Patent Publication Number: US-11658036-B2

Title: Apparatus for processing substrate

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This is a continuation application of U.S. patent application Ser. No. 16/997,125, filed Aug. 19, 2020, which is a continuation of U.S. patent application Ser. No. 16/299,279, filed on Mar. 12, 2019, which is a continuation of Ser. No. 16/194,549, filed on Nov. 19, 2018 and now issued as U.S. Pat. No. 10,475,659, and a continuation of Ser. No. 15/686,285, filed on Aug. 25, 2017, and now issued as U.S. Pat. No. 10,217,643, and claims the benefit of Japanese Patent Application No. 2016-167071 filed on Aug. 29, 2016, the entire disclosures of which are incorporated herein by reference. 
    
    
     TECHNICAL FIELD 
     The embodiments described herein pertain generally to an apparatus for processing a substrate. 
     BACKGROUND 
     A plasma processing may be performed on a target object such as a wafer by using a plasma processing apparatus. A plasma etching is one kind of such a plasma processing. The plasma etching is performed to transcribe a pattern of a mask formed on an etching target layer to the etching target layer. Generally, the mask is implemented by a resist mask. The resist mask is formed by a photolithography technique. Thus, a limit size of the pattern formed on the etching target layer depends on a resolution of the resist mask formed by the photolithography technique. 
     As a demand for high integration of electronic devices is getting higher, it is required to form the pattern smaller than the resolution limit of the resist mask. However, there is a limit in the resolution of the resist mask. Thus, as described in Patent Document 1, there is proposed a technique of adjusting a size of the resist mask and reducing a width of an opening provided in the resist mask by forming a silicon oxide film on the resist mask. 
     Patent Document 1: Japanese Patent Laid-open Publication No. 2004-080033 
     Meanwhile, as the electronic devices are miniaturized to meet the recent trend of the high integration, it is required to control a critical dimension (CD) with high accuracy when forming the pattern on the target object. Further, it may also be required to form various shapes of patterns. 
     As stated above, with regard to the pattern formation on the target object, it is required to develop a technique capable of coping with formation of various shapes of patterns as well as miniaturization of the patterns to meet the recent trend of high integration. 
     SUMMARY 
     In an exemplary embodiment, there is provided an apparatus for processing a substrate. The apparatus includes a chamber having at least one gas inlet and at least one gas outlet, a substrate support in the chamber, a plasma generator and a controller configured to cause (a) placing a substrate on the substrate support, the substrate including a target layer having a recess, (b) exposing the substrate to a silicon-containing precursor, thereby forming an adsorption layer on a sidewall of the recess, (c) generating a plasma from a gas mixture in the chamber, the gas mixture including an oxygen-containing gas and a halogen-containing gas, (d) exposing the substrate to the plasma, thereby forming a protection layer on the adsorption layer while etching a bottom of the recess and (e) repeating (b) to (d) in sequence. 
     In another exemplary embodiment, there is provided an apparatus for processing a substrate. The apparatus includes a chamber having at least one gas inlet and at least one gas outlet, a substrate support in the chamber, a plasma generator and a controller configured to cause (a) placing a substrate on the substrate support, the substrate including a target layer having a recess, (b) exposing the substrate to a first gas containing a precursor, thereby forming an adsorption layer on a sidewall of the recess, (c) supplying a gas mixture into the chamber, the gas mixture including a second gas and a third gas, the second gas being different from the first gas, and the third gas being different from the first gas and the second gas, (d) generating a plasma from the gas mixture, thereby forming a protection layer on the adsorption layer while etching a bottom of the recess and (e) repeating (b) to (d) in sequence. 
     In yet another exemplary embodiment, there is provided a plasma processing apparatus. The plasma processing apparatus includes a plasma chamber configured to accommodate a substrate including a film having an opening defined by a sidewall and a bottom, and a controller configured to control a process to be performed on the substrate in the plasma chamber, wherein the controller includes a sequencer that performs a sequence including (a) forming a first layer on the sidewall of the opening in the film, the first layer including silicon, and (b) generating a plasma to form a second layer on the sidewall of the opening from the first layer and to simultaneously etch a bottom of the opening in the film. 
     According to the exemplary embodiments as described above, in forming the pattern on the target object, it is possible to provide a technique capable of coping with the formation of various shapes of patterns as well as achieving miniaturization of the patterns to meet a trend of higher integration. 
     The foregoing summary is illustrative only and is not intended to be in any way limiting. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features will become apparent by reference to the drawings and the following detailed description. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       In the detailed description that follows, embodiments are described as illustrations only since various changes and modifications will become apparent to those skilled in the art from the following detailed description. The use of the same reference numbers in different figures indicates similar or identical items. 
         FIG.  1 A  is a flowchart for describing major processes of a method according to an exemplary embodiment;  FIG.  1 B  is a flowchart for specifically describing a part of the processes shown in  FIG.  1 A ; and  FIG.  1 C  is another flowchart for specifically describing a part of the processes shown in  FIG.  1 A ; 
         FIG.  2    is a diagram illustrating an example of a plasma processing apparatus; 
         FIG.  3    is a cross sectional view illustrating a state of a target object before the individual processes shown in  FIG.  1 A  to  FIG.  1 C  are performed; 
         FIG.  4 A  and  FIG.  4 B  are cross sectional views sequentially illustrating states of the target object after the individual processes shown in  FIG.  1 A  to  FIG.  1 C  are performed; 
         FIG.  5 A  and  FIG.  5 B  are cross sectional views sequentially illustrating states of the target object after the individual processes shown in  FIG.  1 A  to  FIG.  1 C  are performed; 
         FIG.  6 A  to  FIG.  6 C  are diagrams sequentially and schematically illustrating formation of a protection film in performing a sequence of forming the protection film shown in  FIG.  1 A  to  FIG.  1 C ; and 
         FIG.  7    is a diagram showing an example of a measurement result showing a correspondence between a film thickness of the protection film shown in  FIG.  4 A  and a height of a corner portion of an etching target layer formed by etching shown in  FIG.  4 B . 
     
    
    
     DETAILED DESCRIPTION 
     In the following detailed description, reference is made to the accompanying drawings, which form a part of the description. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. Furthermore, unless otherwise noted, the description of each successive drawing may reference features from one or more of the previous drawings to provide clearer context and a more substantive explanation of the current exemplary embodiment. Still, the exemplary embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. It will be readily understood that the aspects of the present disclosure, as generally described herein and illustrated in the drawings, may be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are explicitly contemplated herein. 
     Hereinafter, various exemplary embodiments will be described in detail with reference to the accompanying drawings. Same or corresponding parts in the various drawings will be assigned same reference numerals. 
       FIG.  1 A  to  FIG.  1 C  are flowcharts for describing a method according to an exemplary embodiment. A method MT of the present exemplary embodiment shown in  FIG.  1 A  to  FIG.  1 C  is directed to processing a target object (hereinafter, referred to as “wafer”). The method MT includes, as shown in  FIG.  1 A , a sequence SQ 1  (a first sequence). The sequence SQ 1  includes a process ST 1  and a process ST 2 . The method MT further includes a process ST 3 . The process ST 1  may include a process ST 1   a  (a first processing) shown in  FIG.  1 B . The process ST 1  may include a process ST 1   b  (a second processing) shown in  FIG.  1 C . Further, though the method MT of the present exemplary embodiment can be performed by using a single plasma processing apparatus (a plasma processing apparatus  10  to be described later), it may be also possible to use a plurality of plasma processing apparatuses  10  for the individual processes of the method MT. 
       FIG.  2    is a diagram showing an example of a plasma processing apparatus.  FIG.  2    schematically illustrates a cross sectional configuration of the plasma processing apparatus  10  which can be used in various exemplary embodiments of processing a target object. As depicted in  FIG.  2   , the plasma processing apparatus  10  is configured as a capacitively coupled plasma etching apparatus. 
     The plasma processing apparatus  10  includes a processing vessel  12 , an exhaust opening  12   e,  a carry-in/out opening  12   g,  a supporting member  14 , a placing table PD, a DC power supply  22 , a switch  23 , a coolant path  24 , a pipeline  26   a,  a pipeline  26   b,  an upper electrode  30 , an insulating shield member  32 , an electrode plate  34 , a gas discharge holes  34   a,  an electrode supporting body  36 , a gas diffusion space  36   a,  gas through holes  36   b,  a gas inlet opening  36   c,  a gas supply line  38 , a gas source group  40 , a valve group  42 , a flow rate controller group  45 , a deposition shield  46 , a gas exhaust plate  48 , a gas exhaust device  50 , a gas exhaust line  52 , a gate valve  54 , a first high frequency power supply  62 , a second high frequency power supply  64 , a matching device  66 , a matching device  68 , a power supply  70 , a control unit Cnt, a focus ring FR, a heater power supply HP, and a heater HT. The placing table PD is equipped with an electrostatic chuck ESC and a lower electrode LE. The lower electrode LE includes a first plate  18   a  and a second plate  18   b.  The processing vessel  12  forms a processing space Sp therein. 
     The processing vessel  12  has a substantially cylindrical shape. The processing vessel  12  is made of, for example, aluminum. An inner wall surface of the processing vessel  12  is anodically oxidized. The processing vessel  12  is frame-grounded. 
     The supporting member  14  is provided on a bottom portion of the processing vessel  12  inside the processing vessel  12 . The supporting member  14  has a substantially cylindrical shape. The supporting member  14  is made of, by way of example, an insulating material. The insulating material forming the supporting member  14  may contain oxygen, for example, quartz. Within the processing vessel  12 , the supporting member  14  is vertically extended from the bottom portion of the processing vessel  12 . 
     The placing table PD is provided within the processing vessel  12 . The placing table PD is supported by the supporting member  14 . The placing table PD holds a wafer W on a top surface thereof. The wafer W is the target object. The placing table PD is equipped with the lower electrode LE and the electrostatic chuck ESC. 
     The lower electrode LE includes the first plate  18   a  and the second plate  18   b.  The first plate  18   a  and the second plate  18   b  are made of a metal such as, but not limited to, aluminum. The first plate  18   a  and the second plate  18   b  have a substantially disc shape. The second plate  18   b  is provided on the first plate  18   a  and electrically connected to the first plate  18   a.    
     The electrostatic chuck ESC is provided on the second plate  18   b.  The electrostatic chuck ESC has a pair of insulating layers or insulating sheets; and an electrode, which serves as a conductive film, embedded therebetween. The electrode of the electrostatic chuck ESC is electrically connected to the DC power supply  22  via the switch  23 . The electrostatic chuck ESC attracts the wafer W by an electrostatic force such as a Coulomb force generated by a DC voltage applied from the DC power supply  22 . With this configuration, the electrostatic chuck ESC is capable of holding the wafer W. 
     The focus ring FR is placed on a peripheral portion of the second plate  18   b  to surround an edge of the wafer W and the electrostatic chuck ESC. The focus ring FR is configured to improve etching uniformity. The focus ring FR is made of a material which is appropriately selected depending on a material of an etching target film. By way of example, the focus ring FR may be formed of quartz. 
     The coolant path  24  is provided within the second plate  18   b.  The coolant path  24  constitutes a temperature controller. A coolant is supplied into the coolant path  24  from a chiller unit provided outside the processing vessel  12  via the pipeline  26   a.  The coolant supplied into the coolant path  24  is then returned back into the chiller unit via the pipeline  26   b.  In this way, the coolant is supplied into the coolant path  24  to be circulated therein. A temperature of the wafer W held by the electrostatic chuck ESC is controlled by adjusting a temperature of the coolant. Through the gas supply line  28 , a heat transfer gas, e.g., a He gas, is supplied from a heat transfer gas supply device into a gap between a top surface of the electrostatic chuck ESC and a rear surface of the wafer W. 
     The heater HT is a heating device. By way of non-limiting example, the heater HT is buried in the second plate  18   b.  The heater HT is connected to a heater power supply HP. As a power is supplied to the heater HT from the heater power supply HP, a temperature of the placing table PD is adjusted, so that a temperature of the wafer W placed on the placing table PD is adjusted. Further, the heater HT may be embedded in the electrostatic chuck ESC. 
     The upper electrode  30  is provided above the placing table PD, facing the placing table PD. The lower electrode LE and the upper electrode  30  are arranged to be substantially parallel to each other. Provided between the upper electrode  30  and the lower electrode LE is the processing space Sp in which a plasma processing is performed on the wafer W. 
     The upper electrode  30  is supported at an upper portion of the processing vessel  12  with the insulating shield member  32  therebetween. The insulating shield member  32  is made of an insulating material and may contain oxygen for example, but not limited to, quartz. The upper electrode  30  may include the electrode plate  34  and the electrode supporting body  36 . The electrode plate  34  faces the processing space Sp, and is provided with a multiple number of gas discharge holes  34   a.  In the exemplary embodiment, the electrode plate  34  may be made of silicon. In another exemplary embodiment, the electrode plate  34  may be made of silicon oxide. 
     The electrode supporting body  36  is configured to support the electrode plate  34  in a detachable manner, and is made of a conductive material such as, but not limited to, aluminum. The electrode supporting body  36  may have a water-cooling structure. The gas diffusion space  36   a  is formed within the electrode supporting body  36 . The multiple gas through holes  36   b  are extended downwards (towards the placing table PD) from the gas diffusion space  36   a,  and these gas through holes  36   b  respectively communicate with the gas discharge holes  34   a.    
     Through the gas inlet opening  36   c,  a processing gas is introduced into the gas diffusion space  36   a.  This gas inlet opening  36   c  is provided at the electrode supporting body  36  and connected with the gas supply line  38 . 
     The gas source group  40  is connected to the gas supply line  38  via the valve group  42  and the flow rate controller group  45 . The gas source group  40  includes a plurality of gas sources. These gas sources may include a source of an aminosilane-based gas, a source of a fluorocarbon gas (hydrofluorocarbon gas), a source of an oxygen (O 2 ) gas, a source of an inert gas, a source of a rare gas and a source of a carbon dioxide gas. As the aminosilane-based gas (which is contained in the first gas G 1  to be described later), one having a molecular structure with a relatively small number of amino groups may be used. By way of non-limiting example, monoaminosilane (H 3 —Si—R (R denotes an amino group which contains an organic group and may be substituted)) may be used. The aforementioned aminosilane-based gas (which is contained in the first gas G 1  to be described later) may include aminosilane having one to three silicon atoms and aminosilane having one to three amino groups. The aminosilane having the one to three silicon atoms may be monosilane (monoaminosilane) having one to three amino groups, disilane having one to three amino groups, or trisilane having one to three amino groups. Further, the aforementioned aminosilane may have an amino group which may be substituted. The amino group may be substituted with any one of a methyl group, an ethyl group, a propyl group or a butyl group. Furthermore, the aforementioned methyl group, the ethyl group, the propyl group or the butyl group may be substituted with a halogen. The fluorocarbon gas may be implemented by, by way of example, but not limitation, a CF 4  gas, a C 4 F 6  gas, a C 4 F 8  gas, or the like. The inert gas may be implemented by, for example, a nitrogen (N 2 ) gas or the like. The rare gas may be implemented by, for example, an Ar gas, or the like. 
     The valve group  42  includes a multiple number of valves, and the flow rate controller group  45  includes a multiple number of flow rate controllers such as mass flow controllers. Each of the gas sources belonging to the gas source group  40  is connected to the gas supply line  38  via each corresponding valve belonging to the valve group  42  and each corresponding flow rate controller belonging to the flow rate controller group  45 . Accordingly, in the plasma processing apparatus  10 , it is possible to supply a gas from one or more gas sources selected from the plurality of gas sources belonging to the gas source group  40  into the processing vessel  12  at individually controlled flow rate(s). Further, in the plasma processing apparatus  10 , a deposition shield  46  is provided along an inner wall of the processing vessel  12  in a detachable manner. The deposition shield  46  is also provided on an outer side surface of the supporting member  14 . The deposition shield  46  is configured to suppress an etching byproduct (deposit) from adhering to the processing vessel  12 , and is formed by coating an aluminum member with Y 2 O 3  or the like. Besides the Y 2 O 3 , the deposition shield may be made of an oxygen-containing material such as, but not limited to, quartz. 
     At a bottom side of the processing vessel  12 , the gas exhaust plate  48  is provided between the supporting member  14  and a side wall of the processing vessel  12 . The gas exhaust plate  48  may be made of, by way of example, an aluminum member coated with ceramic such as Y 2 O 3  or the like. The gas exhaust opening  12   e  is provided in the processing vessel  12  under the gas exhaust plate  48 . The gas exhaust opening  12   e  is connected with the gas exhaust device  50  via the gas exhaust line  52 . The gas exhaust device  50  includes a vacuum pump such as a turbo molecular pump, and is capable of decompressing the space within the processing vessel  12  to a required vacuum level. Through the carry-in/out opening  12   g,  the wafer W is carried into or out of the processing vessel  12 . The carry-in/out opening  12   g  is provided at the side wall of the processing vessel  12 , and the carry-in/out opening  12   g  is opened or closed by the gate valve  54 . 
     The first high frequency power supply  62  is configured to generate a first high frequency power for plasma generation, for example, a high frequency power of 40 MHz having a frequency ranging from 27 MHz to 100 MHz. The first high frequency power supply  62  is connected to the upper electrode  30  via the matching device  66 . The matching device  66  is a circuit configured to match an output impedance of the first high frequency power supply  62  and an input impedance at a load side (lower electrode LE side). The first high frequency power supply  62  may be connected to the lower electrode LE via the matching device  66 . 
     The second high frequency power supply  64  is configured to generate a second high frequency power for attracting ion into the wafer W, that is, a high frequency bias power. By way of example, the second high frequency power supply  64  generates a high frequency bias power of 3.2 MHz having a frequency ranging from 400 kHz to 40.68 MHz. The second high frequency power supply  64  is connected to the lower electrode LE via a matching device  68 . The matching device  68  is a circuit configured to match an output impedance of the second high frequency power supply  64  and the input impedance at the load side (lower electrode LE side). Further, the power supply  70  is connected to the upper electrode  30 . The power supply  70  is configured to apply, to the upper electrode  30 , a voltage for attracting positive ions within the processing space Sp into the electrode plate  34 . As an example, the power supply  70  is a DC power supply configured to generate a negative DC Voltage. If such a voltage is applied to the upper electrode  30  from the power supply  70 , the positive ions existing within the processing space Sp collide with the electrode plate  34 . As a result, secondary electrons and/or silicon is released from the electrode plate  34 . 
     The control unit Cnt is implemented by a computer including a processor, a storage unit, an input device, a display device, and so forth, and is configured to control individual components of the plasma processing apparatus  10 . To elaborate, the control unit Cnt is connected to the valve group  42 , the flow rate controller group  45 , the gas exhaust device  50 , the first high frequency power supply  62 , the matching device  66 , the second high frequency power supply  64 , the matching device  68 , the power supply  70 , the heater power supply HP and the chiller unit. 
     The control unit Cnt is operated to output control signals according to a program based on an input recipe. The selection of the gas supplied from the gas source group and a flow rate of the selected gas, the gas exhaust of the gas exhaust device  50 , power supplies from the first and second high frequency power supplies  62  and  64 , application of the voltage from the power supply  70 , the power supply of the heater power supply HP, the control of the flow rate and the temperature of the coolant from the chiller unit can be achieved in response to the control signals from the control unit Cnt. Further, individual processes of the method MT (shown in  FIG.  1   ) of processing a target object according to the present exemplary embodiment can be performed as the individual components of the plasma processing apparatus  10  are operated under the control of the control unit Cnt. 
     Now, referring back to  FIG.  1 A  to  FIG.  1 C , the method MT will be discussed in detail. In the following, an example where the plasma processing apparatus  10  is used to perform the method MT will be explained. The following description refers to  FIG.  3    to  FIG.  7    as well as  FIG.  1 A  to  FIG.  1 C  and  FIG.  2   .  FIG.  3    is a cross sectional view illustrating a state of a target object before individual processes shown in  FIG.  1 A  to  FIG.  1 C  are performed.  FIG.  4 A  and  FIG.  4 B  are cross sectional views sequentially illustrating states of the target object after the individual processes shown in  FIG.  1 A  to  FIG.  1 C  are performed.  FIG.  5 A  and  FIG.  5 B  are cross sectional views sequentially illustrating states of the target object after the individual processes shown in  FIG.  1 A  to  FIG.  1 C  are performed.  FIG.  6 A  to  FIG.  6 C  are schematic diagrams sequentially illustrating formation of a protection film in performing a sequence of forming the protection film shown in  FIG.  1 A  to  FIG.  1 C . 
     Prior to performing the method MT shown in  FIG.  1 A  to  FIG.  1 C , a wafer W shown in  FIG.  3    is carried into the processing vessel  12 . The wafer W illustrated in  FIG.  3    is an example of the target object to which the method MT of  FIG.  1 A  to  FIG.  1 C  is applied. The wafer W shown in  FIG.  3    is a substrate product formed through a dual damascene etching process. The wafer W shown in  FIG.  3    has a protrusion portion CV 1  (first protrusion portion), a protrusion portion CV 2  (second protrusion portion), an etching target layer PM and a groove portion TR. The etching target layer PM includes a region PM 1  belonging to the protrusion portion CV 1  and a region PM 2  belonging to the protrusion portion CV 2 . The groove portion TR is provided on a main surface SC of the wafer W. The groove portion TR is provided at the etching target layer PM. The groove portion TR is defined by the protrusion portion CV 1  and the protrusion portion CV 2 . 
     The wafer W depicted in  FIG.  3    further includes a mask MK and a deposition film DP. The mask MK is provided on the region PM 1 . Specifically, the mask MK is provided on an end surface SF 1  of the region PM 1  (that is, an interface between the region PM 1  and the mask MK). The deposition film DP is provided on the mask MK. 
     An inner surface SF 2  of the groove portion TR includes a surface SF 2   a,  a surface SF 2   b  and a surface SF 2   c.  The etching target layer PM includes the end surface SF 1  and the surface SF 2   a  at the protrusion portion CV 1 . The surface SF 2   a  is a part of the surface SF 2  at the side of the protrusion portion CV 1 . The surface SF 2   b  is located at a bottom portion BT of the groove portion TR. That is, the surface SF 2   b  is a bottom surface of the groove portion TR. The surface SF 2   c  is a part of the surface SF 2  at the side of the protrusion portion CV 2  and faces the surface SF 2   a.  The etching target layer PM includes the surface SF 2   c  and an end surface SF 3  at the protrusion portion CV 2 . The end surface SF 1 , the surface SF 2  and the end surface SF 3  belong to the main surface SC of the wafer W. 
     A width LP 1  of the groove portion TR is a distance between the surface SF 2   a  and the surface SF 2   c  and is, for example, 3 nm to 5 nm. A height difference LP 2  is a distance between the end surface SF 1  and the end surface SF 3 . A plane including the end surface SF 1  is located above the end surface SF 3 . In this case, the height difference LP 2  has a positive value. By performing the method MT, the region PM 2  of the etching target layer PM at the protrusion portion CV 2  is etched from a side of the end surface SF 3 , so that the height difference LP 2  is increased. 
     The etching target layer PM is a porous film provided with a multiple number of holes. The etching target layer PM has a low dielectric constant (low-k). The etching target layer PM may be made of, by way of non-limiting example, SiOCH. The mask MK may be made of, by way of example, but not limitation, TiN. The deposition film DP may be made of, for example, CF. 
     Referring back to  FIG.  1 A  to  FIG.  1 C , in the method MT, a sequence SQ 1  is performed one or more times. A series of processes from the start of the sequence SQ 1  to a process ST 3  (process ST 3 : YES) to be described later is an etching process for obtaining a required shape of the groove portion TR of the etching target layer PM. After the wafer W shown in  FIG.  3    is carried in, the sequence SQ 1  is performed. In the method MT, the sequence SQ 1  is repeatedly performed N times (N is an integer equal to or lager than 2). The sequence SQ 1  includes a process ST 1  and a process ST 2 . The process ST 1  is performed to form a protection film SX conformally on the main surface SC of the wafer W within the processing vessel  12  of the plasma processing apparatus  10  in which the wafer W is accommodated. An example of the process ST 1  is a process ST 1   a  shown in  FIG.  1 B . Another example of the process ST 1  is a process ST 1   b  shown in  FIG.  1 C . 
     The process ST 1   a  includes a sequence SQ 1   a  (second sequence). The sequence SQ 1   a  includes a process ST 11   a,  a process ST 12   a,  a process ST 13   a  and a process ST 14   a.    
     Between the process ST 1   a  and the process ST 1   b,  the process ST 1   a  will be first explained with reference to  FIG.  1 B . The process ST 1   a  includes the sequence SQ 1   a.  The sequence SQ 1   a  includes the process ST 11   a,  the process ST 12   a,  the process ST 13   a  and the process ST 14   a.  The process ST 1   a  further includes a process ST 15   a.    
     In the process ST 1   a,  the sequence SQ 1   a  is performed one or more times. A series of processes from the start of the sequence SQ 1   a  to the process ST 15   a  (process ST 15   a:  YES) to be described later is a process of forming the protection film SX conformally on the main surface SC (particularly, the surface SF 2   a,  the surface SF 2   b,  the surface SF 2   c  and the end surface SF 3 ) of the wafer W. 
     First, in the process ST 11   a,  the first gas G 1  containing silicon is supplied into the processing vessel  12 . The first gas G 1  contains an aminosilane-based gas. The first gas G 1  is supplied into the processing vessel  12  from a gas source selected from the plurality of gas sources belonging to the gas source group  40 . The first gas G 1  is an aminosilane-based gas such as, but not limited to, monoaminosilane (H 3 —Si—R (R denotes an amino group)). In the process ST 11   a,  plasma of the first gas G 1  is not generated. 
     As shown in  FIG.  6 A , molecules of the first gas G 1  adhere to the main surface SC of the wafer W as reaction precursors. The molecules (monoaminosilane) of the first gas G 1  adhere to the main surface SC of the wafer W by chemical adsorption based on chemical bonding, and plasma is not used in the process ST 11   a.  Further, a gas other than the monoaminosilane may be used as long as the gas contains silicon and can be attached to the surface of the wafer W by the chemical bonding. 
     The monoaminosilane-based gas is selected as the first gas G 1  because the chemical adsorption of the monoaminosilane can take place relatively easily since it has relatively high electronegativity and a molecular structure with polarity. A layer Ly 1  formed as the molecules of the first gas G 1  adhere to the main surface SC of the wafer W comes into a state close to a monomolecular layer (monolayer) since the adhesion is achieved by the chemical adsorption. Here, the smaller the amino group R of the monoaminosilane is, the smaller the molecular structure of the molecules adsorbed to the main surface SC of the wafer W may be and, thus, steric hindrance which depends on the size of the molecules may be reduced. Therefore, the molecules of the first gas G 1  can be uniformly adsorbed to the main surface SC of the wafer W, so that the layer Ly 1  can be formed to have a uniform film thickness on the main surface SC of the wafer W. By way of example, as the monoaminosilane (H 3 —Si—R) contained in the first gas G 1  reacts with OH groups on the main surface SC of the wafer W, H 3 —Si—O as the reaction precursors are formed, so that the layer Ly 1  formed of the monolayer of H 3 —Si—O is obtained. Thus, the layer L 1   y  of the reaction precursor is formed on the main surface SC of the wafer W conformally to have a uniform film thickness without being affected by a pattern density of the wafer W. 
     In the process ST 12   a  following the process ST 11   a,  the space within the processing vessel  12  is purged. To elaborate, the first gas G 1  supplied in the process ST 11   a  is exhausted. In the process ST 12   a,  an inert gas such as a nitrogen gas may be supplied into the processing vessel  12  as a purge gas. That is, the purging in the process ST 12   a  may be implemented by a gas purging of allowing the inert gas to flow in the processing vessel  12  or a purging by vacuum evacuation. In the process ST 12   a,  surplus molecules adhering to the wafer W may be removed. Through the processes as stated above, the layer Ly 1  of the reaction precursor is formed to be a very thin monolayer. 
     In the process ST 13   a  following the process ST 12   a,  plasma P 1  of a second gas is generated within the processing vessel  12 . To elaborate, the second gas containing a carbon dioxide gas is supplied into the processing vessel  12  from a gas source selected from the plurality of gas sources belonging to the gas source group  40 . The second gas may be another gas containing oxygen atoms besides the carbon dioxide gas. By way of non-limiting example, the second gas may be an oxygen gas. The high frequency power is supplied from the first high frequency power supply  62 . At this time, the second high frequency power supply  64  may also apply the bias power. Further, it may be also possible to generate the plasma by using only the second high frequency power supply  64  without using the first high frequency power supply  62 . By operating the gas exhaust device  50 , the pressure of the space within the processing vessel  12  is set to a preset pressure. 
     The molecules (constituting the monolayer of the layer Ly 1 ) adhering to the surface of the wafer W through the process ST 11   a  as stated above includes a bond between silicon and hydrogen. A binding energy of the silicon and the hydrogen is lower than a binding energy of silicon and oxygen. Accordingly, as illustrated in  FIG.  6 B , if the plasma P 1  of the second gas containing the carbon dioxide gas is generated, active species of the oxygen, for example, oxygen radicals are generated, and the hydrogen of the molecules constituting the monolayer of the layer Ly 1  is substituted with oxygen, so that a layer Ly 2  of silicon oxide film (for example, a SiO 2  film) is formed as a monolayer, as illustrated in  FIG.  6 C . 
     In the process ST 14   a  following the process ST 13   a,  the space within the processing vessel  12  is purged. To elaborate, the second gas supplied in the process ST 13   a  is exhausted. In the process ST 14   a,  an inert gas such as a nitrogen gas may be supplied into the processing vessel  12  as a purge gas. That is, the purging in the process ST 14   a  may be implemented by the gas purging of allowing the inert gas to flow in the processing vessel  12  or the purging by vacuum evacuation. 
     In the above-described sequence SQ 1   a,  the purging is performed in the process ST 12   a,  and the hydrogen of the molecules constituting the layer Ly 1  is substituted with the oxygen in the process ST 13   a  following the process ST 12   a.  Accordingly, the same as in an ALD method, by performing the single cycle of the sequence SQ 1   a,  the layer Ly 2  of the silicon oxide film can be conformally formed on the main surface SC of the wafer W in a thin uniform film thickness. 
     In the process ST 15   a  following the sequence SQ 1   a,  it is determined whether or not to finish the repetition of the sequence SQ 1   a.  To elaborate, in the process ST 15   a,  it is determined whether the repetition number of the sequence SQ 1   a  has reached a preset number. Determining the repetition number of the sequence SQ 1   a  is determining a film thickness TH of the protection film SX, which is the silicon oxide film, shown in  FIG.  4 A . That is, the thickness of the protection film SX finally formed on the wafer W is determined by a product of the film thickness of the silicon oxide film formed through a single cycle of the sequence SQ 1   a  and the repetition number of the sequence SQ 1   a.  Accordingly, the repetition number of the sequence SQ 1   a  is set based on the required thickness of the protection film SX formed on the wafer W. 
     If it is determined in the process ST 15   a  that the repetition number of the sequence SQ 1   a  has not reached the preset number (process ST 15   a:  NO), the sequence SQ 1   a  is repeated. Meanwhile, if it is determined in the process ST 15   a  that the repetition number of the sequence SQ 1   a  has reached the preset number (process ST 15   a:  YES), the repetition of the sequence SQ 1   a  is finished. As a result, the protection film SX of the silicon oxide film is formed on the main surface SC of the wafer W, as illustrated in  FIG.  4 A . That is, as the sequence SQ 1   a  is repeatedly performed the preset number of times, the protection film SX having the preset film thickness is conformally formed on the main surface SC of the wafer W in the uniform thickness. The thickness of the protection film SX is reduced as the repetition number of the sequence SQ 1   a  is decreased. 
     Referring back to  FIG.  1 A  to  FIG.  1 C , in the process ST 2  following the process ST 1 , the bottom portion BT (surface SF 2   b ) of the groove portion TR is etched by plasma generated within the processing vessel  12 . First, in the process ST 2 , a mixed gas of a third gas and a fourth gas is supplied into the processing vessel  12 . The third gas may be a processing gas containing a fluorocarbon-based gas, and the fourth gas may be a processing gas containing an oxygen gas. The third gas may be, by way of non-limiting example, a C 4 F 8  gas. The fourth gas may be, by way of example, but not limitation, Ar/N 2 /O 2 . Plasma of the mixed gas supplied into the processing vessel  12  is generated within the processing vessel  12 . To elaborate, a processing gas containing the mixed gas of the third gas and the fourth gas is supplied into the processing vessel  12  from a gas source selected from the plurality of gas sources belonging to the gas source group  40 . The high frequency power is supplied from the first high frequency power supply  62 , and the high frequency bias power is supplied from the second high frequency power supply  64 . Further, by operating the gas exhaust device  50 , the internal pressure of the space within the processing vessel  12  is set to a preset pressure. As a result, the plasma of the mixed gas of the third gas and the fourth gas is generated. Active species of F (fluorine) contained in the plasma generated in the process ST 2  etch the bottom portion BT of the groove portion TR of the etching target layer PM which is the porous film. Subsequently, the space within the processing vessel  12  is purged. To be specific, the processing gas supplied in the process ST 2  is exhausted from the inside of the processing vessel  12 . An inert gas such as a nitrogen gas may be supplied into the processing vessel  12  as a purge gas. That is, the purging performed in the process ST 2  may be the gas purging of allowing the inert gas to flow into the processing vessel  12  or the purging by vacuum evacuation. 
     As depicted in  FIG.  4 B , a depth of the groove portion TR is increased by performing the single cycle of the sequence SQ 1 . Further, since the region PM 2  of the etching target layer PM at the protrusion portion CV 2  is etched from a side of the end surface SF 3  through this single cycle of the sequence SQ 1 , a corner portion CP of the protrusion portion CV 2  is removed (chamfered) by this etching. That is, after the single cycle of the sequence SQ 1  is conducted, there may be generated a height LP 3  (a height of the removed portion of the corner portion CP) between a tip end of the end surface SF 3  of the region PM 2  and an end surface of the protection film SX provided on the surface SF 2   c  of the groove portion TR at the side of the protrusion portion CV 2 . The height LP 3  that may be generated in the method MT can be reduced by adjusting processing conditions such as a thickness of the protection film SX and an etching time. In the following description, the term “removed portion” refers to a portion removed by etching. 
       FIG.  7    is a diagram showing an example of a measurement result of a correspondence between a film thickness TH of the protection film SX shown in  FIG.  4 A  and the height LP 3  of the corner portion CP after the etching shown in  FIG.  4 B . A vertical axis of  FIG.  7    represents an increment K (nm) of the removed portion of the corner portion CP (that is, an increment of the height LP 3 ) in the etching of 1 nm in the process ST 2 , and a horizontal axis of  FIG.  7    indicates a value (nm) of the film thickness TH of the protection film SX provided on the surface SF 2   c  of the groove portion TR at the side of the protrusion portion CV 2  before the etching of the process ST 2 . A result GP 1  is a measurement result obtained when the high frequency bias power supplied from the second high frequency power supply  64  is 0 W; a result GP 2 , a measurement result obtained when the high frequency bias power supplied from the second high frequency power supply  64  is 25 W; and a result GP 3 , a measurement result obtained when the high frequency bias power supplied from the second high frequency power supply  64  is 100 W. 
     Referring to  FIG.  7   , the increment K of the removed portion of the corner portion CP (that is, the increment of the height LP 3 ) that has occurred in the etching of 1 nm in the process ST 2  is found to increase with a decrease of the film thickness TH of the protection film SX provided on the surface SF 2   c  of the groove portion TR at the side of the protrusion portion CV 2  and with an increase of the high frequency bias power supplied from the second high frequency power supply  64 . Further, in case that a DC voltage is supplied from the power supply  70  in the process ST 2 , the increment K of the removed portion of the corner portion CP (that is, the increment of the height LP 3 ) in the etching of 1 nm is found to increase with a rise of the corresponding DC voltage. 
     Further, in any of the results GP 1  to GP 3 , a variation of the increment K of the removed portion of the corner portion CP (the increment of the height LP 3 ) with respect to a variation of the film thickness TH (that is, an inclination of each graph of the results GP 1  to GP 3 ) is found to be larger when the film thickness TH of the protection film SX is equal to or less than 2 nm as compared to a case when the film thickness TH of the protection film SX is larger than 2 nm. Accordingly, as can be seen from  FIG.  7   , if the film thickness TH of the protection film SX before the process ST 2  is in the range form 2 nm to 8 nm, the removed portion of the corner portion CP caused in the etching of the process ST 2  can be reduced, and the height LP 3  of the removed portion of the corner portion CP can be reduced. Thus, degree of deformation of the etching target layer PM caused by the etching of the method MT can be reduced. 
     Now, the degree of anisotropy of the etching in the process ST 2  will be explained. Assuming that an etching rate in a vertical direction (a depth direction of the groove portion TR) is Y 1  (nm/min) and an etching rate in a horizontal direction (a direction which is perpendicular to the vertical direction and in which the main surface SC of the wafer W is expanded) is Y 2  (nm/min), there is satisfied a relationship of α=Y 2 /Y 1 , 0&lt;α&lt;1, which implies that the smaller the α is, the higher the anisotropy of the etching in the vertical direction may be. The value α is decreased with an increase of the high frequency bias power supplied from the second high frequency power supply  64 , and, also, is decreased with an increase of the internal pressure of the processing vessel  12 . As stated, the degree of the anisotropy of the etching in the process ST 2  can be appropriately controlled by adjusting the high frequency bias power supplied from the second high frequency power supply  64  and the internal pressure of the processing vessel  12 . 
     Now, referring to  FIG.  1 C , a case where the process ST 1   b  is used as the process ST 1  shown in  FIG.  1 A  will be explained. The process ST 1   b  is an example of the process ST 1  shown in  FIG.  1 A . The process ST 1   b  includes a process ST 11   b  and a process ST 12   b.  A processing detail of the process ST 11   b  is the same as the processing detail of the process ST 11   a.  A processing detail of the process ST 12   b  is the same as the processing detail of the process ST 12   a.  That is, as depicted in  FIG.  4 A , the protection film SX formed on the main surface SC of the wafer W through the process ST 1   b  is the layer Ly 1 . Accordingly, in case that the process ST 1   b  is used as the process ST 1 , the film thickness of the protection film SX formed through the single cycle of the sequence SQ 1  becomes equal to the film thickness of the protection film (layer Ly 2 ) formed through the single cycle of the sequence SQ 1   a.    
     In case that the process ST 1   b  is used as the process ST 1 , the formation of the layer Ly 2  (see  FIG.  6 C ) by the plasma P 1  of the second gas containing the oxygen atoms for use in the process ST 13   a  of the process ST 1   a  may be implemented by the etching in the process ST 2 , as illustrated in  FIG.  4 B . That is, as the oxygen atoms contained in the fourth gas used in the process ST 2  following the process ST 1   b  act the same way as the oxygen atoms used in the process ST 13   a  of the process ST 1   a,  the layer Ly 2  is obtained from the layer Ly 1 . That is, the layer Ly 1  is formed through the process ST 1   b,  and the layer Ly 2  is formed from the layer Ly 1  by the etching of the process ST 2  following the process ST 1   b.    
     Reference is made back to  FIG.  1 A . In the method MT, the sequence SQ 1  is performed one or more times. In the process ST 3  following the sequence SQ 1 , it is determined whether or not to finish the repetition of the sequence SQ 1 . To elaborate, in the process ST 3 , it is determined whether the repetition number of the sequence SQ 1  has reached a preset number. If it is determined in the process ST 3  that the repetition number of the sequence SQ 1  has not reached the preset number (process ST 3 : NO), the sequence SQ 1  is repeated. Meanwhile, if it is determined in the process ST 3  that the repetition number of the sequence SQ 1  has reached the preset number (process ST 3 : YES), the repetition of the sequence SQ 1  is finished. As a result, the groove portion TR provided on the main surface SC of the wafer W can be formed to have a desired shape (desired width and depth of the groove portion TR), as illustrated in  FIG.  5 B .  FIG.  4 A  and  FIG.  4 B  illustrate the states of the wafer W upon the completion of the first cycle of the sequence SQ 1 , whereas  FIG.  5 A  and  FIG.  5 B  illustrate the states of the wafer W upon the completion of the second cycle of the sequence SQ 1 . 
     The shape of the groove portion TR may be determined based on the repetition number of the sequence SQ 1 . That is, the width of the groove portion TR (that is, the shape of the groove portion TR in a width direction) finally formed on the main surface SC of the wafer W is substantially determined by a product of a film thickness of the silicon oxide film formed by the single cycle of the sequence SQ 1  and the repetition number of the sequence SQ 1 . Further, the depth of the groove portion TR (that is, the shape of the groove portion TR in the depth direction) finally formed on the main surface SC of the wafer W is substantially determined by a product of a depth of the groove portion TR etched by the single cycle of the sequence SQ 1  and the repetition number of the sequence SQ 1 . Thus, the repetition number of the sequence SQ 1  is set based on the required shape of the groove portion TR formed on the main surface SC of the wafer W. 
     Further, if the sequence SQ 1  in which the process ST 1   a  of  FIG.  1 B  is used as the process ST 1  is included in multiple cycles of the sequence SQ 1  repeatedly performed, the detailed shape of the groove portion TR relies on the repetition number of the sequence SQ 1   a  as well as the repetition number of the sequence SQ 1 . For example, in case that the sequence SQ 1  is performed N times, there may be assumed a case where, among the N cycles of the sequence SQ 1 , the sequence SQ 1  including the process ST 1   a  shown in  FIG.  1 B  is performed M times (M is an integer equal to or larger than 1 and equal to or smaller than N−1) and the sequence SQ 1  including the process ST 1   b  shown in  FIG.  1 C  is performed N-M times. Particularly, there may be considered a case where, among the N cycles of the sequence SQ 1 , the sequence SQ 1  including the process ST 1   a  shown in  FIG.  1 B  is first performed a single time, and then, in the second and subsequent cycles, the sequence SQ 1  including the process ST 1   b  shown in  FIG.  1 C  is performed N- 1  times. In this case, through the first cycle of the sequence SQ 1 , the protection film SX having a relatively thick film thickness TH can be first formed. If the repetition number of the sequence SQ 1  including the process ST 1   a  is relatively large, the etching target layer PM at the side of the surface SF 2  of the groove portion TR may be altered by the plasma of the oxygen gas used in the etching of the process ST 13   a.  Further, the deposition film DP may be removed by being etched by the plasma of this oxygen gas. In such a case, as the mask MK is exposed, the shape of the etching target layer PM of the protrusion portion CV 1  may be changed by this etching. 
     Furthermore, referring to  FIG.  5 B , if the width of the groove portion TR is enlarged (the width LP 1  of the groove portion TR is enlarged as the surface SF 2   a  of the groove portion TR is enlarged in a direction DR 1  and the surface SF 2   c  of the groove portion TR is enlarged in a direction DR 2 ) in the etching of the process ST 2  due to the relatively low anisotropy of the etching of the process ST 2 , the repetition number N of the sequence SQ 1  may be determined based on a required value dp of the depth LP 4  of the groove portion TR and a required value lp of the width LP 1  of the groove portion TR. Here, the required value dp of depth LP 4  of the groove portion TR may be determined based on the value Y 1  (nm/min) of the etching rate in the vertical direction, a processing time of each cycle of the sequence SQ 1  and a value thy of the film thickness TH of the protection film SX of each cycle of the sequence SQ 1 . The required value lp of the width LP 1  of the groove portion TR may be determined based on the value Y 2  (nm/min) of the etching rate in the horizontal direction, the processing time of each cycle of the sequence SQ 1  and the value thy of the film thickness TH of the protection film SX of each cycle of the sequence SQ 1 . 
     Further, referring to  FIG.  5 B , if the width (width LP 1 ) of the groove portion TR is maintained in the etching of the process ST 2  due to the relatively high anisotropy of the etching of the process ST 2 , the repetition number N of the sequence SQ 1  may be determined by an expression of N=(dp×tan(θ))/tha by using a required value tha (average value) of the film thickness TH which can be formed through the single cycle of the sequence SQ 1 , the required value dp of the depth LP 4  of the groove portion TR and a required shape of the groove portion TR (specifically, an angle θ shown in  FIG.  5 B ). Here, the required value tha (average value) of the film thickness TH that can be formed through the single cycle of the sequence SQ 1  can be determined based on a required value tht (maximum value) of the film thickness TH of the protection film SX formed through the N cycles of the sequence SQ 1  and the repetition number N of the sequence SQ 1 (tha=tht/N). The required value dp of the depth LP 4  of the groove portion TR can be determined based on the value Y 1  (nm/min) of the etching rate in the vertical direction, the processing time of each cycle of the sequence SQ 1  and the value thy of the film thickness TH of the protection film SX of each cycle of the sequence SQ 1 . The angle θ shown in  FIG.  5 B  can be determined based on the required value dp of the depth LP 4  of the groove portion TR and the required value tht of the film thickness TH of the protection film SX (tan(θ)=tht/dp). 
     Below, examples of major processing conditions of the process ST 2 , the process ST 11   a,  the process ST 13   a,  the sequence SQ 1  and the sequence SQ 1   a  are specified. 
     &lt;Process ST 2 &gt;
         Internal pressure (mTorr) of processing vessel  12 : 80 mTorr   Value (W) of high frequency power of first high frequency power supply  62  and value (MHz) of frequency: 300 W, 40 MHz   Value (W) of high frequency power of second high frequency power supply  64  and value (MHz) of frequency: 25 W, 13 MHz   Value (V) of DC voltage of power supply  70 : 0 V   Processing gas: C 4 F 8 /Ar/N 2 /O 2  gas   Flow rate (sccm) of processing gas: C 4 F 8  gas: 30 sccm, Ar gas: 1000 sccm, N 2  gas: 20 sccm, O 2  gas: 10 sccm   Processing time (s): 30 s       

     &lt;Process ST 11   a&gt; 
         Internal pressure (mTorr) of processing vessel  12 : 100 mTorr   Value (W) of high frequency power of first high frequency power supply  62 : 0 W   Value (W) of high frequency power of second high frequency power supply  64 : 0 W   Value (V) of DC voltage of power supply  70 : 0 V   Processing gas (first gas): monoaminosilane (H 3 —Si—R (R denotes an amino group))   Flow rate (sccm) of processing gas: 50 sccm   Processing time (s): 15 s       

     &lt;Process ST 13   a&gt; 
         Internal pressure (mTorr) of processing vessel  12 : 200 mTorr   Value (W) of high frequency power of first high frequency power supply  62 : 300 W, 10 kHz, Duty  50     Value (W) of high frequency power of second high frequency power supply  64 : 0 W   Value (V) of DC voltage of power supply  70 : 0 V   Processing gas (second gas): CO 2  gas   Flow rate (sccm) of processing gas: 300 sccm   Processing time (s): 5 s       

     &lt;Sequence SQ 1 &gt;
         Repetition number: 5 times       

     &lt;Sequence SQ 1   a&gt; 
         Repetition number 5 times       

     In the above-described method MT, the process ST 1  of conformally forming the protection film SX on the main surface SC of the wafer W (including the inner surface SF 2  of the groove portion TR) and the process ST 2  of etching the bottom portion BT of the groove portion TR provided on the main surface SC after the process ST 1  may be alternately repeated (process ST 3 ). Thus, by appropriately adjusting the film thickness TH of the protection film SX or the like for each of the multiple cycles of the process ST 1  and by appropriately adjusting the etching amount or the like for each of the multiple cycles of the process ST 2 , the groove portion TR can be processed with relatively high accuracy according to the various required shapes of the groove portion TR. 
     Furthermore, in the process ST 1   a,  since the protection film SX is conformally formed on the main surface SC of the wafer W (including the inner surface SF 2  of the groove portion TR) by the same method as the ALD method, the strength of protection of the main surface SC of the wafer W can be improved, and the protection film SX for protecting the main surface SC of the wafer W can be formed in the uniform thickness. 
     Moreover, since the process ST 1   b  only consists of the process ST 11   b  of forming the reaction precursor (layer Ly 1 ) on the main surface SC of the wafer W (including the inner surface SF 2  of the groove portion TR) with the first gas and the process ST 12   b  of purging the internal space of the processing vessel  12  after the completion of the process ST 11   b,  the protection film SX formed through the process ST 1   b  can be formed of the reaction precursor (layer Ly 1 ) formed in the process ST 11   b,  and, accordingly, can be a relatively thin film. In addition, since the plasma of the fourth gas containing oxygen is used in the process ST 2  following the process ST 1   b,  oxygen can be added to the reaction precursor (layer Ly 1 ) formed in the process ST 11   b,  and the protection film SX having the same composition as the protection film formed by the same method as the ALD method can be formed to have a relatively thin thickness. Furthermore, since the addition of the oxygen gas can be performed during the etching of the process ST 2 , high efficiency of the processing can be achieved. 
     Further, in the process ST 1   a,  since the protection film SX is conformally formed on the main surface SC of the wafer W (including the inner surface SF 2  of the groove portion TR) by the same method as the ALD method, the strength of the protection of the main surface SC of the wafer W can be improved, and the protection film SX for protecting the main surface SC of the wafer W can be formed in the uniform thickness. Since the process ST 1   b  only consists of the process ST 11   b  of forming the reaction precursor (layer Ly 1 ) on the main surface SC of the wafer W (including the inner surface SF 2  of the groove portion TR) with the first gas and the process ST 12   b  of purging the internal space of the processing vessel  12  after the completion of the process ST 11   b,  the protection film SX formed through the process ST 1   b  can be formed of the reaction precursor (layer Ly 1 ) formed in the process ST 11   b,  and, accordingly, can become a relatively thin film. In addition, since the plasma of the third gas containing oxygen is used in the process ST 2  following the process ST 1   b,  oxygen can be added to the reaction precursor (layer Ly 1 ) formed in the process ST 11   b,  and the protection film SX having the same composition as the protection film formed by the same method as the ALD method can be formed to have a relatively thin thickness. Furthermore, since the addition of the oxygen gas can be performed during the etching of the process ST 2 , high efficiency of the processing can be achieved. Further, in performing the N cycles of the sequence SQ 1 , since the sequence SQ 1  including the aforementioned process ST 1   a  is performed M times and the sequence SQ 1  including the aforementioned process ST 1   b  is performed N-M times, it is possible to cope with the formation of various shapes of the groove portion TR sufficiently. 
     Further, since the second gas contains oxygen atoms, in the process ST 13   a,  the reaction precursor (layer Ly 1 ) of the silicon formed in the process ST 11   a  is bond with the oxygen atoms, so that the protection film SX of the silicon oxide can be conformally formed. Moreover, in case that the second gas is a carbon dioxide gas, since the second gas contains the carbon atoms, damage caused by the oxygen atoms can be suppressed by the carbon atoms. 
     In addition, since the first gas contains the aminosilane-based gas, the reaction precursor (layer Ly 1 ) of the silicon can be formed along an atomic layer of the main surface SC of the wafer W through the process ST 11   a  and the process ST 11   b.    
     Further, by using the first gas containing the monoaminosilane, the reaction precursor (layer Ly 1 ) of the silicon can be formed through the process ST 11   a  and the process ST 11   b.    
     Furthermore, aminosilane having one to three silicon atoms may be used as the aminosilane-based gas contained in the first gas. Alternatively, aminosilane having one to three amino groups may be used as the aminosilane-based gas contained in the first gas. 
     Further, before the process ST 2  is performed, if the film thickness TH of the protection film SX formed in the process ST 1  is in the range from 2 nm to 8 nm, the etching effect upon the corner portion CP of the wafer W covered with the protection film SX can be reduced, as compared to the case where the film thickness TH of the protection film SX is below 2 nm, particularly. Thus, the degree of deformation of the wafer W caused by the etching of the process ST 2  can be reduced. 
     From the foregoing, it will be appreciated that the exemplary embodiment of the present disclosure has been described herein for purposes of illustration, and that various modifications may be made without departing from the scope and spirit of the present disclosure. Accordingly, the embodiment disclosed herein is not intended to be limiting. The scope of the inventive concept is defined by the following claims and their equivalents rather than by the detailed description of the exemplary embodiment. It shall be understood that all modifications and embodiments conceived from the meaning and scope of the claims and their equivalents are included in the scope of the inventive concept. 
     The claims of the present application are different and possibly, at least in some aspects, broader in scope than the claims pursued in the parent application. To the extent any prior amendments or characterizations of the scope of any claim or cited document made during prosecution of the parent could be construed as a disclaimer of any subject matter supported by the present disclosure, Applicants hereby rescind and retract such disclaimer. Accordingly, the references previously presented in the parent applications may need to be revisited.