Patent Publication Number: US-2022223407-A1

Title: Method and device for forming graphene structure

Description:
TECHNICAL FIELD 
     The present disclosure relates to a method of forming a graphene structure and an apparatus therefor. 
     BACKGROUND 
     Graphene is a thin film of graphite having one to several tens or hundreds of atomic layers formed on a substrate. As a graphene structure, a carbon nanowall (hereinafter, also referred to as “CNW”) in which several layers of graphene sheets are grown at an angle, typically, a right angle with respect to a substrate, is known in addition to ordinary graphene formed parallel to a substrate. 
     Graphene is configured as an aggregate of six-membered ring structures by covalent bonds (sp 2 -bonds) of carbon atoms, and exhibits unique electronic properties, such as a mobility of 200,000 cm 2 /Vs or more, which is 100 times or more than that of silicon (Si), and a current density of 10 9  A/cm 2 , which is 1,000 times or more than that of Cu. 
     Due to these characteristics, graphene has attracted attention as a material for various devices, such as wiring, a field effect transistor (FET) channel, and a barrier film, and, due to the structural characteristics thereof, CNWs have attracted attention as a material for various devices, such as a fuel cell, a field electron emission source, a field electron emission source, and a sensor. 
     As a method for forming graphene, a method in which a catalyst metal layer is formed on a workpiece, the catalyst metal layer is activated, and graphene is then formed through CVD has been proposed. In embodiments of Patent Documents 1 and 2, CVD using microwave plasma is disclosed as an example of CVD. 
     PRIOR ART DOCUMENTS 
     Patent Documents 
     
         
         Patent Document 1: Japanese Laid-Open Patent Publication No. 2013-100205 
         Patent Document 2: Japanese Laid-Open Patent Publication No. 2014-231455 
       
    
     SUMMARY 
     The present disclosure provides a graphene structure forming method capable of forming a graphene structure having high coverage, and an apparatus therefor. 
     A method according to an aspect of the present disclosure relates to a method of forming a graphene structure and includes: providing a substrate; performing preprocessing by supplying a first processing gas including a carbon-containing gas to the substrate while heating the substrate, without using plasma; and after the preprocessing, forming a graphene structure on a surface of the substrate through a plasma CVD using plasma of a second processing gas including a carbon-containing gas. 
     According to the present disclosure, it is possible to form a graphene structure having high coverage. 
    
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
         FIG. 1  is a flowchart illustrating a graphene structure forming method according to an embodiment of the present disclosure. 
         FIG. 2A  is a cross-sectional view illustrating a specific example of a structure of a substrate used in the graphene structure forming method according to the embodiment of the present disclosure. 
         FIG. 2B  is a cross-sectional view illustrating another specific example of a structure of a substrate used in the graphene structure forming method according to the embodiment of the present disclosure. 
         FIG. 2C  is a cross-sectional view illustrating still another specific example of the structure of the substrate used in the method for forming the graphene structure according to the embodiment of the present disclosure. 
         FIG. 3  is a cross-sectional view illustrating a state after step  2  of the graphene structure forming method according to the embodiment of the present disclosure. 
         FIG. 4  is a cross-sectional view illustrating a state in which a graphene structure is formed on the substrate by the graphene structure forming method according to the embodiment of the present disclosure. 
         FIG. 5  is a cross-sectional view illustrating a first example of a processing apparatus suitable for implementing the graphene structure forming method according to the embodiment of the present disclosure. 
         FIG. 6  is a cross-sectional view illustrating a second example of the processing apparatus suitable for implementing the graphene structure forming method according to the embodiment of the present disclosure. 
         FIG. 7  is a block diagram illustrating a configuration of a microwave introduction device in the processing apparatus of  FIG. 6 . 
         FIG. 8  is a cross-sectional view schematically illustrating the microwave radiation mechanism in the processing apparatus of  FIG. 6 . 
         FIG. 9  is a bottom view schematically illustrating a ceiling wall of a processing container in the processing apparatus of  FIG. 6 . 
         FIG. 10  illustrates AFM photographs showing respective surface states when preprocessing times were changed to 0 sec, 180 sec, and 600 sec in Experimental Example 1, respectively. 
         FIG. 11  is a diagram showing a relationship between the processing times in the preprocessing and the values of RMS in Experimental Example 1. 
         FIG. 12  is a diagram showing Raman spectra of a substrate surface when the processing times in the preprocessing were 0 sec, 180 sec, and 600 sec in Experimental Example 1. 
         FIG. 13  is a diagram showing a process sequence of Experimental Example 2. 
         FIG. 14  is a diagram showing a relationship between the preprocessing times and the D band intensities (arbitrary unit) in Experimental Example 2. 
         FIG. 15  illustrates SEM photographs showing respective surfaces when the preprocessing times were 10 sec, 60 sec, and 120 sec in Experimental Example 2. 
     
    
    
     DETAILED DESCRIPTION 
     Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. 
     Embodiment of Graphene Structure Forming Method 
     First, an embodiment of a graphene structure forming method will be described. In Patent Documents 1 and 2 described above, in order to efficiently grow graphene having good crystallinity at a temperature as low as possible, a catalyst metal film serving as a catalyst for promoting the growth of graphene, such as Ni, is formed as a base, the catalyst metal layer is activated by plasma of a H 2  gas, which is a reducing gas, and a N 2  gas, which is a nitrogen-containing gas, and then graphene is grown through plasma CVD (PE-CVD). 
     However, Patent Documents 1 and 2 do not describe forming graphene on the entire surface of a substrate with high coverage. 
     In general CVD, film formation proceeds through nucleation and creeping growth. In this case, an example of a method of controlling nucleation density to improve coverage includes surface activation through plasma preprocessing or the like. 
     However, when trying to sufficiently activate the surface through plasma preprocessing, strong ion damage or charge-up damage to the base may be caused at the same time. 
     Therefore, as a result of the examination performed by the inventors, it has been found that it is effective to perform, prior to the formation of a graphene structure through plasma CVD, preprocessing of supplying a gas including a carbon-containing gas to the substrate while heating the substrate, without using plasma. 
     That is, it has been found that, even if the formation of a graphene film is not based on surface activation through general plasma preprocessing, nucleation is possible by supplying a gas including a carbon-containing gas to the substrate while heating the substrate without using plasma. This makes it possible to form a graphene structure having high coverage by promoting nucleation and creeping growth in a subsequent plasma CVD. 
     In an embodiment, unlike the technique utilizing the catalytic reaction using an activated metal catalyst in Patent Documents 1 and 2 described above, it is possible to cause the film formation reaction of a graphene structure to proceed according to a general crystal growth mode. Therefore, there is an advantage in that complicated steps, such as formation and activation processing of a catalyst metal layer, can be omitted. 
     The method of manufacturing a graphene structure of an embodiment includes step  1  and step  2 , and step  3 , as illustrated in  FIG. 1 . Step  1  is a step of providing a substrate. Step  2  is a step of performing preprocessing by supplying a first processing gas including a carbon-containing gas to the substrate while heating the substrate, without using plasma. Step  3  is a step of forming the graphene structure on a surface of the substrate, which has undergone step  2 , through plasma CVD using a second processing gas including a carbon-containing gas. 
     The substrate in step  1  is not particularly limited as long as film formation using plasma CVD can be performed thereon, but a substrate having a surface, on which film formation of a graphene structure is capable of proceeding by nucleation and creeping growth, is preferable as in general CVD. From this point of view, the substrate preferably has a surface that does not have a catalytic function during plasma CVD. Specifically, as the substrate, a semiconductor or an insulator is suitable. In addition, as the substrate, a metal of which the surface does not have a catalytic function during the plasma CVD step may be used. 
       FIGS. 2A to 2C  illustrate specific examples of the substrate. An example of the substrate  300  typically includes a semiconductor wafer. Examples of the substrate  300  include those illustrated in  FIGS. 2A, 2B, and 2C . In the example of  FIG. 2A , the substrate  300  includes only a semiconductor substrate  301  formed of a semiconductor such as silicon. In the example of  FIG. 2B , in the substrate  300 , an insulating film  302 , such as a SiO 2  film, is formed on the semiconductor substrate  301 , such as silicon. In the example of  FIG. 2C , in the substrate  300 , a metal film  304 , such as a Cu film, is formed on the semiconductor substrate  301  of, for example, silicon, with the insulating film  302 , such as a SiO 2  film, and a barrier film  303 , such as a TaN film, a Ta film, or a TiN film, interposed therebetween. The barrier film  303  may be omitted depending on the metal. In addition, the barrier film  303  may be a laminated film (e.g., Ta/TaN). 
     In step  2 , the substrate  300  is accommodated in the processing container, and a first processing gas including a carbon-containing gas is supplied to the substrate  300  while heating the substrate  300  to a predetermined temperature. As a result, as illustrated in  FIG. 3 , nuclei  310  for forming a graphene structure are formed on the surface of the substrate  300 . 
     The first processing gas used in step  2  may be a carbon-containing gas alone or may include a hydrogen gas (H 2  gas) in addition to the carbon-containing gas. In addition, the first processing gas may include a noble gas as a diluting gas or a carrier gas. As the noble gas, Ar, He, Ne, Kr, Xe, or the like may be used. 
     As the carbon-containing gas included in the first processing gas, a highly reactive gas is preferable, and a hydrocarbon gas is suitable. Among the hydrocarbon gases, those having an unsaturated bond or those having a small number of carbon atoms are more reactive and thus preferable. For example, acetylene (C 2 H 2 ) having a triple bond with 2 carbon atoms, ethylene (C 2 H 4 ) having a double bond, or propylene (C 3 H 6 ) having a double bond with 3 carbon atoms may be suitably used. Hydrocarbons that do not have an unsaturated bond, such as methane (CH 4 ), ethane (C 2 H 6 ), and propane (C 3 H 8 ), may be used. 
     A H 2  gas may be added in order to control nucleation. In the formation of graphene through plasma CVD, the formation of graphene proceeds with nucleation and creeping growth based on the following chemical equilibrium equation. 
       C x H y ⇔C(graphene)+H 2  
 
     Therefore, it is possible to control the nucleation of graphene by adding the H 2  gas. 
     The amount of the added H 2  gas is preferably 300% or less at a volume ratio with respect to the carbon-containing gas from the viewpoint of promoting nucleation. 
     The temperature of the substrate when performing step  2  is preferably 300 to 1,000 degrees C. More preferably, the temperature is 350 to 750 degrees C. The internal pressure of the processing container is preferably in the range of 1.33 to 1,330 Pa (0.01 to 10 Torr), and more preferably 1.33 to 133 Pa (0.01 to 1 Torr). The processing time is preferably 30 sec or more, more preferably 1 to 10 min. 
     By performing the preprocessing in step  2  in this way, nuclei for forming the graphene structure are formed, and the nucleation density is controlled. This makes it possible to improve the coverage of the graphene structure through the plasma CVD of step  3  to be subsequently performed. 
     In the next step  3 , the graphene structure  320  is grown on the substrate  300  as illustrated in  FIG. 4  by causing the plasma of the second processing gas including the carbon-containing gas to act on the substrate  300  on which the nuclei  310  are formed. 
     The plasma at this time is not particularly limited, and microwave plasma, particularly remote microwave plasma, is preferably used. In the present disclosure, the remote microwave plasma is a plasma that is generated by a microwave electric field generated by introducing microwaves into the processing container, is diffused from a plasma generation region, and acts on the substrate  300  disposed at a position spaced apart from the plasma generation region. By using the remote microwave plasma, it is possible to dissociate the carbon-containing gas into a state suitable for growing the graphene structure at a relatively low temperature. 
     In this case, a noble gas may be used as the second processing gas in addition to the carbon-containing gas, which may be used as a film-forming raw material. The noble gas may be used as a plasma generation gas. That is, the microwave plasma is generated by introducing microwaves into the processing container, and introducing the plasma generation gas composed of the noble gas into the processing container. Then, the carbon-containing gas as the film-forming raw material gas is dissociated by the plasma and is supplied to the substrate  300  spaced apart from the plasma generation region. Thus, the graphene structure  320  is grown on the substrate  300 . 
     As the noble gas included in the second processing gas, Ar, He, Ne, Kr, Xe, or the like may be used, but among these, Ar, which is capable of stably generating plasma is preferable. 
     As the carbon-containing gas included in the second processing gas, for example, a hydrocarbon gas, such as ethylene (C 2 H 4 ), methane (CH 4 ), ethane (C 2 H 6 ), propane (C 3 H 8 ), propylene (C 3 H 6 ), or acetylene (C 2 H 2 ), or an alcohol gas, such as methanol (CH 3 OH) or ethanol (C 2 H 5 OH), may be used. The carbon-containing gas used here may be the same as or different from the carbon-containing gas used in step  2 . 
     The second processing gas may also include a hydrogen-containing gas, such as a H 2  gas. The quality of the graphene structure may be improved by the hydrogen-containing gas. In addition, an oxidizing gas, such as an oxygen gas (O 2  gas) or water vapor (H 2 O gas), may be included. The oxidizing gas may etch defects contained in the graphene structure to enhance crystallinity. 
     In the case of using the remote microwave plasma, the film-forming raw material gas may be introduced at an arbitrary position between the plasma generation region and a region near the substrate, depending on a required degree of dissociation. That is, in the plasma generation region, the degree of dissociation increases due to high-energy plasma, and in the region near the substrate, the degree of dissociation becomes lower than that in the plasma generation region due to the plasma diffused from the plasma generation region and having a low electron temperature. Therefore, the degree of dissociation of the film-forming raw material gas may be adjusted depending on the position at which the film-forming raw material gas is introduced. 
     In the case of using the remote microwave plasma CVD, the substrate is disposed in a region spaced apart from the microwave plasma generation region, and the plasma diffused from the plasma generation region is supplied to the substrate. For this reason, on the substrate, the plasma has a low electron temperature and thus causes little damage to the substrate, and is turned into high-density plasma mainly composed of radicals by microwaves. 
     The graphene structure may be simply ordinary graphene formed parallel to the substrate, or may include a carbon nanowall (CNW) grown at an angle with respect to the substrate, in addition to graphene. 
     As the process conditions when using the remote microwave plasma, the temperature of the substrate is preferably 350 to 1,000 degrees C. (more preferably 400 to 800 degrees C.), and the microwave power is preferably 100 to 5,000 W. When the surface of the substrate is an insulator or a semiconductor, the internal pressure of the processing container is preferably 1.33 to 667 Pa (0.01 to 5 Torr), and when the surface of the substrate is a metal, the internal pressure of the processing container is preferably 1.33 to 400 Pa (0.01 to 3 Torr). The time preferably ranges from 1 to 200 min. 
     According to the present embodiment, it is possible to form graphene nuclei on a substrate by supplying, prior to forming a graphene structure film through plasma CVD, a gas including a carbon-containing gas to the substrate while heating the substrate, without using plasma. This makes it possible to form a graphene structure having high coverage by promoting nucleation and creeping growth in the subsequent plasma CVD. Therefore, it is not necessary to use an activated metal catalyst layer. 
     As described above, since the graphene structure is formed according to the general crystal growth mode of nucleation and creeping growth, it is not necessary to utilize the catalytic reaction by an activated metal catalyst as in Patent Documents 1 and 2 described above. 
     Prior to the preprocessing step of step  2 , surface treatment for the purpose of cleaning the substrate surface may be performed. An example of the surface treatment includes a process of supplying, for example, a H 2  gas, or both an Ar gas and the H 2  gas while heating the substrate to a temperature of 300 to 600 degrees C. At this time, plasma may be generated. 
     &lt;Processing Apparatus&gt; 
     Next, examples of a processing apparatus suitable for implementing the graphene structure forming method according to the above-described embodiment will be described. 
     First Example of Processing Apparatus 
       FIG. 5  is a cross-sectional view schematically illustrating a first example of the processing apparatus. A processing apparatus  100  illustrated in  FIG. 5  is configured as, for example, an RLSA (registered trademark) microwave plasma-type plasma processing apparatus. 
     The processing apparatus  100  includes a processing container  1 , a stage  2 , a microwave introduction mechanism  3 , a gas supply mechanism  4 , an exhauster  5 , and a controller  6 . 
     The processing container  1  has a substantially cylindrical shape. A circular opening  10  is formed in a substantially central portion of a bottom wall  1   a  of the processing container  1 . An exhaust chamber  11  is provided in the bottom wall  1   a  to communicate with the opening  10  and to protrude downward. The side wall of the processing container  1  is provided with a loading/unloading port  17  for loading/unloading a wafer W, and a gate valve  18  for opening/closing the loading/unloading port  17 . 
     The stage  2  is provided inside the processing container  1 . For example, a semiconductor wafer (hereinafter simply referred to as a “wafer”) W as a substrate is placed on the stage  2 . The stage  2  has a disk shape and is made of ceramic, such as AlN. The stage  2  is supported by a cylindrical support member  12  made of ceramic, such as AlN, and extending upward from the center of the bottom of the exhaust chamber  11 . A guide ring  13  configured to guide the wafer W is provided on the outer edge of the stage  2 . In addition, inside the stage  2 , lifting pins (not illustrated) for raising/lowering the wafer W are provided to be moved upward or downward with respect to the top surface of the stage  2 . In addition, a resistance heater  14  is embedded in the stage  2 . The heater  14  is supplied with power from a heater power supply  15  and heats the wafer W placed on the stage  2  via the stage  2 . A thermocouple (not illustrated) is inserted into the stage  2 . The heating temperature of the wafer W can be controlled to a predetermined temperature in the range of, for example, 300 to 1,000 degrees C., based on a signal from the thermocouple. In addition, an electrode  16  having a size similar to that of the wafer W is embedded above the heater  14  in the stage  2 . A high-frequency bias power supply  19  is electrically connected to the electrode  16 . A high-frequency bias for attracting ions is applied from the high-frequency bias power supply  19  to the stage  2 . The high-frequency bias power supply  19  may not be provided, depending on the characteristics of plasma processing. 
     The microwave introduction mechanism  3  is configured to introduce microwaves into the processing container  1 , and is provided to face an opening in the upper portion of the processing container  1 . The microwave introduction mechanism  3  includes a planar slot antenna  21 , a microwave generator  22 , and a microwave transmission mechanism  23 . 
     The planar slot antenna  21  is made of, for example, a copper plate or an aluminum plate having a silver or gold-plated surface, and has a configuration in which a plurality of slots  21   a  for radiating microwaves are formed to penetrate the plate in a predetermined pattern. The pattern of the slots  21   a  is appropriately set such that the microwaves are evenly radiated. An example of a suitable pattern includes a radial line slot in which a plurality of pairs of slots  21   a  are concentrically arranged, and the two slots  21   a  in each pair are arranged in a T shape. The lengths and the arrangement intervals of the slots  21   a  are appropriately determined according to an effective wavelength kg of microwaves. The slots  21   a  may have another shape, such as a circular shape or an arc shape. The arrangement form of the slots  21   a  is not particularly limited, and the slots  21   a  may be arranged, for example, in a spiral shape or a radial shape, in addition to the concentric circle shape. The pattern of the slots  21   a  is appropriately set to have a microwave radiation characteristic that can obtain a desired plasma density distribution. 
     A microwave transmission plate  24  made of a dielectric material is provided below the planar slot antenna  21  to be supported by an upper plate  32  provided in a ring shape in the upper portion of the processing container  1 . A water-cooled shield member  25  is provided on the planar slot antenna  21 . In addition, a slow-wave material  26  is provided between the shield member  25  and the planar slot antenna  21 . 
     The slow-wave material  26  is made of a dielectric material having a dielectric constant greater than that of a vacuum, for example, quartz, ceramic (Al 2 O 3 ), or a resin such as polytetrafluoroethylene or polyimide. The slow-wave material  26  functions to make the wavelength of the microwaves shorter than that in a vacuum, thereby reducing the size of the planar slot antenna  21 . The microwave transmission plate  24  is also made of the same dielectric material. 
     The thicknesses of the microwave transmission plate  24  and the slow-wave material  26  are adjusted such that an equivalent circuit formed by the slow-wave material  26 , the planar slot antenna  21 , the microwave transmission plate  24 , and the plasma satisfies resonance conditions. By adjusting the thickness of the slow-wave material  26 , it is possible to adjust the phase of microwaves. By adjusting the thickness of the planar slot antenna such that a joint portion of the planar slot antenna  21  becomes an “antinode” of a standing wave, the reflection of microwaves is minimized and the radiant energy of microwaves is maximized. In addition, when the slow-wave material  26  and the microwave transmission plate  24  are made of the same material, it is possible to prevent the interface reflection of microwaves. 
     The microwave generator  22  is configured to generate microwaves, and has a microwave oscillator. The microwave oscillator may be a magnetron oscillator or a solid-state oscillator. The frequency of microwaves oscillated from the microwave oscillator may be in the range of 300 MHz to 10 GHz. For example, by using the magnetron oscillator as the microwave oscillator, it is possible to oscillate microwaves having a frequency of 2.45 GHz. 
     The microwave transmission mechanism  23  is configured to guide the microwaves from the microwave generator  22  to the planar slot antenna  21 . The microwave transmission mechanism  23  includes a waveguide  27 , a coaxial waveguide  28 , and a mode conversion mechanism  31 . The waveguide  27  guides the microwaves from the microwave generator  22  and extends in the horizontal direction. The coaxial waveguide  28  includes an inner conductor  29  extending upward from the center of the planar slot antenna  21  and an outer conductor  30  provided outside the inner conductor  29 . The mode conversion mechanism  31  is provided between the waveguide  27  and the coaxial waveguide  28 , and is configured to convert a microwave vibration mode. The microwaves generated by the microwave generator  22  propagate through the waveguide  27  in a TE mode, the microwave vibration mode is converted from the TE mode to a TEM mode by the mode conversion mechanism  31 , and the microwaves are guided to the slow-wave material  26  through the coaxial waveguide  28 . Then, the microwaves are radiated from the slow-wave material  26  into the processing container  1  via the slots  21   a  of the planar slot antenna  21  and the microwave transmission plate  24 . A tuner (not illustrated) is provided in the waveguide  27  to match the impedance of a load (plasma) in the processing container  1  with the characteristic impedance of the power supply of the microwave generator  22 . 
     The gas supply mechanism  4  includes a shower plate  41  horizontally provided above the stage inside the processing container  1  to partition upper and lower portions of the interior of the processing container  1 , and a shower ring  42  provided above the shower plate  41  in a ring shape along the inner wall of the processing container  1 . 
     The shower plate  41  includes grid-shaped gas flow members  51 , grid-shaped gas flow paths  52  provided inside the gas flow members  51 , respectively, and a large number of gas ejection holes  53  extending downward from the gas flow paths  52 , respectively. A through hole  54  is formed between adjacent grid-shaped gas flow members  51 . A gas supply path  55  reaching the outer wall of the processing container  1  extends in the gas flow paths  52  of the shower plate  41 , and a gas supply pipe  56  is connected to the gas supply path  55 . The gas supply pipe  56  branches into four branch pipes  56   a ,  56   b ,  56   c , and  56   d . A H 2  gas source  57  is connected to the branch pipe  56   a  to supply a H 2  gas as a hydrogen-containing gas. A C 2 H 2  gas source  58   a  is connected to the branch pipe  56   b  to supply an acetylene (C 2 H 2 ) gas as the carbon-containing gas used for the first processing gas. A C 2 H 4  gas source  58   b  is connected to the branch pipe  56   c  to supply an ethylene (C 2 H 4 ) gas as the carbon-containing gas used for the second processing gas. A N 2  gas source  59  is connected to the branch pipe  56   d  to supply a N 2  gas used as a purge gas or the like. Although not illustrated, each of the branch pipes  56   a ,  56   b ,  56   c , and  56   d  includes a mass flow controller for flow rate control, and valves provided on front and back side of the mass flow controller. 
     The shower ring  42  includes a ring-shaped gas flow path  66  provided therein and a large number of gas ejection holes  67  connected to the gas flow path  66  and opened to the interior of the gas flow path  66 , and a gas supply pipe  61  is connected to the gas flow path. The gas supply pipe  61  branches into three branch pipes  61   a ,  61   b , and  61   c . An Ar gas source  62  is connected to the branch pipe  61   a  to supply an Ar gas as a noble gas serving as a plasma generation gas. An O 2  gas source  63  is connected to the branch pipe  61   b  to supply an O 2  gas as an oxidizing gas for etching a defect (non-graphene structure). An N 2  gas source  64  is connected to the branch pipe  61   c  to supply a N 2  gas used as a purge gas or the like. Although not illustrated, each of the branch pipes  61   a ,  61   b , and  61   c  includes a mass flow controller for flow rate control and valves provided on front and back sides of the mass flow controller. The carbon-containing gas, the oxidizing gas, and the noble gas are not limited to the gases described herein, and various gases described above may be used. 
     The exhauster  5  is configured to evacuate the gas inside the processing container  1 , and includes the exhaust chamber  11 , an exhaust pipe  81  provided in the side surface of the exhaust chamber  11 , and an exhaust device  82  having a vacuum pump connected to the exhaust pipe  81 , a pressure control valve, and the like. 
     The controller  6  is typically configured with a computer, and controls each part of the processing apparatus  100 . The controller  6  includes a storage part that stores a process sequence of the processing apparatus  100  and process recipes as control parameters, an input means, a display and the like, and is able to perform a predetermined control according to a selected process recipe. 
     When forming a graphene structure according to the above-described embodiment using the processing apparatus  100  configured as described above, first, the wafer W as a substrate is loaded into the processing container  1  and placed on the stage  2 . The surface of the wafer W is cleaned as needed. 
     Preferable conditions for this cleaning process are as follows. 
     Gas flow rate: Ar/H 2 =0 to 2,000 sccm/10 to 2,000 sccm 
     Pressure: 0.1 to 10 Torr (13.3 to 1,333 Pa) 
     Wafer temperature: 300 to 600 degrees C. 
     Time: 10 to 120 min 
     Subsequently, the internal pressure of the processing container  1  and the wafer temperature are controlled to predetermined values, and the first processing gas including the carbon-containing gas is supplied to the substrate to perform the preprocessing in Step  2 . Specifically, as the first processing gas, an Ar gas, which is a noble gas, is supplied from the shower ring  42 , and a C 2 H 2  gas as a carbon-containing gas is supplied from the shower plate  41 . At this time, a H 2  gas may be supplied as needed. The preprocessing in step  2  forms nuclei of the graphene structure on the surface of the substrate. 
     Preferable conditions for the preprocessing in step  2  are as follows. 
     Gas Flow Rate:
         Ar gas=0 to 1,000 sccm   C 2 H 2  gas=0.1 to 100 sccm   H 2  gas=0 to 300 sccm       

     Pressure: 1.33 to 133 Pa (0.01 to 1 Torr) 
     Temperature: 300 to 1,000 degrees C. (more preferably, 350 to 750 degrees C.) 
     Time: 1 to 10 min 
     Subsequently, the internal pressure of the processing container  1  and the wafer temperature are controlled to predetermined values, and the graphene structure is formed through the remote microwave plasma CVD in step  3 . 
     Specifically, an Ar gas as a plasma generation gas is supplied from the shower ring  42  to a position directly below the microwave transmission plate  24 , and microwaves generated by the microwave generator  22  are radiated into the processing container  1  to ignite plasma. The microwaves generated by the microwave generator  22  are guided to the slow-wave material  26  via the waveguide  27 , the mode conversion mechanism  31 , and the coaxial waveguide  28 , and are radiated into the processing container  1  from the slow-wave material  26  via the slots  21   a  of the planar slot antenna  21  and the microwave transmission plate  24 . 
     The microwaves spread as surface waves to a region directly below the microwave transmission plate  24  so that surface wave plasma is generated by the Ar gas. This region becomes a plasma generation region. 
     Subsequently, at the time at which the plasma is ignited, the C 2 H 4  gas as a carbon-containing gas serving as a film-forming raw material gas is supplied from the shower plate  41 . At this time, a H 2  gas and an O 2  gas may be supplied as needed. 
     These gases are excited and dissociated by the plasma diffused from the plasma generation region, and are supplied to the wafer W as a substrate placed on the stage  2  below the shower plate  41 . Since the wafer W is arranged in a region spaced apart from the plasma generation region and the plasma diffused from the plasma generation region is supplied to the wafer W, the plasma has a low electron temperature on the wafer W and thus causes little damage to the wafer W, and the plasma is turned into high-density plasma mainly composed of radicals. With such plasma, a graphene structure can be formed on the surface of the substrate on which the nuclei are formed according to a general crystal growth mode of nucleation and creeping growth. 
     At this time, the C 2 H 4  gas as a carbon-containing gas and, if necessary, the H 2  gas are supplied to a location below the plasma generation region from the shower plate  41  and are dissociated by the diffused plasma. Thus, it is possible to suppress excessive dissociation of these gases. However, these gases may be supplied to the plasma generation region. In addition, the Ar gas as a plasma generation gas may not be used, and, for example, the C 2 H 4  gas as a carbon-containing gas may be supplied to the plasma generation region to directly ignite the plasma. 
     Preferable conditions for the remote microwave plasma CVD in the processing apparatus  100  are as follows. 
     Gas Flow Rate:
         Ar gas=0 to 2,000 sccm   C 2 H 4  gas=0.1 to 300 sccm   O 2  gas=0 to 10 sccm   H 2  gas=0 to 500 sccm       

     Pressure:
         1.33 to 667 Pa (0.01 to 5 Torr) when the surface of the wafer is an insulator or a semiconductor   1.33 to 400 Pa (0.01 to 3 Torr) when the surface of the wafer is a metal (not having a catalytic function)       

     Temperature: 350 to 1,000 degrees C. (more preferably, 400 to 800 degrees C.) 
     Microwave power: 100 to 5,000 W (more preferably, 1,000 to 3,500 W) 
     Time: 1 to 200 min 
     The carbon-containing gas in the first processing gas and the carbon-containing gas in the second processing gas may be the same gas and may be both, for example, the C 2 H 2  gas. In that case, the C 2 H 4  gas source  58   b  is unnecessary. 
     Second Example of Processing Apparatus 
       FIG. 6  is a cross-sectional view schematically illustrating a second example of the processing apparatus,  FIG. 7  is a block diagram illustrating a configuration of a microwave introduction device in the processing apparatus of  FIG. 6 ,  FIG. 8  is a cross-sectional view schematically illustrating a microwave radiation mechanism in the processing apparatus of  FIG. 6 , and  FIG. 9  is a bottom view schematically illustrating a ceiling wall of a processing container in the processing apparatus of  FIG. 6 . 
     A processing apparatus  200  includes a processing container  101 , a stage  102 , a gas supply mechanism  103 , an exhaust device  104 , a microwave introduction device  105 , and a controller  106 . 
     The processing container  101  is configured to accommodate the wafer W, is formed of, for example, a metal material, such as aluminum or an alloy thereof, and has a substantially cylindrical shape. The processing container  101  includes a plate-shaped ceiling wall  111 , a bottom wall  113 , and a side wall  112  connecting the ceiling wall  111  and the bottom wall  113  to each other. The microwave introduction device  105  is provided above the processing container  101 , and functions as a plasma generating means that introduces electromagnetic waves (microwaves) into the processing container  101  so as to generate plasma. The microwave introduction device  105  will be described in detail later. 
     The ceiling wall  111  has a plurality of openings into which a microwave radiation mechanism and a gas introduction part of the microwave introduction device  105  to be described later are fitted. The side wall  112  has a loading/unloading port  114  for loading/unloading therethrough the wafer W as a substrate into and from a transfer chamber (not illustrated) adjacent to the processing container  101 . The loading/unloading port  114  is opened/closed by a gate valve  115 . The bottom wall  113  is provided with the exhaust device  104 . The exhaust device  104  is provided in an exhaust pipe  116  connected to the bottom wall  113  and includes a vacuum pump and a pressure control valve. By the vacuum pump of the exhaust device  104 , the gas inside the processing container  101  is exhausted through the exhaust pipe  116 . The internal pressure of the processing container  101  is controlled by the pressure control valve. 
     The stage  102  is disposed inside the processing container  101  to place the wafer W thereon. The stage  102  has a disk shape and is made of ceramic, such as AlN. The stage  102  is supported by a cylindrical support member  120  made of ceramic, such as AlN, and extending upward from the center of the bottom of the processing container  101 . A guide ring  181  configured to guide the wafer W is provided on the outer edge of the stage  102 . In addition, inside the stage  102 , lifting pins (not illustrated) for raising/lowering the wafer W are provided to be moved upward or downward with respect to the top surface of the stage  102 . A resistance heater  182  is embedded in the stage  102 . The heater  182  heats the wafer W placed on the stage  102  via the stage  102  by being supplied with power from a heater power supply  183 . A thermocouple (not illustrated) is inserted into the stage  102 . The heating temperature of the wafer W can be controlled to a predetermined temperature in the range of, for example, 350 to 1,000 degrees C., based on a signal from the thermocouple. In addition, an electrode  184  having a size similar to that of the wafer W is embedded above the heater  182  in the stage  102 . A high-frequency bias power supply  122  is electrically connected to the electrode  184 . A high-frequency bias for attracting ions is applied from the high-frequency bias power supply  122  to the stage  102 . The high-frequency bias power supply  122  may not be provided, depending on the characteristics of plasma processing. 
     The gas supply mechanism  103  is configured to introduce a plasma generation gas and a raw material gas for forming a graphene structure into the processing container  101  and includes a plurality of gas introduction nozzles  123 . The gas introduction nozzles  123  are fitted into respective openings formed in the ceiling wall  111  of the processing container  101 . A gas supply pipe  191  is connected to the gas introduction nozzles  123 . The gas supply pipe  191  branches into six branch pipes  191   a ,  191   b ,  191   c ,  191   d ,  191   e , and  191   f . An Ar gas source  192  is connected to the branch pipe  191   a  to supply an Ar gas as a noble gas serving as a plasma generation gas. An O 2  gas source  193  is connected to the branch pipe  191   b  to supply an O 2  gas as an oxidizing gas. A N 2  gas source  194  is connected to the branch pipe  191   c  to supply a N 2  gas used as a purge gas or the like. A H 2  gas source  195  is connected to the branch pipe  191   d  to supply a H 2  gas as a hydrogen-containing gas. A C 2 H 2  gas source  196  is connected to the branch pipe  191   e  to supply an acetylene (C 2 H 2 ) gas as the carbon-containing gas used for the first processing gas. A C 2 H 4  gas source  197  is connected to the branch pipe  191   f  to supply an ethylene (C 2 H 4 ) gas as the carbon-containing gas used for the second processing gas. Although not illustrated, each of the branch pipes  191   a ,  191   b ,  191   c ,  191   d ,  191   e , and  191   f  includes a mass flow controller for flow rate control and valves provided on front and back sides of the mass flow controller. As in the first example, it is possible to adjust the dissociation of gas by providing a shower plate and supplying, for example, the C 2 H 4  gas, to a position close to the wafer W. The same effects can also be obtained by extending nozzles configured to supply these gases downward. As in the first example, the carbon-containing gas, the oxidizing gas, and the noble gas are not limited to the aforementioned gases, and various gases described above may be used. 
     As described above, the microwave introduction device  105  is provided above the processing container  101 , and functions as a plasma generating means that introduces electromagnetic waves (microwaves) into the processing container  101  to generate plasma. As illustrated in  FIG. 6 , the microwave introduction device  105  includes a ceiling wall  111  of the processing container  101 , which functions as a ceiling plate, a microwave output part  130 , and an antenna unit  140 . 
     The microwave output part  130  generates microwaves, and distributes and outputs the microwaves to a plurality of routes. As illustrated in  FIG. 7 , the microwave output part  130  includes a microwave power supply  131 , a microwave oscillator  132 , an amplifier  133 , and a distributor  134 . The microwave oscillator  132  is a solid-state oscillator and oscillates microwaves at, for example, 860 MHz (e.g., PLL oscillation). The frequency of microwaves is not limited to 860 MHz, and may be in the range of 700 MHz to 10 GHz, such as 2.45 GHz, 8.35 GHz, 5.8 GHz, or 1.98 GHz. The amplifier  133  amplifies microwaves oscillated by the microwave oscillator  132 . The distributor  134  distributes microwaves amplified by the amplifier  133  to the plurality of routes, and distributes the microwaves while matching the impedances on the input side and the output side. 
     The antenna unit  140  introduces the microwaves output from the microwave output part  130  into the processing container  101 . The antenna unit  140  includes a plurality of antenna modules  141 , as illustrated in  FIG. 7 . Each of the plurality of antenna modules  141  introduces the microwaves distributed by the distributor  134  into the processing container  101 . The configurations of all of the antenna modules  141  are the same. Each antenna module  141  includes an amplifier part  142  configured mainly to amplify and output the distributed microwaves, and a microwave radiation mechanism  143  configured to radiate, into the processing container  101 , the microwaves output from the amplifier part  142 . 
     The amplifier part  142  includes a phase shifter  145 , a variable gain amplifier  146 , a main amplifier  147 , and an isolator  148 . The phase shifter  145  changes a phase of microwaves. The variable gain amplifier  146  adjusts a power level of the microwaves input to the main amplifier  147 . The main amplifier  147  is configured as a solid-state amplifier. The isolator  148  separates reflected microwaves, which are reflected from an antenna part of the microwave radiation mechanism  143  (to be described later) and are directed toward the main amplifier  147 . 
     As illustrated in  FIG. 6 , a plurality of microwave radiation mechanisms  143  are provided on the ceiling wall  111 . As illustrated in  FIG. 8 , each microwave radiation mechanism  143  includes a coaxial tube  151 , a power feeder  155 , a tuner  154 , and an antenna part  156 . The coaxial tube  151  includes a cylindrical outer conductor  152 , an inner conductor  153  provided inside the outer conductor  152  coaxially with the outer conductor  152 , and a microwave transmission path provided between the outer conductor  152  and the inner conductor  153 . 
     The power feeder  155  feeds the amplified microwaves from the amplifier part  142  to the microwave transmission path. The microwaves amplified by the amplifier part  142  are introduced into the power feeder  155  from a lateral side of an upper end portion of the outer conductor  152  via a coaxial cable. For example, by radiating the microwaves from the power feeding antenna, microwave power is fed to the microwave transmission path between the outer conductor  152  and the inner conductor  153  and propagates toward the antenna part  156 . 
     The antenna part  156  radiates microwaves from the coaxial tube  151  into the processing container  101 , and is provided in a lower end portion of the coaxial tube  151 . The antenna part  156  includes a disk-like planar antenna  161 , which is connected to a lower end portion of the inner conductor  153 , a slow-wave material  162  disposed on the side of the top surface of the planar antenna  161 , and a microwave transmission plate  163  disposed on the side of the bottom surface of the planar antenna  161 . The microwave transmission plate  163  is fitted into the ceiling wall  111 , and the bottom surface thereof is exposed to the internal space of the processing container  101 . The planar antenna  161  has slots  161   a  formed to penetrate therethrough. The shape of each slot  161   a  is appropriately set such that microwaves are efficiently radiated. A dielectric material may be inserted into each slot  161   a . The slow-wave material  162  is formed of a material having a dielectric constant higher than a vacuum, and the phase of microwaves can be adjusted based on the thickness of the slow-wave material  162  so that the radiation energy of the microwaves can be maximized. The microwave transmission plate  163  is also made of a dielectric material, and has a shape capable of efficiently radiating microwaves in a TE mode. Then, the microwaves transmitted through the microwave transmission plate  163  generate plasma in the internal space of the processing container  101 . As a material for constituting the slow-wave material  162  and the microwave transmission plate  163 , for example, quartz, ceramic, a fluorine-based resin such as a polytetrafluoroethylene resin, a polyimide resin or the like, may be used. 
     The tuner  154  matches the impedance of a load with the characteristic impedance of the microwave power supply  131 . The tuner  154  constitutes a slug tuner. For example, as illustrated in  FIG. 8 , the tuner  154  includes two slugs  171   a  and  171   b , an actuator  172  configured to independently drive these two slugs  171   a  and  171   b , and a tuner controller  173  configured to control the actuator  172 . The slugs  171   a  and  171   b  are arranged in a portion closer to the proximal end (upper end) than the antenna part  156  of the coaxial tube  151 . 
     The slugs  171   a  and  171   b  have an annular plate shape, are made of a dielectric material such as ceramic, and are disposed between the outer conductor  152  and the inner conductor  153  of the coaxial tube  151 . In addition, the actuator  172  individually drives each of the slugs  171   a  and  171   b , for example, by rotating two screws, which are provided inside the inner conductor  153  and to which the slugs  171   a  and  171   b  are screwed, respectively. Then, based on a command from the tuner controller  173 , the actuator  172  moves the slugs  171   a  and  171   b  in the vertical direction. The tuner controller  173  adjusts positions of the slugs  171   a  and  171   b  such that the impedance at the terminal end portions thereof becomes 50Ω. 
     The main amplifier  147 , the tuner  154 , and the planar antenna  161  are arranged close to each other. The tuner  154  and the planar antenna  161  constitute a lumped constant circuit and also function as a resonator. Impedance mismatch exists in the portion in which the planar antenna  161  is mounted, but since the impedance mismatch is directly tuned by the tuner  154  with respect to plasma load, it is possible to tune the impedance mismatch including plasma with high precision. Therefore, the influence of reflection on the planar antenna  161  can be eliminated. 
     As illustrated in  FIG. 9 , in this example, seven microwave radiation mechanisms  143  are provided, and microwave transmission plates  163  corresponding to the seven microwave radiation mechanisms  143  are provided so as to be evenly arranged in a closely packed hexagonal structure. That is, one of the seven microwave transmission plates  163  is arranged in the center of the ceiling wall  111 , and the other six microwave transmission plates  163  are arranged therearound. These seven microwave transmission plates  163  are arranged such that adjacent microwave transmission plates are evenly spaced apart from each other. In addition, the plurality of gas introduction nozzles  123  of the gas supply mechanism  103  are arranged to surround the periphery of the central microwave transmission plate. The arrangement of the microwave radiation mechanisms  143  is not limited thereto, and the number of microwave radiation mechanisms  143  is not limited to seven. 
     The controller  106  is typically configured with a computer, and controls each part of the processing apparatus  200 . The controller  106  includes a storage part that stores a process sequence of the processing apparatus  200  and process recipes as control parameters, an input part, a display and the like, and is able to perform predetermined control according to a selected process recipe. 
     When forming a graphene structure according to the above-described embodiment using the processing apparatus  200  configured as described above, first, as a substrate, for example, the wafer W having a surface made of an insulator, a semiconductor, or a metal is loaded into the processing container  101  and placed on the stage  102 . The surface of the wafer W is cleaned as needed. 
     Preferable conditions for this surface treatment are as follows. 
     Gas flow rate: Ar/H 2 =0 to 2,000 sccm/10 to 2,000 sccm 
     Pressure: 0.1 to 10 Torr (13.3 to 1,333 Pa) 
     Wafer temperature: 300 to 600 degrees C. 
     Time: 10 to 120 min 
     Subsequently, the internal pressure of the processing container  101  and the wafer temperature are controlled to predetermined values, and the first processing gas including the carbon-containing gas is supplied to the substrate to perform the preprocessing in step  2 . Specifically, an Ar gas as the noble gas and a C 2 H 2  gas as the carbon-containing gas are supplied from the gas introduction nozzles  123  as the first processing gas. At this time, a H 2  gas may be supplied as needed. Nuclei of the graphene structure are formed on the surface of the substrate through step  2 . 
     Preferable conditions for the preprocessing in step  2  are as follows. 
     Gas Flow Rate:
         Ar gas=0 to 1,000 sccm   C 2 H 2  gas=0.1 to 100 sccm   H 2  gas=0 to 300 sccm       

     Pressure: 1.33 to 133 Pa (0.01 to 1 Torr) 
     Temperature: 300 to 1,000 degrees C. (more preferably, 350 to 750 degrees C.) 
     Time: 1 to 10 min 
     Subsequently, the internal pressure of the processing container  101  and the wafer temperature are controlled to predetermined values, and the graphene structure is formed through the remote microwave plasma CVD in step  3 . 
     Specifically, from the gas introduction nozzles  123 , an Ar gas as the plasma generation gas is supplied to a position directly below the ceiling wall  111  of the processing container  101 , and microwaves are radiated into the processing container  101  to ignite plasma. The radiated microwaves are those output distributedly into the plurality of routes from the microwave output part  130  of the microwave introduction device  105 , guided into the plurality of antenna modules  141  of the antenna unit  140 , and radiated from the microwave radiation mechanisms  143 . 
     In each antenna module  141 , the microwaves are individually amplified by the main amplifier  147  constituting the solid-state amplifier, fed to each microwave radiation mechanism  143 , and transmitted to the coaxial tube  151 , thereby reaching the antenna part  156 . At that time, the impedances of the microwaves are automatically matched by the slugs  171   a  and  171   b  of the tuner  154 . Therefore, in the state in which there is substantially no power reflection, the microwaves are radiated from the tuner  154  through the slow-wave material  162  of the antenna part and from the slots  161   a  of the planar antenna  161 . Then, the microwaves further pass through the microwave transmission plate  163  and are transmitted to the surface (bottom surface) of the microwave transmission plate  163 , which is in contact with the plasma, thereby forming surface waves. The electric power from each antenna part  156  is spatially synthesized inside the processing container  101 , and surface wave plasma is generated by the Ar gas in a region directly below the ceiling wall  111 . This region becomes a plasma generation region. 
     Then, at the time at which the plasma is ignited, the C 2 H 4  gas as the carbon-containing gas serving as a film-forming raw material gas is supplied from the gas introduction nozzle  123 . At this time, a H 2  gas and an O 2  gas may be supplied as needed. 
     These gases are excited by plasma, dissociated, and supplied to the wafer W, which is the substrate placed on the stage  102 . Since the wafer W is arranged in a region spaced apart from the plasma generation region and the plasma diffused from the plasma generation region is supplied to the wafer W, the plasma has a low electron temperature on the wafer W and thus causes little damage to the wafer W, and the plasma is turned into high-density plasma mainly composed of radicals. With such plasma, a graphene structure can be formed according to a general crystal growth mode of nucleation and creeping growth. 
     In this example, the C 2 H 4  gas as the carbon-containing gas and, if necessary, the H 2  gas are supplied to the plasma generation region and dissociated. However, by using the same shower plate as in the first example or extending the gas introduction nozzle, the C 2 H 4  gas and, if necessary, the H 2  gas may be dissociated by plasma diffused from the plasma generation region to suppress the dissociation. In addition, the Ar gas as the plasma generation gas may not be used, and, for example, the C 2 H 4  gas as the carbon-containing gas may be supplied to the plasma generation region to directly ignite the plasma. 
     In the processing apparatus  200  of this example, the microwaves distributed into a plurality of routes are individually amplified by each main amplifier  147  constituting a solid-state amplifier, and are individually introduced into the processing container  101  from the plurality of antenna parts  156 , thereby forming surface waves. Then, the surface waves are synthesized in the internal space of the processing container  101  to generate microwave plasma. Therefore, a large-sized isolator or synthesizer is not required, and the processing apparatus can be made compact. In addition, the main amplifier  147 , the tuner  154 , and the planar antenna  161  are provided close to each other, and the tuner  154  and the planar antenna  161  constitute a lumped constant circuit and also function as a resonator. This makes it possible to tune the flat slot antenna mounting portion in which impedance mismatching exists, including plasma using the tuner  154  with high precision. Therefore, it is possible to reliably eliminate the influence of reflection, which enables high-precision plasma control. In addition, since the plurality of microwave transmission plates  163  are provided, the total area may be made smaller than that of the single microwave transmission plate  24  in the processing apparatus of the first example. This makes it possible to reduce the microwave power that is required to stably ignite and discharge plasma. 
     Preferable conditions for the remote microwave plasma CVD in the processing apparatus  200  are basically the same as those in the first example, but preferable conditions of some items are different from each other. The preferable conditions are as follows. 
     Gas Flow Rate:
         Ar gas=0 to 2,000 sccm   C 2 H 4  gas=0.1 to 300 sccm   O 2  gas=0.1 to 10 sccm   H 2  gas=0 to 500 sccm       

     Pressure:
         1.33 to 667 Pa (0.01 to 5 Torr) when the surface of the wafer is an insulator or a semiconductor   1.33 to 400 Pa (0.01 to 3 Torr) when the surface of the wafer is a metal (not having a catalytic function)       

     Temperature: 350 to 1,000 degrees C. (more preferably, 400 to 800 degrees C.) 
     Microwave power: 100 to 5,000 W in total (more preferably, 1,000 to 3,500 W) 
     Time: 1 to 200 min 
     In the apparatus in this example as well, the carbon-containing gas in the first processing gas and the carbon-containing gas in the second processing gas may be the same gas and may be both, for example, the C 2 H 2  gas. In that case, the C 2 H 4  gas source  197  may be omitted. 
     Experimental Example 
     Next, test examples will be described. 
     Experimental Example 1 
     In Experimental Example 1, bare Si substrates were prepared as substrates, and the effects of preprocessing performed prior to the film formation of a graphene structure through plasma CVD were confirmed. As the first processing gases, the C 2 H 2  gas, the H 2  gas, and the Ar gas were used, and the flow rates were set to 1 sccm, 0.1 sccm, and 50 sccm, respectively. In addition, the pressure was set to 0.4 Torr, the substrate temperature was set to 700 degrees C., and the processing times were changed to 0 sec (without processing), 180 sec, and 600 sec. 
       FIG. 10  illustrates AFM photographs showing the surface states of the substrates. As illustrate in  FIG. 10 , when no processing was performed (0 sec), the surface roughness (RMS) value was 0.095 nm, whereas, when the processing times were 180 sec and 600 sec, the RMS values were increased to 0.098 nm and 0.103 nm, respectively.  FIG. 11  shows a relationship between the processing times and the RMS values at this time. As shown in this figure, it can be seen that the RMS values increase as the processing times are longer. In addition,  FIG. 12  shows Raman spectrums of the surfaces of the substrates when the processing times were 0 sec, 180 sec, and 600 sec. From  FIG. 12 , it can be seen that the background intensities of Raman spectrum increases as the processing times are longer. 
     These results suggest that there may be microcrystals or carbon that does not have a clear structure on the surfaces of the substrates due to the processing performed with the processing gas including the carbon-containing gas prior to the plasma CVD. 
     Experimental Example 2 
     In Experimental Example 2, graphene structures were formed through the plasma CVD after surface treatment and preprocessing were performed on the Si substrates as the substrates, using the processing apparatus of the first example illustrated in  FIG. 5 . The surface treatment and the plasma CVD were carried out under fixed conditions, and the time during the preprocessing was changed. 
     As the manufacturing conditions, the substrate temperature was set to 700 degrees C., and the pressure was set to 0.4 Torr. Other conditions were set as follows. The process sequences at this time are summarized in  FIG. 13 . 
     Surface Treatment
         Ar gas: 35 sccm   H 2  gas: 2 sccm   Microwave power: 300 W   Time: 10 min       

     Preprocessing
         Ar gas: 50 sccm   H 2  gas: 0.1 sccm   C 2 H 2  gas: 1 sccm   Time: 10 to 600 sec       

     Plasma CVD
         Ar gas: 50 sccm   H 2  gas: 0.1 sccm   C 2 H 2  gas: 1 sccm   Microwave power: 425 W   Time: 1.5 min       

     For the graphene structures formed under respective conditions, the amounts of formed films were determined based on the D band intensities of Raman spectrums (the D band intensities increased as the amounts of formed films increased).  FIG. 14  is a diagram showing a relationship between the preprocessing times and the D band intensities (arbitrary unit). As shown in this figure, it was confirmed that the D-band intensities, that is, the amounts of formed films, increased as the preprocessing times were increased.  FIG. 15  illustrates SEM photographs of surfaces when the preprocessing times were 10 sec, 60 sec, and 120 sec, respectively. It can be seen from the SEM photographs that the coverage increases as the preprocessing time increases. The above results suggest that the nucleation density of a graphene structure increases as the preprocessing time increases. 
     &lt;Other Applications&gt; 
     Although embodiments have been described above, it should be considered that the embodiments disclosed herein are exemplary in all respects and are not restrictive. The embodiments described above may be omitted, replaced, or modified in various forms without departing from the scope and spirit of the appended claims. 
     For example, the plasma CVD is not limited to microwave plasma CVD. In addition, the processing apparatus for performing the remote microwave plasma CVD is not limited to the above-described examples, and various types of processing apparatuses may be used. 
     Furthermore, as the substrate for forming a graphene structure thereon, a semiconductor wafer based on a semiconductor, such as Si, has been described as an example, but the present disclosure is not limited thereto. 
     EXPLANATION OF REFERENCE NUMERALS 
       1 ,  101 : processing container,  2 ,  102 : stage,  3 : microwave introduction mechanism,  4 ,  103 : gas supply mechanism,  5 : exhauster,  6 ,  106 : controller,  82 ,  104  exhaust device,  100 ,  200 : processing apparatus,  105 : microwave introduction device,  300 : substrate,  301 : semiconductor substrate,  302 : insulating film,  303 : barrier film,  304 : metal film,  310 : nuclei,  320  graphene structure, W: wafer