwave pulse control unit 11.

  The microwave pulse is projected from the microwave oscillator 12 via the isolator 17, the tuner 18, the waveguide 19, the coaxial waveguide converter (not shown) from the waveguide 19, and the coaxial waveguide 21 projected from the waveguide 19. It is supplied to the treated surface of the holder 9 and the material 8 to be processed through a microwave supply port 22 made of a dielectric material such as quartz that transmits microwaves. The isolator 17 prevents the reflected wave of the microwave from returning to the microwave oscillator 12. The tuner 18 matches the impedance before and after the tuner 18 so that the reflected wave of the microwave becomes the minimum.

  The outer peripheral surface excluding the upper end surface of the microwave supply port 22, that is, the outer peripheral surface excluding the microwave introduction surface 22A is covered with a side surface conductor 23 formed of a metal such as stainless steel. The side surface conductor 23 is fixed to the inner side surface of the processing container 2 by screwing or the like, and is electrically connected to the processing container 2. The center conductor of the coaxial waveguide 21 extends in the center of the microwave supply port 22.

  As shown in FIG. 1, the side surface conductor 23 has a cylindrical surrounding wall portion 23A protruding from the portion in contact with the outer circumference of the microwave introduction surface 22A into the processing container 2 over the entire circumference of the side surface conductor 23. Has been formed. The surrounding wall portion 23A is formed over the entire circumference of the microwave introduction surface 22A so as to surround the central conductor 24 composed of the holder 9 and the processed material 8 inward. That is, the surrounding wall portion 23A is formed of a metal such as stainless steel. Thereby, between the inner peripheral surface of the surrounding wall portion 23A and the outer peripheral surface of the central conductor 24, the microwave introducing surface 22A side is closed, and the substantially cylindrical surrounding space 20 in which the inside of the processing container 2 is opened is formed. Has been formed.

  Therefore, since the outer peripheral surface of the microwave supply port 22 excluding the microwave introduction surface 22A is covered with the side surface conductor 23, the microwave pulse supplied to the microwave supply port 22 causes the microwave provided to the holder 9 to be held. The microwave propagates near the wave introducing surface 22A. As a result, plasma is generated along the enclosed space 20 and the processed surface of the processed material 8. Further, the portion of the material to be processed 8 opposite to the holder 9 is arranged so as to project toward the inside of the processing container 2 with respect to the microwave supply port 22, and a negative bias voltage pulse is applied. The negative voltage electrode 25 is electrically connected.

  Between the central conductor of the microwave supply port 22 and the holder 9, a dielectric such as quartz is arranged between them to maintain a vacuum. The material 8 to be processed has, for example, a rod shape and is held on an extension line of the central conductor of the microwave supply port 22.

  The negative voltage power supply 15 supplies a negative bias voltage to the negative voltage pulse generator 16 according to an instruction from the controller 6. The negative voltage pulse generation unit 16 makes a pulse of the negative bias voltage supplied from the negative voltage power supply 15. In the pulsing process, the negative voltage pulse generation unit 16 controls the magnitude, period, and duty ratio of the negative bias voltage pulse having a pulse frequency of 250 kHz or less according to an instruction from the control unit 6, and This is a process of controlling to generate a predetermined voltage, for example, a positive bias voltage of +10 V to +60 V while the negative bias voltage pulse is not being generated. The negative bias voltage pulse, which is the pulsed negative bias voltage, and the positive bias voltage pulse, which is the positive bias voltage, cause the negative voltage electrode 25 to the workpiece 8 held inside the processing container 2. Applied through.

  That is, even when the material 8 to be processed is a metal base material, or when the ceramic or resin is coated with a conductive material, a negative bias voltage pulse is applied to at least the entire processed surface of the material 8 to be processed. Is applied. A negative bias voltage pulse is also applied to the entire surface of the holder 9 via the material 8 to be processed.

  As shown in FIG. 3, by controlling the generated microwave pulse 38 having a pulse frequency of 39 kHz or less and the negative bias voltage pulse 39 having a pulse frequency of 250 kHz or less to be simultaneously applied, as shown in FIG. Then, the surface wave excited plasma 28 is generated. The microwave is not limited to 2.45 GHz and may have a frequency of 0.3 GHz to 50 GHz. While the negative bias voltage pulse 39 is not applied, a positive bias voltage pulse 41 of a predetermined voltage, for example, + 10V to + 60V is applied. The negative voltage power supply 15 and the negative voltage pulse generation unit 16 are examples of the negative voltage application unit of the present invention.

  The microwave pulse control unit 11, the microwave oscillator 12, the microwave power supply 13, the isolator 17, the tuner 18, the waveguide 19, and the coaxial waveguide 21 are examples of the microwave supply unit of the present invention. Although the film forming apparatus 1 includes the negative voltage power supply 15 and the negative voltage pulse generation unit 16, it may further include a positive voltage power supply and a positive voltage pulse generation unit, or instead of the negative voltage pulse generation unit 16. In addition, a negative voltage generator that applies a continuous negative bias voltage instead of the pulsed negative bias voltage may be provided.

  A radiation thermometer 29 is arranged at a position near the outside of the quartz window 27 provided on the side wall of the processing container 2. The radiation thermometer 29 is a surface temperature of the processing surface of the processing material 8 at an arbitrary position of the processing surface in the range H1 in FIG. 1 facing the upper end of the processing material 8 to the upper end of the surrounding wall 23A. Is continuously measured. The radiation thermometer 29 is electrically connected to the control unit 6. A liquid crystal display (LCD) 30 is electrically connected to the control unit 6. Further, a buzzer or the like (not shown) is electrically connected to the control unit 6.

The radiation thermometer 29 receives infrared rays having a central wavelength λ of the measurement wavelength band from the processed surface of the material to be processed 8 and calculates the intensity V of the received infrared rays. The radiation thermometer 29 calculates an output temperature TP1 that is output as the surface temperature of the processed surface of the material 8 to be processed from the calculated infrared intensity V and the thermometer setting emissivity ε ₁ stored in advance. The radiation thermometer 29 outputs the calculated output temperature TP1 to the control unit 6 every predetermined time, for example, every 0.1 seconds.

The radiation thermometer 29 may output the calculated infrared intensity V to the control unit 6 every predetermined time, for example, every 0.1 seconds. The control unit 6 may calculate the surface temperature TP1 of the processed surface of the workpiece 8 from the intensity V of the input infrared ray and the thermometer setting emissivity ε ₁ stored in advance.

For example, the radiation thermometer 29 calculates the output temperature TP1 output as the surface temperature of the processed surface of the material 8 to be processed by the following formula (1) disclosed in “Tribologist 2008, 53, No. 5, page 301”. To do. In the following formula (1), α is a device constant, C ₂ is Planck's second constant, λ is a center wavelength of an infrared measurement wavelength band measured by the radiation thermometer 29, and ε ₁ is a thermometer. It is a set emissivity, and V is the intensity of infrared rays.

TP1 = C ₂ / λ / Ln {α × ε ₁ / V + 1} (1)

  As shown in FIG. 2, the control unit 6 includes a pressure adjusting valve 7, an atmosphere opening valve 10, a vacuum gauge 26, a radiation thermometer 29, a liquid crystal display (LCD) 30, a negative voltage power supply 15, and a negative voltage pulse generator 16. , The microwave pulse control unit 11, the gas supply unit 5, and the microwave power supply 13 are electrically connected.

  The control unit 6 outputs a control signal to the negative voltage power supply 15 and the microwave power supply 13 to control the applied power of the microwave pulse and the applied voltage of the negative voltage pulse. The control unit 6 outputs a control signal to the negative voltage pulse generation unit 16 and the microwave pulse control unit 11 so that the pulse frequency of the pulsed negative bias voltage pulse, the supply voltage, the duty ratio, and the microwave oscillator 12 are generated. The pulse frequency, the duty ratio, and the supplied power of the microwave pulse generated from the control unit are controlled.

  The control unit 6 outputs a flow rate control signal to the gas supply unit 5 to control the supply of the raw material gas and the inert gas. The control unit 6 outputs a control signal to the pressure adjusting valve 7 based on the pressure signal representing the pressure inside the processing container 2 input from the vacuum gauge 26 attached to the processing container 2. The pressure control valve 7 to which this control signal is input controls the pressure inside the processing container 2 by adjusting the valve opening based on the pressure signal included in this control signal.

  The control unit 6 outputs a fully open and fully closed control signal to the atmosphere opening valve 10. The atmosphere opening valve 10 to which the control signal of full opening is input fully opens the valve. The atmosphere opening valve 10 to which the fully closed control signal is input fully closes the valve opening degree. When the atmosphere opening valve 10 is fully opened, the internal pressure of the processing container 2 becomes the same as the outside pressure through the atmosphere opening valve 10.

  The control unit 6 includes a CPU 31, a RAM 32, a ROM 33, a hard disk drive (hereinafter referred to as “HDD”) 34, a timer 35, an end determination timer 36, and the like, and is configured by a computer. The CPU 31 temporarily stores various information in a volatile storage device such as the RAM 32, executes a program such as the film formation process shown in FIG. 8, and controls the entire film formation device 1. The timer 35 measures the elapsed time of the entire film forming process. The end determination timer 36 is configured to perform the ion cleaning, the intermediate layer film 42 formed on the processed surface of the material 8 to be processed, and the DLC layer film 43 (see FIG. 4) formed on the surface of the intermediate layer film 42. Determine the end of membrane processing.

  The ROM 33 and the HDD 34 are non-volatile storage devices, and include a program for film formation processing shown in FIG. 8, a pulse frequency of a negative bias voltage pulse shown in FIG. 3, a supply voltage, a duty ratio, and a pulse frequency of a microwave pulse. , Duty ratio, and information indicating the supplied power, and the data tables 45 to 47 shown in FIGS. 5 to 7 are stored.

  The program of the film forming process shown in FIG. 8 may be read from a storage medium such as a CD-ROM or a DVD-ROM by a driver (not shown) or may be downloaded from a network such as the Internet (not shown). It may also be executed by a server connected to a network such as the Internet (not shown).

[Explanation of surface wave excited plasma]
Usually, in the case of generating surface wave excited plasma, microwaves are supplied along the interface between plasma having an electron (ion) density of a certain level or more and a dielectric in contact with the plasma. The supplied microwave is propagated as a surface wave with the energy of the electromagnetic wave concentrated on this interface. As a result, the plasma contacting the interface is excited and further amplified by the high energy density surface wave. As a result, high density plasma is generated and maintained. However, when the dielectric material is replaced with a conductive material, the conductive material does not function as a waveguide for the surface wave, and the desired surface wave propagation and plasma excitation cannot occur.

  On the other hand, an essentially unipolar charged particle layer, a so-called sheath layer, is formed in the vicinity of the surface of the object in contact with the plasma. When the object is the material to be processed 8 having a negative bias voltage applied thereto, the sheath layer is a layer having a low electron density, that is, it has a positive polarity, and has a relative dielectric constant in the microwave frequency band. It is a layer of ε≈1. Therefore, the sheath thickness of the sheath layer can be increased by making the absolute value of the applied negative bias voltage larger than the absolute value of −100 V, for example. That is, the sheath layer expands. This sheath layer acts as a dielectric that propagates surface waves to the interface between the plasma and an object in contact with the plasma.

  Therefore, the microwave is supplied from the microwave supply port 22 arranged close to one end of the holder 9 that holds the material 8 to be processed, and a negative bias voltage is applied to the material 8 and the holder 9. Then, the microwave propagates as a surface wave along the interface between the sheath layer and the plasma. As a result, high-density excited plasma based on surface waves is generated along the surfaces of the material 8 to be processed and the holder 9. This high density excited plasma is the surface wave excited plasma 28 described above.

The electron density of high-density plasma due to surface wave excitation near the surface of the material 8 to be processed reaches 10 ¹¹ to 10 ¹² cm ⁻³ . When the DLC film formation process is performed by the plasma CVD using the MVP method, the film formation rate is 3 to 30 (nano m / sec) which is one to two orders of magnitude higher than when the DLC film formation process is performed by the normal plasma CVD. Therefore, high-speed film formation is possible.

  In this MVP method, since high-density excited plasma is generated in the vicinity of the surfaces of the material to be processed 8 and the holder 9 which are metal substrates, the surface temperature of the material to be processed 8 and the holder 9 is equal to or higher than the tempering temperature, for example, The temperature rises from about 250 ° C to about 300 ° C. However, since high-speed film formation is possible, the film formation time is 1/10 to 1/100 of the film formation time of normal plasma CVD. That is, since the film forming time can be shortened to several tens of seconds to several minutes, even if the surface temperature of the work material 8 exceeds the tempering temperature, the softening of the work material 8 can be suppressed.

Here, an example of waveforms to which the microwave pulse and the negative bias voltage pulse are applied will be described with reference to FIG.
As shown in FIG. 3, the cycle of the microwave pulse 38 is T1 (second). The supply time of each pulse of the microwave pulse 38 is T11 (seconds). Therefore, the duty ratio (second duty ratio), which is the ratio of the supply time of each pulse of the microwave pulse 38 to the cycle of the microwave pulse 38, is T11 / T1.

  The cycle of the negative bias voltage pulse 39 is T2 (second) shorter than the cycle of the microwave pulse 38. The application time of the negative bias voltage pulse 39 is T21 (seconds). Therefore, the duty ratio (first duty ratio), which is the ratio of the application time of each pulse of the negative bias voltage pulse 39 to the period of the negative bias voltage pulse 39, is T21 / T2. The application time of the positive bias voltage pulse 41 is T22 = T2-T21 (seconds).

  Then, a plurality of negative bias voltage pulses 39, for example, 2 to 6 negative bias voltage pulses 39, are supplied within the supply stop time (T1-T11) (seconds) during which the microwave is not supplied within one cycle of the microwave pulse 38. The bias voltage pulse 39 is set to be applied. Further, the application time of one cycle of the negative bias voltage pulse 39, that is, T21 (seconds) is longer than the supply time of one cycle of the microwave pulse 38, that is, T11 (seconds). It is set. The information indicating each time T1, T11, T2, T21, T22 (seconds) is calculated by the CPU 31 from the data stored in each of the data tables 45 to 47 stored in the ROM 33 or the HDD 34 of the control unit 6.

  Next, an example of the cleaning data table 45 stored in the ROM 33 or the HDD 34 will be described with reference to FIG. The cleaning data table 45 stores "basic ion cleaning conditions" for performing ion cleaning on the processed surface of the material 8 to be processed, which is executed by the CPU 31 in steps 14 to 16 of the flowchart shown in FIG.

  As shown in FIG. 5, the cleaning data table 45 includes a “work type” representing the type of the material 8 to be processed, a “basic ion cleaning condition” corresponding to the “work type”, and a vacuum before starting ion cleaning. It is composed of respective data indicating "attainment vacuum degree (Pa)" representing the degree of vacuum inside the processing container 2 exhausted by the pump 3. The “work type” stores that it is common to all types of the material 8 to be processed.

  Basic ion cleaning conditions are "negative bias voltage (V)", "frequency of negative bias voltage pulse (kHz)", "duty ratio of negative bias voltage pulse (%)", and "microwave output (kW)". , “Microwave pulse frequency (kHz)”, “microwave pulse duty ratio (%)”, “gas flow rate (sccm)”, “pressure (Pa)”, and “processing time (sec)”. It is composed of each data shown.

  The applied voltage of the negative bias voltage pulse 39 is stored in the “negative bias voltage (V)”. The frequency of the negative bias voltage pulse is stored in the “frequency of negative bias voltage pulse (kHz)”. The duty ratio (first duty ratio) of the negative bias voltage pulse 39 is stored in the “duty ratio (%) of negative bias voltage pulse”. The “microwave output (kW)” stores the supply power of the microwave pulse 38. The frequency of the microwave pulse is stored in the “frequency of microwave pulse (kHz)”. The duty ratio (%) of the microwave pulse stores the duty ratio of the microwave pulse 38.

The "gas flow rate (sccm)" includes the inert gas _{Ar, CH 4, C 2 H} 2, gas flow rate in the order of the raw material gas TMS (sccm) is stored. The “pressure (Pa)” stores the pressure of the inert gas Ar in the processing container 2 at the time of ion cleaning. The “processing time (sec)” stores the processing time for performing the ion cleaning.

  Next, an example of the intermediate layer film formation data table 46 stored in the ROM 33 or the HDD 34 will be described with reference to FIG. In the intermediate layer film formation data table 46, in the steps 17 to 19 of the flowchart shown in FIG. 8, the “intermediate layer” when the intermediate layer film 42 (see FIG. 4) which is the DLC film executed by the CPU 31 is formed. The basic film forming conditions of the film are stored. Here, as shown in FIG. 4, the intermediate layer film 42 is a DLC film formed on the processed surface of the material 8 to be processed.

  As shown in FIG. 6, the intermediate layer film formation data table 46 indicates “work type” representing the type of the material 8 to be processed and “intermediate layer film basic film formation conditions” corresponding to the “work type”. It is composed of each data. The “work type” stores that it is common to all types of the material 8 to be processed. The basic film forming conditions for the intermediate layer film are "negative bias voltage (V)", "frequency of negative bias voltage pulse (kHz)", "duty ratio of negative bias voltage pulse (%)", and " "Microwave output (kW)", "frequency of microwave pulse (kHz)", "duty ratio of microwave pulse (%)", "gas flow rate (sccm)", "pressure (Pa)", and "treatment" It is composed of each data indicating "time (sec)".

  "Negative bias voltage (V)", "Negative bias voltage pulse frequency (kHz)", "Negative bias voltage pulse duty ratio (%)", "Microwave output (kW)", "Microwave pulse" The frequency (kHz) ", the" duty ratio (%) of the microwave pulse ", and the" gas flow rate (sccm) "are different in the numerical values, but the same data as the cleaning data table 45 is stored.

  The “pressure (Pa)” stores the pressure (total pressure) of the inert gas Ar and the source gas inside the processing container 2 when the intermediate layer film 42 is formed. The “processing time (sec)” stores the film forming processing time for forming the intermediate layer film 42.

  Next, an example of the DLC layer film formation data table 47 stored in the ROM 33 or the HDD 34 will be described with reference to FIG. 7. In this DLC layer film formation data table 47, "Basic configuration of DLC layer film" when the DLC layer film 43 (see FIG. 4) executed by the CPU 31 is formed in steps 20 to 22 of the flowchart shown in FIG. Membrane conditions "are stored. Here, as shown in FIG. 4, the DLC layer film 43 is a DLC film formed on the surface of the intermediate layer film 42. The intermediate layer film 42 corresponds to the first film of the first layer of the present invention, and the DLC layer film 43 corresponds to the second film of the second layer of the present invention.

  As shown in FIG. 7, the DLC layer film formation data table 47 indicates “work type” indicating the type of the material 8 to be processed and “basic film forming condition of DLC layer film” corresponding to the “work type”. It is composed of each data. The “work type” stores that it is common to all types of the material 8 to be processed. The “basic film formation conditions for the DLC layer film” have substantially the same configuration as the “basic film formation conditions for the intermediate layer film” in the intermediate layer film formation data table 46, although the numerical values are different.

  However, the “pressure (Pa)” stores the pressure (total pressure) of the inert gas Ar and the source gas inside the processing container 2 when the DLC layer film 43 is formed. The “processing time (sec)” stores the film forming processing time for forming the DLC layer film 43.

[Basic film formation processing]
Next, a basic film forming process for forming a DLC film on the processed surface of the material 8 to be processed, which is a process executed by the CPU 31 of the film forming apparatus 1 configured as described above, will be described with reference to FIG. .. In this film forming process, the material 8 to be processed held by the holder 9 is set inside the processing container 2 by an operator. In the present embodiment, the material of the material 8 to be processed is SCM415 steel (carburized and tempered, 200 ° C. tempered).

  After that, the CPU 31 detects the “basic configuration” by automatically or by detecting that a film formation start instruction by the operator is input to the control unit 6 through an operation button provided on an operation unit (not shown). "Membrane treatment" is started. The type of the material 8 to be processed set in the processing container 2 is detected by a sensor (not shown), and the corresponding “work type” is detected from the intermediate layer film formation data table 46 or the DLC layer film formation data table 47. Extract. The extracted “work type” is stored in the RAM 32. The “work type” may be input by the operator via an operation unit (not shown) and stored in the RAM 32.

  As shown in FIG. 8, first, in step (hereinafter abbreviated as “S”) 11, the CPU 31 reads the “intermediate layer film basics” corresponding to the “work type” stored in the RAM 32 from the intermediate layer film formation data table 46. Each data of “film forming conditions” is read out and stored in the RAM 32.

For example, as shown in FIG. 6, when the “work type” is “A”, the CPU 31 sets “−600 V” as the “negative bias voltage (V)” and “frequency of negative bias voltage pulse (kHz). ) "Is" 200 kHz "," duty ratio (%) of negative bias voltage pulse "is" 80% "," microwave output (kW) "is" 1 (kW) "," frequency of microwave pulse (kHz) " ) ”As“ 30 kHz ”,“ microwave pulse duty ratio (%) ”as“ 8% ”, and“ gas flow rate (sccm) ”as inert gas Ar as“ 100 sccm ”and C ₂ H ₂ as“ 100 sccm ”. , TMS is “15 sccm”, H ₂ is “100 sccm”, “Pressure (Pa)” is “80 Pa”, and “Processing time (sec)” is “5 seconds”. It is read from the memory 46 and stored in the RAM 32.

  Subsequently, in S <b> 12, the CPU 31 reads, from the DLC layer film formation data table 47, each data of “basic film formation conditions of DLC layer film” corresponding to “work type” stored in the RAM 32, and stores the data in the RAM 32.

For example, as shown in FIG. 7, when the “work type” is “A”, the CPU 31 sets “−600 V” as the “negative bias voltage (V)” and “frequency of negative bias voltage pulse (kHz). ) "Is" 200 kHz "," duty ratio (%) of negative bias voltage pulse "is" 80% "," microwave output (kW) "is" 1 (kW) "," frequency of microwave pulse (kHz) " ) ”Is“ 30 kHz ”,“ duty ratio (%) of microwave pulse ”is“ 75% ”, and“ gas flow rate (sccm) ”is“ 100 sccm ”for the inert gas Ar and“ 100 sccm ”for C ₂ H _2. , TMS is “15 sccm”, H ₂ is “100 sccm”, “pressure (Pa)” is “80 Pa”, and “treatment time (sec)” is “17 seconds”. It is read from the table 47 and stored in the RAM 32.

  In S11, the operator inputs each data of the "basic film forming conditions of the intermediate layer film" to the control unit 6 through the operation unit (not shown), and the CPU 31 stores each data in the RAM 32. Good. Further, in S12, the operator inputs each data of the "basic film forming conditions of the DLC layer film" to the control unit 6 through the operation unit (not shown), and the CPU 31 stores each data in the RAM 32. Good.

  Then, in S <b> 13, the CPU 31 reads the data of “the ultimate vacuum (Pa)” from the cleaning data table 45 and stores it in the RAM 32. After that, the CPU 31 sets the pressure adjusting valve 7 to full open after activating the vacuum pump 3, and based on the pressure signal input from the vacuum gauge 26, the inside of the processing container 2 indicates “the ultimate vacuum (Pa ) ”Vacuum degree, for example, wait until it becomes“ 1 Pa ”. When the inside of the processing container 2 reaches this degree of vacuum, the CPU 31 proceeds to the processing of S14.

  In S <b> 14, the CPU 31 reads out each data of “gas flow rate (sccm)” and “pressure (Pa)” from the cleaning data table 45 and stores it in the RAM 32. Then, the CPU 31 reads the gas flow rate value of the inert gas Ar out of the “gas flow rate (sccm)” from the RAM 32, and reads the gas flow rate value for the gas supply unit 5, for example, “20 sccm” in the processing container 2 A supply signal instructing to supply the inert gas Ar is output. As a result, the gas supply unit 5 supplies the inert gas Ar to the inside of the processing container 2 at, for example, “20 sccm” according to the supply signal. That is, the supply of the inert gas Ar is started.

  After that, the CPU 31 sets the inert gas in the processing container 2 to be exhausted at a constant flow rate via the pressure adjusting valve 7. Then, the CPU 31 reads "pressure (Pa)" from the RAM 32, and adjusts the inside of the processing container 2 to a pressure value of this "pressure (Pa)", for example, "15 Pa". Subsequently, the CPU 31 waits for the inside of the processing container 2 to reach a pressure value of “pressure (Pa)”, for example, “15 Pa”, based on the pressure signal input from the vacuum gauge 26. Then, when the inside of the processing container 2 reaches the pressure value of “pressure (Pa)”, for example, “15 Pa”, the CPU 31 shifts to the processing of S15.

  In S15, the CPU 31 reads "negative bias voltage (V)", "frequency of negative bias voltage pulse (kHz)", "duty ratio (%) of negative bias voltage pulse", and "micro" from the cleaning data table 45. The data of “wave output (kW)”, “frequency of microwave pulse (kHz)”, “duty ratio of microwave pulse (%)”, and “processing time (sec)” are read out and stored in the RAM 32.

  Then, the CPU 31 reads the applied voltage value of the “negative bias voltage (V)” from the RAM 32 and sends it to the negative voltage power supply 15 (control step). The CPU 31 reads the frequency of the “frequency of negative bias voltage pulse (kHz)” and the duty ratio of “duty ratio (%) of negative bias voltage pulse” from the RAM 32 and sends it to the negative voltage pulse generator 16. (Control process). The CPU 31 reads the supplied power value of “microwave output (kW)” from the RAM 32 and transmits it to the microwave power supply 13 (control step). The CPU 31 reads the frequency of the “microwave pulse frequency (kHz)” and the duty ratio of the “microwave pulse duty ratio (%)” from the RAM 32 and sends the frequency to the microwave pulse control unit 11 (control step). ..

  As a result, the negative voltage power supply 15 applies a negative applied voltage of, for example, -600V and a predetermined voltage, for example, + 10V to + 60V to the negative voltage pulse generator 16 according to the received applied voltage, for example, "-600V". Supply the applied voltage of. As shown in the lower part of FIG. 3, the negative voltage pulse generator 16 receives the “negative bias voltage pulse” at the frequency of the received “negative bias voltage pulse frequency (kHz)” with the supplied negative applied voltage. A negative bias voltage pulse 39 having a duty ratio of "(duty ratio (%))" is generated and applied to the material 8 to be processed via the negative voltage electrode 25 (negative voltage applying step).

  Further, as shown in the lower part of FIG. 3, the negative voltage pulse generator 16 has a predetermined voltage, for example, a positive voltage of + 10V to + 60V, within the application stop time of the negative bias voltage within one cycle of the negative bias voltage pulse 39. Bias voltage pulse 41 is generated and applied to the material 8 to be processed through the negative voltage electrode 25.

  Further, the microwave power supply 13 supplies the microwave oscillator 12 with power of, for example, 1 kW in accordance with the output power of the received microwave, for example, “1 kW”. As shown in the upper part of FIG. 3, the microwave pulse control unit 11 receives the pulse signal having the frequency of “frequency of microwave pulse (kHz)” and the duty ratio of “duty ratio of microwave pulse (%)”. Is generated and transmitted to the microwave oscillator 12. The microwave oscillator 12 generates the microwave pulse 38 according to the received pulse signal with the supplied electric power, for example, the microwave electric power of 2.45 GHz corresponding to 1 kW to generate the isolator 17, the tuner 18, and the waveguide 19. , Through the coaxial waveguide 21 and the microwave supply port 22 toward the holder 9 and the material 8 to be processed (microwave supply step).

  As a result, the sheath layer along the surface of the material 8 to be processed is expanded in the direction orthogonal to the propagation direction of the microwave, that is, in the lateral direction of FIG. A plasma of the inert gas Ar is generated by the microwave pulse 38 propagating in the layer.

  The propagation direction of the microwave is a direction perpendicular to the microwave introduction surface 22A near the microwave supply port 22, but the microwave propagates along the sheath layer generated along the surface of the material 8 to be processed. Therefore, the propagation direction of the microwave is along the extending direction of the material 8 to be processed. The surface of the material 8 to be processed is ion-cleaned by the plasma of the generated inert gas Ar. When the ion cleaning is started, the CPU 31 resets the respective measurement times of the timer 35 and the end determination timer 36 to “0”, and then starts counting the elapsed time of the entire film forming process and the ion cleaning process time. Then, the process proceeds to S16.

  In S16, the CPU 31 stores the output temperature TP1 input from the radiation thermometer 29 in the RAM 32. Then, the CPU 31 reads the output temperature TP1 from the RAM 32 and executes a determination process of determining whether the output temperature TP1 is equal to or higher than a predetermined temperature, for example, 250 ° C. or higher. That is, the CPU 31 executes a determination process of determining whether to end the ion cleaning.

  The CPU 31 reads out the processing time for performing the ion cleaning of “processing time (sec)”, for example, “60 seconds” from the cleaning data table 45, and the measurement time of the end determination timer 36 reaches the processing time of ion cleaning. A determination process for determining whether or not to perform may be performed to determine whether to end the ion cleaning. Further, the CPU 31 may determine whether to end the ion cleaning based on whether the arcing occurrence frequency is less than a predetermined frequency.

  Then, when it is determined that the output temperature TP1 input from the radiation thermometer 29 is lower than a predetermined temperature, for example, less than 250 ° C. (S16: NO), the CPU 31 is stored in advance from the ROM 33 or the HDD 34. "Temperature measurement interval τ (sec)", for example, 0.2 sec is read, and waits until the temperature measurement interval τ (sec) elapses. When the temperature measurement interval τ (sec) has elapsed, the CPU 31 executes the processing of S16 and thereafter again.

  On the other hand, when it is determined that the output temperature TP1 input from the radiation thermometer 29 is equal to or higher than a predetermined temperature, for example, 250 ° C. or higher (S16: YES), the CPU 31 causes the microwave pulse control unit 11 to use the microwave oscillator. A stop signal instructing to stop the pulse signal being transmitted to 12 is transmitted (control step). As a result, the microwave oscillator 12 stops the output of the microwave pulse 38 (microwave supply step).

  Further, the CPU 31 transmits a stop signal instructing the negative voltage pulse generator 16 to stop the application of the negative bias voltage pulse 39 and the positive bias voltage pulse 41 (control process). As a result, the negative voltage pulse generator 16 stops the application of the negative bias voltage pulse 39 and the positive bias voltage pulse 41 to the material 8 to be processed (negative voltage application step). Further, the CPU 31 outputs a stop signal instructing the gas supply unit 5 to stop the supply of the inert gas Ar. After that, the CPU 31 shifts to the processing of S17.

In S17, CPU 31 reads out the respective gas flow rate to supply the inert gas Ar and the material gas _{CH 4, C 2 H 2,} TMS of stored in RAM32 in the S11 "Gas flow rate (sccm)", Gas It is transmitted to the supply unit 5 as a flow rate control instruction. Thereby, the gas supply unit 5 supplies the inert gas Ar and the source gases CH ₄ , C ₂ H ₂ , and TMS to the inside of the processing container 2 in accordance with the flow rate control instruction. That is, the supply of the inert gas Ar and each raw material gas is started.

After that, the CPU 31 sets the inert gas Ar and the raw material gas in the processing container 2 to be exhausted at a constant flow rate through the pressure adjusting valve 7, and the pressure of “pressure (Pa)” stored in the RAM 32 in S11. The value is adjusted to, for example, “80 Pa”. Further, the CPU 31 displays the flow rates of the inert gas Ar and the source gases CH ₄ , C ₂ H ₂ , and TMS on the liquid crystal display 30, and prompts to supply each gas at the displayed flow rate. Then, when the pressure in the processing container 2 input from the vacuum gauge 26 is stable at the pressure value of “pressure (Pa)”, the CPU 31 proceeds to the processing of S18.

  The intermediate layer gas stabilization waiting time T31 (seconds) may be stored in the ROM 33 or the HDD 34 in advance. Then, the CPU 31 reads the intermediate layer gas stabilization waiting time T31 (seconds) from the ROM 33 or the HDD 34, and when the measurement time of the end determination timer 36 reaches the intermediate layer gas stabilization waiting time T31 (seconds), the process of S18 is performed. You may make it transfer to a process.

  In S18, the CPU 31 reads the applied voltage value of the "negative bias voltage (V)" stored in the RAM 32 in S11, for example, "-600 V", and transmits it to the negative voltage power supply 15 (control step). The CPU 31 stores the frequency of the “frequency of negative bias voltage pulse (kHz)” stored in the RAM 32 in S11, for example, “200 kHz” and the duty ratio of “duty ratio (%) of negative bias voltage pulse”, for example, , “80%” are read out and transmitted to the negative voltage pulse generator 16 (control step).

  Further, the CPU 31 reads out the supply power value of “microwave output (kW)”, for example, “1 kW” stored in the RAM 32 in S11 and transmits it to the microwave power supply 13 (control step). The CPU 31 determines the frequency of the “frequency of microwave pulse (kHz)” stored in the RAM 32 in S11, eg, “30 kHz” and the duty ratio of “duty ratio of microwave pulse (%)”, eg, “8%. Is read out and transmitted to the microwave pulse control unit 11 (control step).

  As a result, the negative voltage power supply 15 applies a negative applied voltage of, for example, -600V and a predetermined voltage, for example, + 10V to + 60V to the negative voltage pulse generator 16 according to the received applied voltage, for example, "-600V". Supply the applied voltage of. As shown in the lower part of FIG. 3, the negative voltage pulse generation unit 16 uses the supplied negative applied voltage and the frequency of the received “frequency of negative bias voltage pulse (kHz)”, for example, “200 kHz”, A negative bias voltage pulse 39 having a duty ratio of “duty ratio (%) of negative bias voltage pulse”, for example, a duty ratio (first duty ratio) of “80%” is generated and passed through the negative voltage electrode 25. And is applied to the material 8 to be processed (negative voltage applying step).

  Further, as shown in the lower part of FIG. 3, the negative voltage pulse generator 16 has a predetermined voltage, for example, a positive voltage of + 10V to + 60V, within the application stop time of the negative bias voltage within one cycle of the negative bias voltage pulse 39. Bias voltage pulse 41 is generated and applied to the material 8 to be processed through the negative voltage electrode 25.

  Further, the microwave power supply 13 supplies the microwave oscillator 12 with power of, for example, 1 kW in accordance with the output power of the received microwave, for example, “1 kW”. As shown in the upper part of FIG. 3, the microwave pulse control unit 11 sets the frequency of the received “frequency of microwave pulse (kHz)”, for example, “30 kHz”, and “duty ratio (%) of microwave pulse”. A pulse signal having a duty ratio of, for example, “8%” duty ratio (second duty ratio) is generated and transmitted to the microwave oscillator 12. The microwave oscillator 12 generates the microwave pulse 38 according to the received pulse signal with the supplied electric power, for example, the microwave electric power of 2.45 GHz corresponding to 1 kW to generate the isolator 17, the tuner 18, and the waveguide 19. , Through the coaxial waveguide 21 and the microwave supply port 22 toward the holder 9 and the material 8 to be processed (microwave supply step).

  As a result, the sheath layer along the surface of the material 8 to be processed is expanded in the lateral direction of FIG. 1 by these negative bias voltage pulses 39, and the inert gas Ar and the raw material gas are generated by the microwave pulse 38 propagating in the sheath layer. Plasma is generated. Then, the formation of the intermediate layer film 42 shown in FIG. 4 is started on the processed surface of the material to be processed 8. When the film formation of the intermediate layer film 42 is started, the CPU 31 resets the measurement time of the end determination timer 36 to “0”, and then starts counting the film formation time of the intermediate layer film 42. Move to processing.

  In S19, the CPU 31 reads the “processing time (sec)” stored in the RAM 32 in S11, for example, “5 sec”, and the measurement time of the end determination timer 36 reaches the film formation time of the intermediate layer film 42. A determination process for determining whether or not it is performed is executed. That is, the CPU 31 executes the determination process of determining whether or not to finish the film formation of the intermediate layer film 42.

  When it is determined that the time measured by the end determination timer 36 has not reached the “processing time (sec)”, for example, “5 sec” (S19: NO), the CPU 31 again sets the end determination timer 36. A determination process for determining whether or not the measurement time of “process time (sec)”, for example, “5 sec” has been reached is executed. On the other hand, when it is determined that the time measured by the end determination timer 36 has reached the “processing time (sec)”, for example, “5 sec” (S19: YES), the CPU 31 causes the microwave pulse control unit 11 to perform a microwave operation. A stop signal instructing the wave oscillator 12 to stop the pulse signal being transmitted is transmitted (control step). As a result, the microwave oscillator 12 does not receive the pulse signal, and thus stops the output of the microwave pulse 38 (microwave supply step).

  Further, the CPU 31 transmits a stop signal instructing the negative voltage pulse generator 16 to stop the application of the negative bias voltage pulse 39 and the positive bias voltage pulse 41 (control process). As a result, the negative voltage pulse generator 16 stops the application of the negative bias voltage pulse 39 and the positive bias voltage pulse 41 to the material 8 to be processed (negative voltage application step). Further, the CPU 31 outputs a stop signal instructing the gas supply unit 5 to stop the supply of the inert gas Ar and the raw material gas. As a result, the supply of the inert gas Ar and the raw material gas is stopped. That is, the formation of the intermediate layer film 42 is stopped. After that, the CPU 31 shifts to the processing of S20.

  Thereby, as described below, the intermediate layer film 42 having a thickness of about 30 nm to 60 nm is formed on the processed surface of the material to be processed 8 in a short time, for example, 3 seconds to 5 seconds, and HF1 It is possible to form a DLC film having an adhesive property of ˜HF4 (see FIG. 12).

In S20, CPU 31 reads out the respective gas flow rate to supply the inert gas Ar and the material gas _{CH 4, C 2 H 2,} TMS of stored in RAM32 in S12 above "Gas flow rate (sccm)", Gas It is transmitted to the supply unit 5 as a flow rate control instruction. Thereby, the gas supply unit 5 supplies the inert gas Ar and the source gases CH ₄ , C ₂ H ₂ , and TMS to the inside of the processing container 2 in accordance with the flow rate control instruction. That is, the supply of the inert gas Ar and each raw material gas is started.

After that, the CPU 31 sets the inert gas Ar and the raw material gas in the processing container 2 to be exhausted at a constant flow rate through the pressure adjusting valve 7, and the pressure of “pressure (Pa)” stored in the RAM 32 in S12. The value is adjusted to, for example, “80 Pa”. Further, the CPU 31 displays the flow rates of the inert gas Ar and the source gases CH ₄ , C ₂ H ₂ , and TMS on the liquid crystal display 30, and prompts to supply each gas at the displayed flow rate. Then, when the pressure in the processing container 2 input from the vacuum gauge 26 becomes stable at the pressure value of “pressure (Pa)”, the CPU 31 proceeds to the processing of S21.

  The DLC layer gas stabilization waiting time T32 (seconds) may be stored in the ROM 33 or the HDD 34 in advance. Then, the CPU 31 reads the DLC layer gas stabilization waiting time T32 (seconds) from the ROM 33 or the HDD 34, and when the measurement time of the end determination timer 36 reaches the DLC layer gas stabilization waiting time T32 (seconds), the process of S21 is performed. You may make it transfer to a process.

  In S21, the CPU 31 reads the applied voltage value of the "negative bias voltage (V)" stored in the RAM 32 in S12, for example, "-600V", and transmits it to the negative voltage power supply 15 (control step). The CPU 31 stores the frequency of the “frequency of negative bias voltage pulse (kHz)” stored in the RAM 32 at S12, for example, “200 kHz” and the duty ratio of “duty ratio (%) of negative bias voltage pulse”, for example, , “80%” are read out and transmitted to the negative voltage pulse generator 16 (control step).

  Further, the CPU 31 reads out the supply power value of “microwave output (kW)”, for example, “1 kW” stored in the RAM 32 in S12 and transmits it to the microwave power supply 13 (control step). The CPU 31 determines the frequency of the “frequency of microwave pulse (kHz)” stored in the RAM 32 in S12, eg, “30 kHz” and the duty ratio of “duty ratio of microwave pulse (%)”, eg, “75%”. Is read out and transmitted to the microwave pulse control unit 11 (control step).

  As a result, the negative voltage power supply 15 applies a negative applied voltage of, for example, -600V and a predetermined voltage, for example, + 10V to + 60V to the negative voltage pulse generator 16 according to the received applied voltage, for example, "-600V". Supply the applied voltage of. As shown in the lower part of FIG. 3, the negative voltage pulse generation unit 16 uses the supplied negative applied voltage and the frequency of the received “frequency of negative bias voltage pulse (kHz)”, for example, “200 kHz”, A negative bias voltage pulse 39 having a duty ratio of “duty ratio (%) of negative bias voltage pulse”, for example, a duty ratio (first duty ratio) of “80%” is generated and passed through the negative voltage electrode 25. And is applied to the material 8 to be processed (negative voltage applying step).

  Further, as shown in the lower part of FIG. 3, the negative voltage pulse generator 16 has a predetermined voltage, for example, a positive voltage of + 10V to + 60V, within the application stop time of the negative bias voltage within one cycle of the negative bias voltage pulse 39. Bias voltage pulse 41 is generated and applied to the material 8 to be processed through the negative voltage electrode 25.

  Further, the microwave power supply 13 supplies the microwave oscillator 12 with power of, for example, 1 kW in accordance with the output power of the received microwave, for example, “1 kW”. As shown in the upper part of FIG. 3, the microwave pulse control unit 11 sets the frequency of the received “frequency of microwave pulse (kHz)”, for example, “30 kHz”, and “duty ratio (%) of microwave pulse”. A pulse signal having a duty ratio of, for example, “75%” duty ratio (second duty ratio) is generated and transmitted to the microwave oscillator 12. The microwave oscillator 12 generates the microwave pulse 38 according to the received pulse signal with the supplied electric power, for example, the microwave electric power of 2.45 GHz corresponding to 1 kW to generate the isolator 17, the tuner 18, and the waveguide 19. , Through the coaxial waveguide 21 and the microwave supply port 22 toward the holder 9 and the material 8 to be processed (microwave supply step).

  As a result, the sheath layer along the surface of the material 8 to be processed is expanded in the lateral direction of FIG. 1 by these negative bias voltage pulses 39, and the inert gas Ar and the raw material gas are generated by the microwave pulse 38 propagating in the sheath layer. Plasma is generated. Then, the formation of the DLC layer film 43 shown in FIG. 4 is started on the processed surface of the material to be processed 8. When the film formation of the DLC layer film 43 is started, the CPU 31 resets the measurement time of the end determination timer 36 to “0”, and then starts counting the film formation time of the DLC layer film 43. Move to processing.

  In S22, the CPU 31 reads the “processing time (sec)” stored in the RAM 32 in S12, for example, “17 sec”, and the measurement time of the end determination timer 36 reaches the film formation time of the DLC layer film 43. A determination process for determining whether or not it is performed is executed. That is, the CPU 31 executes a determination process of determining whether or not to finish the film formation of the DLC layer film 43.

  When it is determined that the time measured by the end determination timer 36 has not reached the “processing time (sec)”, for example, “17 sec” (S22: NO), the CPU 31 again sets the end determination timer 36. The determination process of determining whether or not the measurement time of "reach the processing time (sec)", for example, "17 sec" is executed. On the other hand, when it is determined that the measurement time of the end determination timer 36 has reached the “processing time (sec)”, for example, “17 sec” (S22: YES), the CPU 31 causes the microwave pulse control unit 11 to perform a microwave operation. A stop signal instructing the wave oscillator 12 to stop the pulse signal being transmitted is transmitted (control step). As a result, the microwave oscillator 12 does not receive the pulse signal, and thus stops the output of the microwave pulse 38 (microwave supply step).

  Further, the CPU 31 transmits a stop signal instructing the negative voltage pulse generator 16 to stop the application of the negative bias voltage pulse 39 and the positive bias voltage pulse 41 (control process). As a result, the negative voltage pulse generator 16 stops the application of the negative bias voltage pulse 39 and the positive bias voltage pulse 41 to the material 8 to be processed (negative voltage application step). Further, the CPU 31 outputs a stop signal instructing the gas supply unit 5 to stop the supply of the inert gas Ar and the raw material gas. As a result, the supply of the inert gas Ar and the raw material gas is stopped. That is, the film formation of the DLC layer film 43 is stopped. After that, the CPU 31 shifts to the processing of S23.

  As a result, as described later, a DLC layer film 43 having a predetermined thickness, for example, a thickness of about 2 μm is formed on the processed surface of the material to be processed 8 to form a DLC film having an adhesive property of HF1 to HF4. It becomes possible to form a film (see FIG. 12). That is, since the intermediate layer film 42 which is the first layer is formed on the surface of the material 8 to be processed, the adhesion of the DLC film is maintained even if the deposition rate of the DLC layer film 43 which is the second layer is increased. Be done.

  In S23, the CPU 31 transmits an exhaust signal instructing the pressure adjusting valve 7 to fully open the exhaust. The pressure adjusting valve 7 is fully opened and the raw material gas and the inert gas remaining in the processing container 2 are quickly exhausted by the vacuum pump 3. After that, the CPU 31 gives an instruction to fully close the pressure adjusting valve 7 after stopping the vacuum pump 3. Further, the CPU 31 transmits a control signal instructing to fully open the atmosphere opening valve 10 after the pressure adjusting valve 7 is fully closed. The atmosphere opening valve 10 is fully opened, and the internal pressure of the processing container 2 becomes the same as the external atmospheric pressure.

  After the vacuum pump 3 is stopped, the CPU 31 outputs a signal to the liquid crystal display (LCD) 30 when the internal pressure of the processing container 2 becomes the same as the external atmospheric pressure based on the signal from the vacuum gauge 26. The fact that the film is finished is displayed and the film forming process is finished. As a result, the work material 8 on which the DLC film is formed is taken out by the operator or the automatic carrier.

[Experimental Example 1]
Next, the results of Experimental Example 1 will be described based on FIGS. 9 to 11. In Experimental Example 1, the “negative bias” in each of the “basic film forming conditions of the intermediate layer film” of the intermediate layer film forming data table 46 and the “basic film forming condition of the DLC layer film” of the DLC layer film forming data table 47 was used. The data of “frequency of voltage pulse (kHz)” and “duty ratio of negative bias voltage pulse (%)” are changed, and the processed surface of the work material 8 is formed by the basic film forming process (S11 to S23). The adhesion test of the formed DLC film was performed.

  The adhesion test was performed by a peeling judgment test of the German Engineers Association standard (VDI3198 Coating of cold forging tools). A diamond indenter was attached to a Rockwell hardness tester, and an adhesion test was conducted by observing an indentation formed by applying a load of 150 kgf to a test piece. In addition, as a criterion of the adhesiveness in the present embodiment, “HF1” to “HF4” were determined to be acceptable (◯), and “HF5” and “HF6” were determined to be unacceptable (×). This is because when the DLC film is used for general industrial purposes, a DLC film having adhesion of “HF1” to “HF4” is usually required.

  In addition, in each of the "basic film forming conditions of the intermediate layer film" of the intermediate layer film forming data table 46 and the "basic film forming condition of the DLC layer film" of the DLC layer film forming data table 47, "negative bias voltage (V ) ”,“ Microwave output (kW) ”,“ frequency of microwave pulse (kHz) ”,“ duty ratio of microwave pulse (%) ”,“ gas flow rate (sccm) ”,“ pressure (Pa) ”, As each data of “processing time (sec)”, each data of the intermediate layer film formation data table 46 shown in FIG. 6 and the DLC layer film formation data table 47 shown in FIG. 7 was used.

  Specifically, in S11 and S12 of the basic film forming process, the operator operates the "basic film forming condition of the intermediate layer film" and the "basic film forming condition of the DLC layer film" through an operation unit (not shown). As the data of “frequency of negative bias voltage pulse (kHz)” in “,” each frequency of “20 kHz”, “75 kHz”, “200 kHz”, and “250 kHz” is input to the control unit 6 for each film formation, and the CPU 31 Each data is stored in the RAM 32.

  Further, the application time T22 of the positive bias voltage pulse 41 shown in FIG. 3 is “0.4 μsec”, “1 μsec”, “2 μsec” for each frequency “20 kHz”, “75 kHz”, “200 kHz”, and “250 kHz”. , “5 μsec”, “6 μsec”, and “8.5 μsec”, the “duty ratio (%) of the negative bias voltage pulse” is set via the operation unit (not shown). The data of the “duty ratio (%) of the negative bias voltage pulse” in the “basic film forming conditions” and the “basic film forming conditions of the DLC layer film” is input to the control unit 6 for each film formation, and the CPU 31 inputs each data. It is stored in the RAM 32.

  As a result, as shown in the first adhesion measurement result table 51 (see FIG. 9), the negative voltage application time table 52 (see FIG. 10), and the first duty ratio table 53 (see FIG. 11), the “intermediate layer When the “frequency of negative bias voltage pulse (kHz)” in “basic film forming conditions of film” and “basic film forming condition of DLC layer film” is set to “20 kHz”, the positive bias voltage pulse 41 is applied. In all of the time T22 set to “0.4 μsec” to “8.5 μsec”, that is, each “duty ratio (%) of the negative bias voltage pulse” is set to “99%” to “83%”. In all of the tests performed, the adhesion test was “HF5”, which was unacceptable (x).

  In addition, when the "frequency of negative bias voltage pulse (kHz)" in "basic film formation conditions for intermediate layer film" and "basic film formation conditions for DLC layer film" is set to "75 kHz", a positive bias is applied. When the application time T22 of the voltage pulse 41 is set to “1 μsec” to “5 μsec”, that is, the “duty ratio (%) of the negative bias voltage pulse” is set to “93%” to “63%”. At that time, the adhesion test was “HF1” to “HF3”, which was a pass (◯). On the other hand, when the application time T22 of the positive bias voltage pulse 41 is set to “0.4 μsec” and “6 μsec”, that is, the “duty ratio (%) of the negative bias voltage pulse” is “97%” and When it was set to "55%", the adhesion test was "HF5", which was unacceptable (x).

  In addition, when the "frequency of negative bias voltage pulse (kHz)" in "basic film formation conditions for intermediate layer film" and "basic film formation conditions for DLC layer film" is set to "200 kHz", a positive bias is applied. When the application time T22 of the voltage pulse 41 is set to “0.4 μsec” and “1 μsec”, that is, the “duty ratio (%) of the negative bias voltage pulse” becomes “92%” and “80%”. When set, the adhesion test was "HF1" and passed (○). On the other hand, when the application time T22 of the positive bias voltage pulse 41 is set to “2 μsec”, that is, when the “duty ratio (%) of the negative bias voltage pulse” is set to “60%”, the close contact The sex test was “HF5”, which was unacceptable (x).

  In addition, if the “frequency of negative bias voltage pulse (kHz)” in “basic film formation conditions for intermediate layer film” and “basic film formation conditions for DLC layer film” is set to “250 kHz”, positive bias is applied. When the application time T22 of the voltage pulse 41 is set to “0.4 μsec”, that is, when the “duty ratio (%) of the negative bias voltage pulse” is set to “90%”, the adhesion test is performed. Was “HF1” and was a pass (◯). On the other hand, when the application time T22 of the positive bias voltage pulse 41 is set to “1 μsec”, that is, when the “duty ratio (%) of the negative bias voltage pulse” is set to “75%”, the close contact The sex test was “HF5”, which was unacceptable (x).

  When the frequency of the microwave pulse is set to "30 kHz" and the frequency of the negative bias voltage pulse is set to "20 kHz", it is within the supply stop time during which the microwave is not supplied within one cycle of the microwave pulse. Multiple negative bias voltage pulses are not applied. On the other hand, when the frequencies of the negative bias voltage pulse are set to “75 kHz”, “200 kHz”, and “250 kHz”, a plurality of microwaves are supplied within one period of the microwave pulse during which the supply of the microwave is stopped. A negative bias voltage pulse is applied. As a result, the number of impacts of ions and electrons is increased and the adhesion of the DLC film is improved.

[Experimental Example 2]
Next, the results of Experimental Example 2 will be described based on FIGS. 12 and 13. In Experimental Example 2, “negative bias” in each of “basic film forming conditions of intermediate layer film” of the intermediate layer film forming data table 46 and “basic film forming condition of DLC layer film” of the DLC layer film forming data table 47. Each data of “frequency of voltage pulse (kHz)” and “duty ratio of microwave pulse (%)” was changed, and a film was formed on the processed surface of the material 8 to be processed by the basic film forming process (S11 to S23). The film formation rate (nm / sec) of the DLC film was measured and the adhesion test was performed.

  The film forming rate (nm / sec) is a total of processing times of the intermediate layer film 42 and the DLC layer film 43, which is obtained by measuring the thickness of the DLC film from the surface of the material 8 to be processed by so-called CALOTEST by the spherical polishing method. It was calculated by dividing by the time (22 seconds).

  In addition, in each of the "basic film forming conditions of the intermediate layer film" of the intermediate layer film forming data table 46 and the "basic film forming condition of the DLC layer film" of the DLC layer film forming data table 47, "negative bias voltage (V ) ”,“ Duty ratio (%) of negative bias voltage pulse ”,“ microwave output (kW) ”,“ frequency of microwave pulse (kHz) ”,“ gas flow rate (sccm) ”,“ pressure (Pa) ” "," "Processing time (sec)", each data of the intermediate layer film formation data table 46 shown in FIG. 6 and the DLC layer film formation data table 47 shown in FIG. 7 was used. Therefore, the microwave oscillator 12 generates and supplies the microwave of 2.45 GHz at the frequency of 30 kHz and the microwave pulse 38 having the “duty ratio (%) of the microwave pulse”.

  Specifically, in S11 and S12 of the basic film forming process, the operator operates the "basic film forming condition of the intermediate layer film" and the "basic film forming condition of the DLC layer film" through an operation unit (not shown). As the data of “frequency of negative bias voltage pulse (kHz)” in “,” each frequency of “20 kHz”, “75 kHz”, “200 kHz”, and “250 kHz” is input to the control unit 6 for each film formation, and the CPU 31 Each data is stored in the RAM 32.

  Also, every time the frequency of the negative bias voltage pulse is set to any one of the frequencies “20 kHz”, “75 kHz”, “200 kHz”, “250 kHz”, the operator operates the operating unit (not shown). Then, the data of “duty ratio (%) of microwave pulse” in “basic film forming conditions of intermediate layer film” and “basic film forming conditions of DLC layer film” are “0%”, “8%”, “ 16% ”,“ 24% ”,“ 32% ”, and“ 75% ”each duty ratio (second duty ratio) is input to the control unit 6 for each film formation, and the CPU 31 inputs each data. It is stored in the RAM 32.

  Therefore, every time the frequency of the negative bias voltage pulse is set to any one of "20 kHz", "75 kHz", "200 kHz", and "250 kHz", the microwave oscillator 12 outputs the microwave of 2.45 GHz. At a frequency of 30 kHz, any one of "0%", "8%", "16%", "24%", "32%", and "75%" "microwave pulse duty ratio (%)" , Microwave pulse 38 is generated and supplied.

  As a result, as shown in the film formation rate table 55 (see FIG. 12) and the second adhesion measurement result table 56 (see FIG. 13), “basic film formation conditions for the intermediate layer film” and “DLC layer film When "frequency of negative bias voltage pulse (kHz)" in "basic film forming conditions" is set to "20 kHz", when "duty ratio of microwave pulse (%)" is set to "0%" The film forming rate was "0.3 nm / sec", and the adhesion test was "HF1", which was a pass (◯). On the other hand, when the “duty ratio (%) of microwave pulse” is set to “8%” to “75%”, the film formation rate is “12.9 nm / sec” to “42.0 nm / sec”, The adhesion test was “HF5”, which was unacceptable (x).

  In addition, when the “frequency of negative bias voltage pulse (kHz)” in “basic film formation conditions for intermediate layer film” and “basic film formation conditions for DLC layer film” is set to “75 kHz”, When the pulse duty ratio (%) is set to "0%" to "24%", the film formation rate is "1 nm / sec" to "24.5 nm / sec" and the adhesion test is "HF1". "-" HF3 ", and was a pass (○). On the other hand, when the “microwave pulse duty ratio (%)” is set to “32%” and “75%”, the film formation rates are “33.6 nm / sec” and “82.0 nm / sec”, The adhesion test was “HF5”, which was unacceptable (x).

  In addition, when the “frequency of negative bias voltage pulse (kHz)” in “basic film forming conditions for intermediate layer film” and “basic film forming conditions for DLC layer film” is set to “200 kHz”, When the pulse duty ratio (%) "is set to" 0% "to" 24% ", the film formation rate is" 1.7 nm / sec "to" 26.5 nm / sec ", and the adhesion test The results were "HF1" to "HF3", which were acceptable (○). On the other hand, when the “microwave pulse duty ratio (%)” is set to “32%” and “75%”, the film formation rates are “36.5 nm / sec” and “118.0 nm / sec”, The adhesion test was “HF5”, which was unacceptable (x).

  In addition, when the “frequency of negative bias voltage pulse (kHz)” in “basic film formation conditions for intermediate layer film” and “basic film formation conditions for DLC layer film” is set to “250 kHz”, When the pulse duty ratio (%) "is set to" 0% "to" 24% ", the film formation rate is" 1.9 nm / sec "to" 28.1 nm / sec ", and the adhesion test The results were "HF1" to "HF3", which were acceptable (○). On the other hand, when the “microwave pulse duty ratio (%)” is set to “32%” and “75%”, the film formation rates are “38.1 nm / sec” and “120.0 nm / sec”, The adhesion test was “HF5”, which was unacceptable (x).

[Experimental Example 3]
Next, the results of Experimental Example 3 will be described based on FIGS. 14 and 15. In Experimental Example 3, the “microwave pulse” in each of the “basic film forming conditions of the intermediate layer film” of the intermediate layer film forming data table 46 and the “basic film forming condition of the DLC layer film” of the DLC layer film forming data table 47 is used. Frequency (kHz) ”, and the number of abnormal discharges (the number of arcing) (number of times) during the film formation of the DLC film on the processed surface of the material 8 to be processed by the basic film forming process (S11 to S23) is performed. The measurement and the adhesion test were performed. Regarding the number of abnormal discharges, "0" to "59" were regarded as acceptable (◯).

  Here, if an abnormal discharge (arcing) occurs during the formation of the DLC film on the processed surface of the material to be processed 8, it is necessary to stop the application of the negative bias voltage pulse for a predetermined time, for example, 150 microseconds. .. Therefore, a large number of abnormal discharges leads to a decrease in the film formation rate of the DLC film and a variation in film quality. Further, if abnormal discharge occurs on the surface of the material 8 to be processed, discharge marks are generated on the surface of the DLC film, and if the number of abnormal discharges is large, it leads to generation of surface defects.

  The “negative bias voltage (V ) ”,“ Frequency of negative bias voltage pulse (kHz) ”,“ duty ratio of negative bias voltage pulse (%) ”,“ microwave output (kW) ”,“ duty ratio of microwave pulse (%) ” , "Gas flow rate (sccm)", "pressure (Pa)" and "processing time (sec)" are the intermediate layer film formation data table 46 shown in FIG. 6 and the DLC layer film formation data shown in FIG. Each data in Table 47 was used.

  Specifically, in S11 and S12 of the basic film forming process, the operator operates the "basic film forming condition of the intermediate layer film" and the "basic film forming condition of the DLC layer film" through an operation unit (not shown). As the data of “frequency of microwave pulse (kHz)” in “,” each frequency of “1 kHz”, “5 kHz”, “10 kHz”, “20 kHz”, “30 kHz”, and “40 kHz” is controlled by the control unit 6 for each film formation. The CPU 31 stores each data in the RAM 32.

  Therefore, the negative voltage pulse generation unit 16 generates the negative bias voltage pulse 39 having the duty ratio (first duty ratio) of “80%” at the frequency of “200 kHz” and outputs the negative bias voltage “−600V”. It is applied to the material 8 to be processed through the negative voltage electrode 25. Further, the microwave oscillator 12 outputs the microwave of 2.45 GHz at each frequency of “1 kHz” to “40 kHz” with the “duty ratio (%) of each microwave pulse” of “8%” and “75%”. A microwave pulse 38 is generated and supplied with a power supply of "1 kW".

  As a result, as shown in the abnormal discharge count table 57 (see FIG. 14) and the third adhesion measurement result table 58 (see FIG. 15), the “basic film formation conditions for the intermediate layer film” and the “DLC layer film” are shown. When "frequency of microwave pulse (kHz)" in "basic film formation condition" is set to "1 kHz", the number of abnormal discharges during film formation of the DLC film is "3335", and the adhesion test is " It was HF5 "and was unacceptable (x). Further, when the “frequency of microwave pulse (kHz)” was set to “5 kHz”, the adhesion test was “HF3”, but the number of abnormal discharges during the formation of the DLC film was “60 times”. And was rejected (x).

  On the other hand, when the “frequency of microwave pulse (kHz)” is set to “10 kHz” to “30 kHz”, the number of abnormal discharges during the formation of the DLC film is “4 times” to “0 times”, The adhesion test was “HF3” to “HF1”, and was passed (◯). When the “frequency of microwave pulse (kHz)” is set to “40 kHz”, the adhesion test is “HF3”, and the number of abnormal discharges during the DLC film formation is “1 time”. However, "surface roughness" occurred on the surface of the DLC layer film 43, and it was unacceptable (x).

[Experimental Example 4]
Next, the results of Experimental Example 4 will be described based on FIGS. 16 and 17. In Experimental Example 4, "negative bias" in each of "basic film forming conditions of intermediate layer film" in the intermediate layer film forming data table 46 and "basic film forming condition of DLC layer film" in the DLC layer film forming data table 47 is shown. The data of "voltage (V)" is changed for each film formation, and the number of surface defects (pieces / mm ² ) of the DLC film formed on the processed surface of the material 8 to be processed by the basic film formation process (S11 to S23). Was measured and the above adhesion test was performed.

For the measurement of the number of surface defects (pieces / mm ² ), the DLC film was photographed, and the fact that the surface defects were photographed darker than the surroundings was used to perform binarization processing with a density threshold indicating brightness. The image processing range is set to 1 × 1 mm ² for the surface image of the DLC film. Then, a portion where the diameter of the circumscribing circle inscribed by the darkly imaged portion within the set image processing range is 10 μm or more was extracted and measured as a threshold value for determining one surface defect. Regarding the number of surface defects, “0 / mm ² ” to “18 / mm ² ” was accepted (◯). When the number of surface defects is large, there is a risk that the surface defects may serve as a starting point and lead to peeling of the DLC film, which is a problem.

  The “basic film formation conditions for the intermediate layer film” in the intermediate layer film formation data table 46 and the “basic film formation conditions for the DLC layer film” in the DLC layer film formation data table 47 indicate the “negative bias voltage pulse "Frequency (kHz)", "duty ratio of negative bias voltage pulse (%)", "microwave output (kW)", "frequency of microwave pulse (kHz)", "duty ratio of microwave pulse (%)" "," Gas flow rate (sccm) "," pressure (Pa) ", and" processing time (sec) "are the intermediate layer deposition data table 46 shown in FIG. 6 and the DLC layer deposition shown in FIG. Each data in the data table 47 was used.

  Specifically, in S11 and S12 of the basic film forming process, the operator operates the "basic film forming condition of the intermediate layer film" and the "basic film forming condition of the DLC layer film" through an operation unit (not shown). The negative bias voltage (V) of "-100V", "-200V", "-400V", "-600V", and "-800V" is sequentially set as the data of "negative bias voltage (V)" in The data is input to the control unit 6 and the CPU 31 stores each data in the RAM 32.

  Therefore, the negative voltage pulse generation unit 16 generates the negative bias voltage pulse 39 having the duty ratio (first duty ratio) of “80%” at the frequency of “200 kHz”, and each negative bias voltage “−100V”. ~ "-800 V" is applied to the work material 8 through the negative voltage electrode 25. Further, the microwave oscillator 12 generates a microwave pulse 38 of 2.45 GHz at a frequency of "30 kHz" and a microwave pulse 38 of "duty ratio (%) of microwave pulse" of "8%" and "75%", respectively. It is generated and supplied with "1 kW" supply power.

As a result, as shown in the surface defect number table 59 (see FIG. 16) and the fourth adhesion measurement result table 61, "basic film forming conditions for intermediate layer film" and "basic film forming conditions for DLC layer film" when set "negative bias voltage (V)" to "-100V" is the surface number of defects of the DLC film is a was the "three / mm ^2", the adhesion test "HF5" and in , Was unacceptable (x).

On the other hand, when the “negative bias voltage (V)” is set to “−200V” to “−600V”, the number of surface defects of the DLC film is “1 / mm ² ” to “10 / mm ^2”. ", And the adhesion test was" HF1 ", which was a pass (◯). Further, when the "negative bias voltage (V)" was set to "-800V", the adhesion test was "HF1", but the number of surface defects of the DLC film was "420 / mm ² ". And was rejected (x).

[Experimental Example 5]
Next, the results of Experimental Example 5 will be described based on FIGS. 12 and 18. In Experimental Example 5, the “negative bias” in each of the “basic film forming conditions of the intermediate layer film” of the intermediate layer film forming data table 46 and the “basic film forming condition of the DLC layer film” of the DLC layer film forming data table 47 is shown. The “voltage pulse frequency (kHz)” data and the “processing time (sec)” data in the “intermediate layer film formation condition” of the intermediate layer film formation data table 46 are changed for each film formation. An adhesion test of the DLC film formed on the processed surface of the material to be processed 8 by the basic film forming process (S11 to S23) was performed. That is, the film thickness of the intermediate layer film 42 formed in S19 is changed from "0 nm" to "1000 nm" for each film formation, and the DLC film formed on the processed surface of the material 8 to be processed is adhered as described above. A sex test was conducted.

  In addition, in each of the "basic film forming conditions of the intermediate layer film" of the intermediate layer film forming data table 46 and the "basic film forming condition of the DLC layer film" of the DLC layer film forming data table 47, "negative bias voltage (V ) ”,“ Negative bias voltage pulse duty ratio (%) ”,“ Microwave output (kW) ”,“ Microwave pulse frequency (kHz) ”,“ Microwave pulse duty ratio (%) ”, For each data of “gas flow rate (sccm)” and “pressure (Pa)”, each data of the intermediate layer film formation data table 46 shown in FIG. 6 and the DLC layer film formation data table 47 shown in FIG. 7 was used. Further, as the data of “processing time (sec)” in “basic film forming conditions of DLC layer film” of the DLC layer film forming data table 47, data of the DLC layer film forming data table 47 shown in FIG. 7 was used.

  Specifically, in S11 and S12 of the basic film forming process, the operator operates the "basic film forming condition of the intermediate layer film" and the "basic film forming condition of the DLC layer film" through an operation unit (not shown). As the data of “frequency of negative bias voltage pulse (kHz)” in “,” each frequency of “20 kHz”, “75 kHz”, “200 kHz”, and “250 kHz” is input to the control unit 6 for each film formation, and the CPU 31 Each data is stored in the RAM 32.

  Further, every time the frequency of the negative bias voltage pulse is set to any one of the frequencies “20 kHz”, “75 kHz”, “200 kHz”, “250 kHz” ”, the intermediate layer film 42 shown in FIG. Data of "processing time (sec)" in "basic film forming conditions of intermediate layer film" at which the film thickness becomes "0 nm", "10 nm", "30 nm", "50 nm", "100 nm", "1000 nm" It is calculated based on the film formation rate table 55 shown in FIG. 12, and is input to the control unit 6 for each film formation, and the CPU 31 stores each data in the RAM 32.

  Here, from the film formation rate table 55 shown in FIG. 12, the “microwave pulse frequency (kHz)” of the “basic film formation condition of the intermediate layer film” of the intermediate layer film formation data table 46 is “30 kHz”, and “ When the duty ratio (%) of the microwave pulse is set to "8%", the "frequency of negative bias voltage pulse (kHz)" is "20 kHz", "75 kHz", "200 kHz", "250 kHz". The film forming rates of the intermediate layer film 42 at the respective frequencies are "12.9 nm / sec", "13.2 nm / sec", "12.8 nm / sec", and "13.2 nm / sec".

  Therefore, the “frequency of negative bias voltage pulse (kHz)” in the “basic film formation conditions of the intermediate layer film” in the intermediate layer film formation data table 46 is “20 kHz”, “75 kHz”, “200 kHz”, “250 kHz”. The film thickness of the intermediate layer film 42 when set to each frequency is “0 nm”, “10 nm”, “30 nm”, “50 nm”, “100 nm”, and “1000 nm”. The “processing time (sec)” in the “film condition” can be calculated by dividing by the film formation rate of the intermediate layer film 42 at each frequency.

  For example, when the “frequency of negative bias voltage pulse (kHz)” in the “basic film forming conditions for the intermediate layer film” is set to “200 kHz”, the film thickness of the intermediate layer film 42 is “0 nm”, The "processing time (sec)" in the "basic film forming conditions of the intermediate layer film" which becomes 10 nm "," 30 nm "," 50 nm "," 100 nm ", and" 1000 nm "is" 0 sec "and" 10/12 ", respectively. .8 = 0.8 sec "," 30 / 12.8 = 2.3 sec "," 50 / 12.8 = 3.9 sec "," 100 / 122.8 = 7.8 sec "," 1000 / 122.8 ". = 78.1 sec ”.

  The “frequency of negative bias voltage pulse (kHz)” in the “basic film forming conditions of DLC layer film” of the DLC layer film formation data table 47 is “200 kHz” and the frequency of microwave pulse (kHz) is “ 30 kHz "," duty ratio (%) of microwave pulse "is" 75% ", and" processing time (sec) "is" 17 sec ", the DLC layer film is obtained from the film formation rate table 55 (see FIG. 12). The film forming rate of 43 is “118.0 nm / sec”. Therefore, the film thickness of the DLC layer film 43 (see FIG. 4) is 118.0 × 17 = 2006 nm, and a DLC film having a film thickness of about 2 μm is formed on the processed surface of the material 8 to be processed.

  As a result, as shown in the fifth adhesion measurement result table 63 (see FIG. 18), the “basic film formation conditions of the intermediate layer film” of the intermediate layer film formation data table 46 and the “DLC film formation data table 47 of the“ DLC film formation data ”are shown. When the “frequency of negative bias voltage pulse (kHz)” in “basic film forming conditions of layer film” is set to “20 kHz”, the film of the intermediate layer film 42 formed on the processed surface of the material 8 to be processed. In all of the cases where the thickness was set to "0 nm" to "1000 nm", the adhesion test was "HF5", which was unacceptable (x).

  Further, the "frequency of negative bias voltage pulse (kHz)" in "basic film forming conditions of intermediate layer film" and "basic film forming condition of DLC layer film" is set to "75 kHz", "200 kHz", and "250 kHz", respectively. In the case of setting the frequency, when the film thickness of the intermediate layer film 42 formed on the processed surface of the material to be processed 8 is set to "0 nm", the adhesion test becomes "HF5" and fails ( X). On the other hand, when the film thickness of the intermediate layer film 42 formed on the processed surface of the material to be processed 8 is set to "10 nm" to "1000 nm", the adhesion test becomes "HF1" to "HF4", and the test passes. It was (○). Therefore, if the film thickness of the intermediate layer film 42 is “10 nm” or more, the adhesion test passes (◯), and preferably, if it is “30 nm” or more, the adhesion test becomes “HF1”, Pass (○).

  If the thickness of the intermediate layer film 42 is too thin, the intermediate layer film 42 is formed in an island shape on the processed surface of the material 8 to be processed, and it is difficult to cover the entire processed surface of the material 8 to be processed. May not be obtained. However, if the film thickness of the intermediate layer film 42 is about 10 nm or more, it is possible to cover the entire processed surface of the material to be processed 8 and sufficiently secure the adhesion of the DLC film to the material to be processed 8. ..

  As described above in detail, in the film forming apparatus 1 according to the present embodiment, the “basic film forming conditions for the intermediate layer” in the intermediate layer film forming data table 46 from FIG. By setting according to the film forming conditions of the intermediate layer film forming condition table 65 shown in FIG. 6, the intermediate layer film 42 having the adhesion test of “HF1” to “HF4” can be formed on the processed surface of the material 8 to be processed. It will be possible.

  Specifically, as shown in FIG. 19, the “negative bias voltage (V)” in the “basic film formation conditions for the intermediate layer film” in the intermediate layer film formation data table 46 is “−200 V” to “−800 V”. , "Negative bias voltage pulse frequency (kHz)" is set to "75 kHz" to "250 kHz", and "negative bias voltage pulse duty ratio (%)" is "63%" to It is set to “93%”, that is, the application time T21 (see FIG. 3) of the negative bias voltage pulse 39 is set to “3.6 μsec” to “12.3 μsec”.

  In addition, "microwave output (kW)" in "basic film formation conditions for intermediate layer film" of the intermediate layer film formation data table 46 is set to "1 (kW)", and "frequency of microwave pulse (kHz)". Is set to "6 kHz" to "39 kHz", the "microwave pulse duty ratio (%)" is set to "8%" to "24%", that is, the supply time T11 of the microwave pulse 38 (Fig. 3) is set to “2.6 μsec” to “10 μsec”.

  Preferably, the “negative bias voltage (V)” in the “basic film formation conditions for the intermediate layer film” in the intermediate layer film formation data table 46 is set to “−200 V”, and the “frequency of the negative bias voltage pulse ( "kHz)" is set to "200 kHz" and the "duty ratio (%) of the negative bias voltage pulse" is set to "80%". In addition, "microwave output (kW)" in "basic film formation conditions for intermediate layer film" of the intermediate layer film formation data table 46 is set to "1 (kW)", and "frequency of microwave pulse (kHz)". Is set to "6 kHz" and the "microwave pulse duty ratio (%)" is set to "8%".

  Then, by setting the “processing time (sec)” in the “basic film forming conditions of the intermediate layer film” in the intermediate layer film formation data table 46 to “3 sec” to “5 sec”, the processed surface of the material 8 to be processed is set. It becomes possible to form the intermediate layer film 42 having a film thickness of “30 nm” or more. Therefore, the film formation processing time of the DLC film (intermediate layer film 42 + DLC layer film 43) for which the adhesion test is "HF1" to "HF4" can be significantly shortened as compared with the conventional case.

  Further, the “microwave pulse duty ratio (%)” in the “basic film formation conditions for the intermediate layer film” of the intermediate layer film formation data table 46 is set to “24%”, and the “frequency of the negative bias voltage pulse ( (kHz) ”to each frequency of“ 75 kHz ”,“ 200 kHz ”, and“ 250 kHz ”, the film deposition rate (nm / sec) of the intermediate layer film 42 is maintained while maintaining“ HF3 ”of the adhesion test. It becomes possible to improve.

Further, the number of abnormal discharges is suppressed by setting the “microwave pulse frequency (kHz)” in the “basic film formation conditions for the intermediate layer film” of the intermediate layer film formation data table 46 to “6 kHz” to “39 kHz”. Thus, it becomes possible to stably form a film, and the number of surface defects of the DLC film formed on the processed surface of the material to be processed 8 can be 18 (pieces / mm ² ) or less.

  It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that various improvements and modifications can be made without departing from the spirit of the present invention. For example, the following may be done. In the following description, the same reference numerals as those of the film forming apparatus 1 according to the above-described embodiment shown in FIGS. 1 to 19 indicate the same or corresponding portions as those of the film forming apparatus 1 according to the above-described embodiment. Is.

[Other First Embodiment]
For example, the CPU 31 of the film forming apparatus 1 according to the other first embodiment executes the “second film forming process” shown in FIG. 20 in place of the “basic film forming process” to process the material 8 to be processed. A DLC film may be formed on the surface. First, similarly to the film forming apparatus 1, the work material 8 held by the holder 9 is set inside the processing container 2 by an operator.

  After that, the CPU 31 automatically or by detecting that a film formation start instruction by an operator is input to the control unit 6 via an operation button provided on an operation unit (not shown), the “second The film forming process "is started. The type of the material 8 to be processed set in the processing container 2 is detected by a sensor (not shown), and the corresponding “work type” is detected from the intermediate layer film formation data table 46 or the DLC layer film formation data table 47. Extract. The extracted “work type” is stored in the RAM 32. The “work type” may be input by the operator via an operation unit (not shown) and stored in the RAM 32.

[Second film forming process]
As shown in FIG. 20, the CPU 31 executes the processes of S11 to S16 of the “basic film forming process” so that the output temperature TP1 input from the radiation thermometer 29 is equal to or higher than a predetermined temperature, for example, 250 ° C. or higher. When it is determined that there is, that is, when it is determined that the ion cleaning of the surface of the material 8 to be processed is completed (S16: YES), the pulse signal transmitted to the microwave oscillator 12 is transmitted to the microwave pulse controller 11. Send a stop signal instructing to stop. As a result, the microwave oscillator 12 stops the output of the microwave pulse 38.

  Further, the CPU 31 transmits a stop signal instructing the negative voltage pulse generator 16 to stop the application of the negative bias voltage pulse 39 and the positive bias voltage pulse 41. As a result, the negative voltage pulse generator 16 stops the application of the negative bias voltage pulse 39 and the positive bias voltage pulse 41 to the material 8 to be processed. Further, the CPU 31 outputs a stop signal instructing the gas supply unit 5 to stop the supply of the inert gas Ar. After that, the CPU 31 shifts to the processing of S16-2.

  In S16-2, the CPU 31 reads the data of the “exhaust vacuum degree (Pa)” stored in advance from the ROM 33 or the HDD 34 and stores it in the RAM 32. After that, the CPU 31 sets the pressure adjusting valve 7 to full open after activating the vacuum pump 3, and based on the pressure signal input from the vacuum gauge 26, the inside of the processing container 2 becomes “exhaust vacuum degree (Pa ) ”Vacuum degree, for example, wait until it becomes“ 1 Pa ”. Then, when the inside of the processing container 2 reaches the vacuum degree of “exhaust vacuum degree (Pa)”, the CPU 31 shifts to the processing of S17. As a result, the CPU 31 can shift to the process of S17 after exhausting the inert gas for ion cleaning in the processing container 2, for example, the inert gas Ar.

  Then, the CPU 31 executes the processes of S17 to S19 of the above "basic film forming process", and determines that the measurement time of the end determination timer 36 has reached "processing time (sec)", for example, "5 sec". If so, that is, if it is determined that the formation of the intermediate layer film 42 is completed (S19: YES), the microwave pulse control unit 11 is caused to stop the pulse signal being transmitted to the microwave oscillator 12. Send a stop signal to instruct. As a result, the microwave oscillator 12 does not receive the pulse signal and thus stops the output of the microwave pulse 38.

  Further, the CPU 31 transmits a stop signal instructing the negative voltage pulse generator 16 to stop the application of the negative bias voltage pulse 39 and the positive bias voltage pulse 41. As a result, the negative voltage pulse generator 16 stops the application of the negative bias voltage pulse 39 and the positive bias voltage pulse 41 to the material 8 to be processed. Further, the CPU 31 outputs a stop signal instructing the gas supply unit 5 to stop the supply of the inert gas Ar and the raw material gas. As a result, the supply of the inert gas Ar and the raw material gas is stopped. That is, the formation of the intermediate layer film 42 is stopped. After that, the CPU 31 shifts to the processing of S19-2.

In S19-2, the “exhaust vacuum degree (Pa)” data stored in advance from the ROM 33 or the HDD 34 is read again and stored in the RAM 32. After that, the CPU 31 sets the pressure adjusting valve 7 to full open after activating the vacuum pump 3, and based on the pressure signal input from the vacuum gauge 26, the inside of the processing container 2 becomes “exhaust vacuum degree (Pa ) ”Vacuum degree, for example, wait until it becomes“ 1 Pa ”. Then, when the inside of the processing container 2 reaches the vacuum degree of “exhaust vacuum degree (Pa)”, the CPU 31 shifts to the processing of S20. As a result, the CPU 31 exhausts the remaining intermediate layer gas (for example, the inert gas Ar and each source gas CH ₄ , C ₂ H ₂ , TMS, etc.) after forming the intermediate layer film 42 in the processing container 2. , S20 can be performed.

  Subsequently, when the CPU 31 executes the processes of S20 to S23 of the "basic film forming process", and the pressure inside the processing container 2 becomes the same as the external atmospheric pressure based on the signal from the vacuum gauge 26. Indicates that the film formation is completed on the liquid crystal display (LCD) 30, and the film formation process ends. As a result, the work material 8 on which the DLC film is formed is taken out by the operator or the automatic carrier.

  Therefore, in the "second film forming process", the CPU 31 executes the processes of S11 to S16 in the "basic film forming process", and then in S16-2, an inert gas for ion cleaning in the processing container 2, For example, the inert gas Ar is exhausted. Subsequently, the CPU 31 executes the processes of S17 to S19 of the "basic film forming process", and then, in S19-2, exhausts the remaining intermediate layer gas in which the intermediate layer film 42 in the processing container 2 is formed. .. After that, the CPU 31 executes the processes of S20 to S23 of the "basic film forming process", and ends the film forming process.

  The CPU 31 executes the processes of S11 to S16-2 of the “second film forming process” to exhaust the inert gas for ion cleaning in the processing container 2, for example, the inert gas Ar, and then You may make it complete | finish the film-forming process by performing the process of S17-S23 of said "basic film-forming process." That is, only the exhaust step of exhausting the inert gas for ion cleaning in the processing container 2 may be provided.

  Further, the CPU 31 executes the processes of S11 to S19 of the "basic film forming process", and then executes the processes of S19-2 to S23 of the "second film forming process", and ends the film forming process. You may do it. That is, only the exhaust step of exhausting the remaining intermediate layer gas in which the intermediate layer film 42 is formed in the processing container 2 may be provided.

[Experimental Example 6]
Here, the results of Experimental Example 6 will be described based on FIG. Experimental Example 6 is the above-mentioned "basic film forming process", that is, a film forming process of "no exhaust process" in which an inert gas exhaust process for ion cleaning and an intermediate layer gas exhaust process are not provided (S11). -S16-S17-S23), the above-mentioned adhesion test of the DLC film formed was performed. Further, the adhesion test was performed on the DLC film formed by the film forming process (S11 to S16 to S16-2 to S17 to S23) of "exhaust process for only gas for ion cleaning".

  Further, the above-mentioned adhesion test of the DLC film formed by the film forming process (S11 to S19 to S19-2 to S20 to S23) of "exhaust process for only intermediate layer gas" was performed. Further, the above-mentioned "second film forming process", that is, the film forming process of "there is a step of exhausting the ion cleaning gas and the intermediate layer gas" (S11 to S16 to S16-2 to S17 to S19 to S19-2 to S20 to The above-mentioned adhesion test of the DLC film formed in S23) was performed.

  In Experimental Example 6, in S11 and S12 described above, the “basic film formation conditions for the intermediate layer film” in the intermediate layer film formation data table 46 and the “basic film formation for DLC layer film” in the DLC layer film formation data table 47 are described. Data of “frequency of negative bias voltage pulse (kHz)” in each of “conditions” and data of “processing time (sec)” in “basic film formation condition of intermediate layer film” in the intermediate layer film formation data table 46 A DLC film having a film thickness of “2 μm” with the film thickness of the intermediate layer film 42 being “10 nm” was formed on the processed surface of the material 8 to be processed.

  In addition, in each of the "basic film forming conditions of the intermediate layer film" of the intermediate layer film forming data table 46 and the "basic film forming condition of the DLC layer film" of the DLC layer film forming data table 47, "negative bias voltage (V ) ”,“ Negative bias voltage pulse duty ratio (%) ”,“ Microwave output (kW) ”,“ Microwave pulse frequency (kHz) ”,“ Microwave pulse duty ratio (%) ”, For each data of “gas flow rate (sccm)” and “pressure (Pa)”, each data of the intermediate layer film formation data table 46 shown in FIG. 6 and the DLC layer film formation data table 47 shown in FIG. 7 was used. Further, as the data of “processing time (sec)” in “basic film forming conditions of DLC layer film” of the DLC layer film forming data table 47, data of the DLC layer film forming data table 47 shown in FIG. 7 was used.

  Specifically, in S11 and S12 of the basic film forming process, the operator operates the "basic film forming condition of the intermediate layer film" and the "basic film forming condition of the DLC layer film" through an operation unit (not shown). As the data of “frequency of negative bias voltage pulse (kHz)” in “,” each frequency of “20 kHz”, “75 kHz”, “200 kHz”, and “250 kHz” is input to the control unit 6 for each film formation, and the CPU 31 Each data is stored in the RAM 32.

  In addition, "basic film forming conditions of the intermediate layer film" in which the film thickness of the intermediate layer film 42 shown in FIG. 4 becomes "10 nm" for each frequency "20 kHz", "75 kHz", "200 kHz", "250 kHz" The data of the “processing time (sec)” in FIG. 12 is obtained when the “duty ratio (%) of 30 kHz microwave pulse” of the film forming rate table 55 shown in FIG. 12 is set to “8%”. (Nm / sec) ”(for example, about 0.8 sec to about 1 sec), and inputs it to the control unit 6 for each film formation, and the CPU 31 stores each data in the RAM 32.

  As a result, as shown in the sixth adhesion measurement result table 67 (see FIG. 21), the “basic film forming conditions of the intermediate layer film” of the intermediate layer film forming data table 46 and the “DLC film forming data table 47 of the“ DLC film forming data table 47 ”. When the “frequency of negative bias voltage pulse (kHz)” in the “basic film forming conditions for layer film” is set to “20 kHz”, the above-mentioned “basic film forming process”, that is, film formation without “exhaust step” Process, film forming process of "exhaust process only for ion cleaning gas", film forming process of "exhaust process of only intermediate layer gas", and the above "second film forming process", that is, "ion cleaning gas and gas In all of the film forming treatments including "the step of exhausting the intermediate layer gas," the adhesion test was "HF5", which was unacceptable (x).

  Further, the "frequency of negative bias voltage pulse (kHz)" in "basic film forming conditions of intermediate layer film" and "basic film forming condition of DLC layer film" is set to "75 kHz", "200 kHz", and "250 kHz", respectively. When the frequency is set, the adhesion test of the DLC film formed in the above "basic film forming process", that is, the film forming process of "no exhaust process" is all "HF4" and passes (○). Met.

  In addition, the adhesion test of the DLC film formed in the film forming process of “exhaust step for only gas for ion cleaning” was “HF3”, which was acceptable (◯). Further, the adhesion test of the DLC film formed in the film formation process of “exhaust process for only intermediate layer gas” was all “HF3”, and passed (◯). Further, the adhesion test of the DLC film formed in the above-mentioned "second film forming process", that is, "there is a step of exhausting the ion cleaning gas and the intermediate layer gas" is "HF2", It was a pass (○).

  Therefore, after the ion cleaning of the processed surface of the processed material 8 is completed, the “exhaust step of the gas for ion cleaning” (S16-2) is performed to form the DLC film on the processed surface of the processed material 8, so that the DLC film is formed. It is possible to improve the adhesion of the film. Further, after the intermediate layer film 42 is formed on the processed surface of the material to be processed 8, the “exhaust step of intermediate layer gas” (S19-2) is performed to form the DLC film on the processed surface of the material to be processed 8. This makes it possible to improve the adhesion of the DLC film.

  Further, a film was formed on the processed surface of the material to be processed 8 by performing both the "exhausting step of gas for ion cleaning" (S16-2) and the "exhausting step of intermediate layer gas" (S19-2). It is possible to further improve the adhesion of the DLC film. By adding these exhaust steps, it becomes possible to prepare a film in a film forming environment without being affected by the gas ratio in the previous step, which is preferable for improving the adhesion and the film forming speed.

DESCRIPTION OF SYMBOLS 1 Film-forming apparatus 2 Processing container 5 Gas supply part 6 Control part 8 Work material 9 Holding tool 11 Microwave pulse control part 12 Microwave oscillator 13 Microwave power supply 15 Negative voltage power supply 16 Negative voltage pulse generation part 17 Isolator 18 Tuner 19 Waveguide 21 Coaxial waveguide 22 Microwave supply port 22A Microwave introduction surface 25 Negative voltage electrode 31 CPU
32 RAM
33 ROM
34 HDD

Claims (11)

A processing container in which a conductive material to be processed can be placed,
A gas supply unit for supplying a raw material gas and an inert gas to the processing container,
A microwave supply unit for supplying a pulsed microwave pulse for generating plasma along the processed surface of the material to be processed,
A negative voltage applying unit that applies a pulsed negative bias voltage pulse to the material to be processed, which enlarges the sheath layer along the processed surface of the material to be processed,
A microwave pulse supplied from the microwave supply unit is passed through a microwave introduction surface along a processing surface of the material to be processed arranged so as to project into the processing container with respect to the microwave introduction surface. A microwave supply port that propagates as a surface wave to the expanded sheath layer,
A control unit,
A film forming method executed by a film forming apparatus comprising:
The control unit executes,
A microwave supplying step of supplying a microwave pulse for generating plasma along the processed surface of the material to be processed through the microwave supplying section;
A negative voltage applying step of applying a negative bias voltage pulse to the processed surface of the material to be processed via the negative voltage applying section,
A control step of controlling the microwave supply section and the negative voltage application section;
Equipped with
The control unit, in the control step,
Control is performed such that a period for supplying a microwave pulse having a pulse frequency of 6 kHz or higher is provided via the microwave supply unit,
When the supply time of the microwave is longer than 0 in one cycle of the microwave pulse, the microwave is not supplied within the one cycle of the microwave pulse through the negative voltage applying unit. applies a plurality of negative bias voltage pulses in the supply stop time, the supply of the microwave application time of a negative bias voltage in one cycle of the negative bias voltage pulses in one cycle of the microwave pulses A film forming method characterized by controlling the time to be longer than the time.   The film forming method according to claim 1, wherein in the control step, the control unit controls to apply a negative bias voltage pulse of 75 kHz or more via the negative voltage application unit.   In the control step, the control unit sets the first duty ratio, which is a ratio of the application time of one pulse of the negative bias voltage to the period of the negative bias voltage pulse, to 63% or more, via the negative voltage application unit. To 93% or less, and the application time of the negative bias voltage within one cycle of the negative bias voltage pulse is controlled to be 3.6 microseconds or more. 2. The film forming method as described in 2.   The film forming method according to claim 1, wherein the raw material gas includes a hydrocarbon-based gas.   In the control step, the control unit sets the second duty ratio, which is the ratio of the supply time of one pulse of the microwave to the cycle of the microwave pulse, to 24% or less via the microwave supply unit. It controls, The film-forming method in any one of Claim 1 thru | or 4 characterized by the above-mentioned.   The said control part is controlled so that the microwave pulse of less than 40 kHz may be supplied via the said microwave supply part in the said control process, It is characterized by the above-mentioned. Deposition method. The control unit, in the control step,
After forming the first coating film of the first layer to a predetermined thickness on the surface of the material to be processed, when forming the second coating film of the second layer, the microwave is supplied via the microwave supply unit. The second duty ratio, which is the ratio of the supply time of one pulse of the microwave to the period of the wave pulse, is controlled to be larger than that during the film formation of the first coating. The film forming method as described in any one of 1. The control unit, in the control step,
The film forming method according to claim 7, wherein the thickness of the first coating of the first layer is controlled to be 10 nm or more. The control unit, in the control step,
The negative bias voltage pulse of −600 V and 200 kHz is controlled to be applied to the material to be processed through the negative voltage application unit, and the negative bias voltage is set to 1 of the negative bias voltage with respect to the cycle of the negative bias voltage pulse. The first duty ratio, which is the ratio of the pulse application time, is controlled to be 80%,
Control is performed so as to supply the microwave pulse of 30 kHz at 1 kW via the microwave supply unit, and a second duty ratio which is a ratio of a supply time of one pulse of the microwave to a cycle of the microwave pulse is set. The film forming method according to claim 1, wherein the film thickness is controlled to 8%. A processing container in which a conductive material to be processed can be placed,
A gas supply unit for supplying a raw material gas and an inert gas to the processing container,
A microwave supply unit for supplying a pulsed microwave pulse for generating plasma along the processed surface of the material to be processed,
A negative voltage applying unit that applies a pulsed negative bias voltage pulse to the material to be processed, which enlarges the sheath layer along the processed surface of the material to be processed,
A microwave pulse supplied from the microwave supply unit is passed through a microwave introduction surface along a processing surface of the material to be processed arranged so as to project into the processing container with respect to the microwave introduction surface. A microwave supply port that propagates as a surface wave to the expanded sheath layer,
A control unit that controls the microwave supply unit and the negative voltage application unit;
Equipped with
The control unit is
Control is performed such that a period for supplying a microwave pulse having a pulse frequency of 6 kHz or more is provided via the microwave supply unit,
When the supply time of the microwave is longer than 0 in one cycle of the microwave pulse, the microwave is not supplied within the one cycle of the microwave pulse through the negative voltage applying unit. applies a plurality of negative bias voltage pulses in the supply stop time, the supply of the microwave application time of a negative bias voltage in one cycle of the negative bias voltage pulses in one cycle of the microwave pulses A film forming apparatus, which is controlled to be longer than the time. A processing container in which a conductive material to be processed can be placed,
A gas supply unit for supplying a raw material gas and an inert gas to the processing container,
A pulsed microwave supply unit for supplying a microwave pulse for generating plasma along the processing surface of the work piece,
A negative voltage applying unit that applies a pulsed negative bias voltage pulse to the material to be processed, which enlarges the sheath layer along the processed surface of the material to be processed,
A microwave pulse supplied from the microwave supply unit is passed through a microwave introduction surface along a processing surface of the material to be processed arranged so as to project into the processing container with respect to the microwave introduction surface. A microwave supply port that propagates as a surface wave to the expanded sheath layer,
To a computer that controls the film deposition apparatus equipped with
A microwave supply step of supplying a microwave pulse for generating plasma along the processed surface of the material to be processed through the microwave supply unit;
A negative voltage applying step of applying a negative bias voltage pulse to the processed surface of the material to be processed via the negative voltage applying section,
A control step of controlling the microwave supply section and the negative voltage application section;
Run
In the control step,
Control is performed such that a period for supplying a microwave pulse having a pulse frequency of 6 kHz or higher is provided via the microwave supply unit,
When the supply time of the microwave is longer than 0 in one cycle of the microwave pulse, the microwave is not supplied within the one cycle of the microwave pulse through the negative voltage applying unit. applies a plurality of negative bias voltage pulses in the supply stop time, the supply of the microwave application time of a negative bias voltage in one cycle of the negative bias voltage pulses in one cycle of the microwave pulses A film forming program, which is executed so as to be controlled so that the time is longer than the time.

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