Method of processing a workpiece

Abstract

The present application provides a technology for forming a film on a processed object with good controllability with region selectivity. A method according to an embodiment includes a step of anisotropically etching an etched layer of a processed object through an opening of the processed object by generating plasma of a first gas in a processing container in which the processed object is accommodated, and further includes a step of forming a film on an inner side surface of the opening by repeatedly performing a process including a first step of supplying a second gas into the processing container, a second step of purging a space in the processing container, a third step of generating plasma of a third gas containing an oxygen atom in the processing container, and a fourth step of purging the space in the processing container, the first gas containing a carbon atom and a fluorine atom, the second gas containing an aminosilane-based gas, the etched layer being a hydrophilic insulating layer containing silicon, and the first step not generating plasma of the first gas.

Description

[0001] This application is a divisional application of application No. 201810349214.8, filed on April 18, 2018, entitled "Method of processing a processed object". TECHNICAL FIELD

[0002] Embodiments of the present application relate to a method of processing a processed object. BACKGROUND

[0003] In a manufacturing process of electronic devices, in order to form a mask on a processed layer, etching is performed to transfer a pattern of the mask to the processed layer. Patent Literature 1 discloses a technology aimed at improving the shape of a hole of a pattern produced by etching. Patent Literature 2 discloses a technology aimed at forming a recess pattern on a substrate well by an etching step and a film forming step. Patent Literature 3 discloses a technology of cyclically performing etching while forming a protective film of a mask.

[0004] Prior Art Documents

[0005] Patent Literature

[0006] Patent Literature 1: International Publication No. WO2014 / 046083

[0007] Patent Literature 2: Japanese Patent Application Publication No. 2014-17438

[0008] Patent Literature 3: Japanese Patent Application Publication No. 2006-523030 SUMMARY

[0009] Technical Problem to be Solved by the Invention

[0010] A technology of forming a film on a processed object with good controllability with region selectivity is required.

[0011] Technical Solution to Solve the Technical Problem

[0012] In one embodiment, a method of processing a processed object is provided. The processed object includes an etching layer and a mask provided on the etching layer. An opening to the etching layer is formed in the mask. The method of processing the processed object includes: a step of anisotropically etching the etching layer via the opening (hereinafter referred to as step a); and a step of forming a film on a surface on an inner side of the opening after the execution of step a (hereinafter referred to as step b). Step a generates plasma of a first gas in a processing container of a plasma processing apparatus in which the processed object is accommodated. Step b repeatedly executes a process including: a first step of supplying a second gas into the processing container; a second step of purging a space in the processing container after the execution of the first step; a third step of generating plasma of a third gas containing an oxygen atom in the processing container after the execution of the second step; and a fourth step of purging the space in the processing container after the execution of the third step, to form a film on the surface on the inner side of the opening. The first gas contains a carbon atom and a fluorine atom. The second gas contains an aminosilane-based gas containing an organic group. The etching layer is a hydrophilic insulating layer containing silicon. The first step does not generate plasma of the first gas.

[0013] By the etching in step a, there is a case where a deposited portion as a reaction product due to the first gas is attached to the opening, and a portion (a portion where the etching layer is exposed) where the deposited portion is not attached is formed in an arc shape (recess) in the surface on the inner side of the opening. According to the method of one embodiment of the present application, by step b executed after step a, the deposited portion attached to the opening can be removed, and by forming a film in the portion where the arc shape is formed, the arc shape can be moderated.

[0014] In one embodiment, in the first step, the etching layer is etched via the opening while adjusting the temperature of the processed object to be uniform in a plurality of regions of the processed object. In the first step using the second gas, since a chemical reaction is used without generating plasma, the thickness of the film formed by step b including the first step increases as the temperature of the processed object (particularly, the etching layer) to which the film is formed increases. Therefore, according to the method of one embodiment of the present application, the thickness of the film formed in step b can be made uniform in a plurality of regions of the processed object.

[0015] In one embodiment, the processing container is provided with a first gas introduction port and a second gas introduction port. The first gas introduction port is provided above the object to be processed. The second gas introduction port is provided laterally of the object to be processed. In step a, the first gas is supplied from the first gas introduction port into the processing container, and the backflow prevention gas is supplied from the second gas introduction port into the processing container. In the first step of step b, the second gas is supplied from the second gas introduction port into the processing container, and the backflow prevention gas is supplied from the first gas introduction port into the processing container. In the third step of step b, the third gas is supplied from the first gas introduction port into the processing container, and the backflow prevention gas is supplied from the second gas introduction port into the processing container. The piping connected to the first gas introduction port and the piping connected to the second gas introduction port do not intersect each other. According to the method of this one embodiment, the second gas containing the organyl group-containing aminosilane-based gas having relatively high reactivity, which is used in the first step, is introduced into the second gas introduction port of the processing container, the first gas containing the carbon atom and the fluorine atom, which is used in step a, and the third gas containing the oxygen atom, which is used in the third step, are introduced into the first gas introduction port of the processing container, and the gas supply pipe connected to the first gas introduction port and the gas supply pipe connected to the second gas introduction port do not intersect each other, so that the reaction product that can be generated in the gas supply pipe due to the second gas containing the organyl group-containing aminosilane-based gas having relatively high reactivity and the first gas and the third gas can be reduced. In addition, by using the backflow prevention gas, the backflow of any of the first gas, the second gas, and the third gas in the gas supply pipe in a state in which none of the first gas, the second gas, and the third gas is flowing can be avoided.

[0016] In one embodiment, the first gas contains a fluorocarbon-based gas. As described above, the etching of the etching layer that is the hydrophilic insulating layer containing silicon using the first gas containing the fluorocarbon-based gas can be performed in step a.

[0017] In one embodiment, the second gas contains a monoamino silane. As described above, the formation of the silicon reaction precursor using the second gas containing the monoamino silane can be performed in the first step.

[0018] In one embodiment, the aminosilane-based gas contained in the second gas contains an aminosilane having 1 to 3 silicon atoms. The aminosilane-based gas contained in the second gas contains an aminosilane having 1 to 3 amino groups. As described above, the aminosilane-based gas contained in the second gas can use an aminosilane having 1 to 3 silicon atoms. In addition, the aminosilane-based gas contained in the second gas can use an aminosilane having 1 to 3 amino groups.

[0019] In one embodiment, a method of processing a processed object is provided. The method includes: a step of selectively forming a first film on a surface of the processed object; and a step of forming a second film on the surface of the processed object by atomic layer deposition while removing the first film.

[0020] In one embodiment, the deposition includes a process including: a first step of supplying a second gas into a processing container to form an adsorption layer on the surface of the processed object; a second step of purging a space in the processing container; and a third step of generating plasma of a third gas in the processing container.

[0021] In one embodiment, the deposition further includes a fourth step of exposing the second film to plasma of an inert gas after the third step.

[0022] In one embodiment, in the step of forming the second film, the first film is removed by the third step or the fourth step.

[0023] In one embodiment, the second gas is any of an aminosilane-based gas, a silicon-containing gas, a titanium-containing gas, a hafnium-containing gas, a tantalum-containing gas, a zirconium-containing gas, and an organic-containing gas, and the third gas is any of an oxygen-containing gas, a nitrogen-containing gas, and a hydrogen-containing gas.

[0024] In one embodiment, the first film is formed by plasma etching.

[0025] In one embodiment, the plasma etching is atomic layer etching.

[0026] In one embodiment, a method of processing a processed object is provided. The method includes: a step of preparing a processed object having a first region formed of a first material and a second region formed of a second material different from the first material; a step of etching the first region with a first plasma to form a first film on the second region; and a step of forming a second film on the first region by atomic layer deposition while removing the first film.

[0027] In one embodiment, the first gas contains a fluorocarbon gas, the first material contains silicon and oxygen, and the second material contains any of silicon, an organic substance, and a metal.

[0028] In one embodiment, the first gas contains a fluorocarbon gas, the first material contains silicon and oxygen, and the second material contains any of silicon, an organic substance, and a metal.

[0029] In one embodiment, the second film contains silicon.

[0030] In one embodiment, the second film formed on the processed object has a plurality of film thicknesses.

[0031] In one embodiment, the first film is removed by repeatedly performing the process, and a second film is formed on the surface of the object to be treated from which the first film has been removed.

[0032] Effects of Invention

[0033] A technique for selectively forming a film on a region of an object to be treated with good controllability is provided in the manner described above. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 is a flowchart showing a method of processing an object to be treated according to one embodiment.

[0035] Figure 2 is a diagram showing Figure 3 one example of a plasma processing apparatus that the processing system shown in

[0036] Figure 3 is a diagram schematically showing a part of a plurality of regions of a main surface of an object to be treated that are divided in a method of processing an object to be treated according to one embodiment.

[0037] Figure 4 (a), (b), and (c), Figure 4 (a) of the (a), (b), and (c), Figure 1 is a cross-sectional view showing a state of an object to be treated before implementation of the steps shown in Figure 4 (b) is a cross-sectional view showing a state of an object to be treated after implementation of the etching shown in Figure 1 Figure 4 (c) is a cross-sectional view showing a state of an object to be treated after implementation of the process shown in Figure 1

[0038] Figure 5 is a diagram showing Figure 1 the implementation of each step of the method shown in

[0039] Figure 6 (a), (b), and (c), Figure 6 (a) of the (a), (b), and (c), Figure 1 is a diagram showing a state of an object to be treated before implementation of the process shown in Figure 6 (b) is a diagram schematically showing a state of an object to be treated during implementation of the process shown in Figure 1 Figure 6 (c) is a diagram schematically showing a state of an object to be treated after implementation of the process shown in Figure 1

[0040] Figure 7 is another flowchart showing a method of processing an object to be treated according to one embodiment. ​​​​

[0041] Figure 8 Including (a) and (b), which schematically represent the passage Figure 7 The flowchart shows the process of forming a film on the surface of the object being treated.

[0042] Figure 9 Including (a) and (b), which are schematic representations based on Figure 7 The flowchart shows the method used to etch and form the film.

[0043] Figure 10 It means based on Figure 7 The flowchart illustrates the variation in film thickness during the implementation of the method.

[0044] Figure 11 It means based on Figure 7 The flowchart shows the variation of film thickness in the method.

[0045] Explanation of reference numerals in the attached figures

[0046] 10…Plasma processing device; 12…Processing container; 12e…Exhaust port; 12g…Inlet / outlet; 14…Support; 18a…First plate; 18b…Second plate; 22…DC power supply; 23…Switch; 24…Refrigerator flow path; 26a…Piping; 26b…Piping; 28…Gas supply passage; 30…Upper electrode; 32…Insulating shielding component; 34…Electrode plate; 34a…Gas exhaust port; 36…Electrode support ; 36a…Gas diffusion chamber; 36b…Gas flow port; 36c…Gas inlet; 38…Gas supply pipe; 40…Gas source group; 42…Valve group; 44…Flow controller group; 46…Deposit shield; 48…Exhaust plate; 50…Exhaust device; 52…Exhaust pipe; 52a…Gas inlet; 54…Gate valve; 62…First high-frequency power supply; 64…Second high-frequency power supply; 66…Matching device; 68…Matching device; 70…Power supply ; 82…Gas supply pipe; BF…Membrane; Cnt…Control section; EL…Etched layer; ELa…Main surface; ELb…Side surface; ELc…Bottom surface; ER…Region; ESC…Electrostatic chuck; FR…Focusing ring; FW…Main surface; G1…Second gas; HP…Heater power supply; HT…Temperature control section; La…First region; Lb…Second region; LE…Lower electrode; LP1…Line segment; LP1a…Line segment; LP2…Line segment; LP2a…Line segment; LP3…Line segment; LP4…Line segment; Ly1…Layer; Ly2…Layer; MK…Mask; MKa…Side surface; MKb…Front surface; M1…First membrane; M2…Second membrane; MT…Method; NC…Accumulation section; OP…Opening; OPa…Surface; P1…Plasma; PD…Stage; SFa…Surface; SFb…Surface; Sp…Processing space; TM1…Time; TM2…Time; W…Wafer. DETAILED DESCRIPTION

[0047] Hereinafter, each embodiment will be described in detail with reference to the drawings. In addition, the same or corresponding portions are denoted by the same reference numerals throughout the drawings.

[0048] (1st Embodiment)

[0049] When etching an etching film using a mask that delineates a pattern shape, reaction products are accumulated on the inner side surface of the opening (opening of the mask) as etching proceeds. Therefore, there is a case where a necking occurs in which the opening is plugged due to the accumulation of the reaction products. When the accumulation portion of the reaction products is formed in the opening, the accumulation portion collides with ions in the plasma, and the traveling direction of the ions is bent to lose anisotropy. Therefore, the ions collide with the inner side surface of the opening, and a bowing shape is formed in the side surface. When the bowing shape becomes significant, the inner sides of two adjacent openings can be penetrated. Therefore, a technique that mitigates the bowing shape of the inner side surface of the opening due to etching is desired. The 1st embodiment provides a technique that mitigates the bowing shape of the inner side surface of the opening due to etching.

[0050] Figure 1 is a flowchart showing a method of processing a processed body (hereinafter referred to as a wafer W) according to one embodiment. Figure 1 The method MT shown is one embodiment of a method of processing a processed body. The method MT (method of processing a processed body) is implemented by the plasma processing apparatus 10.

[0051] Figure 2 is a flowchart showing a method of processing a processed body (hereinafter referred to as a wafer W) according to one embodiment. Figure 1 is a view showing one example of a plasma processing apparatus according to one embodiment used in the implementation of the method MT. Figure 2 The cross-sectional configuration of the plasma processing apparatus 10 that can be utilized in various embodiments of the method MT is schematically shown. As shown in Figure 2 The plasma processing apparatus 10 is a plasma etching apparatus having electrodes of parallel flat plates, and has a processing container 12. The processing container 12 has a substantially cylindrical shape, and delineates a processing space Sp. The processing container 12 is, for example, composed of aluminum, and the inner wall surface thereof is subjected to an anodization treatment. The processing container 12 is securely grounded.

[0052] A substantially cylindrical support portion 14 is provided on the bottom portion of the processing container 12. The support portion 14 is, for example, composed of an insulating material. The insulating material that constitutes the support portion 14 can contain oxygen like quartz. The support portion 14 extends in the vertical direction from the bottom portion of the processing container 12 within the processing container 12. A stage PD is provided within the processing container 12. The stage PD is supported by the support portion 14.

[0053] As for the stage PD, the wafer W is held on the upper surface of the stage PD. The main surface FW of the wafer W is on the opposite side of the back surface of the wafer W from the upper surface of the stage PD, toward the upper electrode 30. The stage PD includes a lower electrode LE and an electrostatic chuck ESC. The lower electrode LE includes a first plate 18a and a second plate 18b. The first plate 18a and the second plate 18b are, for example, made of a metal such as aluminum, and are in a substantially disc shape. The second plate 18b is provided on the first plate 18a, and is electrically connected to the first plate 18a.

[0054] The electrostatic chuck ESC is provided on the second plate 18b. The electrostatic chuck ESC has a configuration in which an electrode made of a conductive film is arranged between a pair of insulating layers or a pair of insulating sheets. The electrode of the electrostatic chuck ESC is electrically connected to the direct current power supply 22 via the switch 23. The wafer W is in contact with the electrostatic chuck ESC when placed on the stage PD. The back surface of the wafer W (a surface on the opposite side of the main surface FW) is in contact with the electrostatic chuck ESC. The electrostatic chuck ESC adsorbs the wafer W using an electrostatic force such as a Coulomb force generated by a direct current voltage from the direct current power supply 22. Thus, the electrostatic chuck ESC can hold the wafer W.

[0055] A focus ring FR is arranged on the peripheral portion of the second plate 18b in a manner that surrounds the edge of the wafer W and the electrostatic chuck ESC. The focus ring FR is provided in order to improve the uniformity of etching. The focus ring FR can be made of a material selected as appropriate according to the material of the film to be etched, for example, can be made of quartz.

[0056] A refrigerant flow path 24 is provided inside the second plate 18b. The refrigerant flow path 24 constitutes a temperature adjustment mechanism. The refrigerant flow path 24 is supplied with a refrigerant from a cooling device (not shown) provided outside the processing container 12 via a pipe 26a. The refrigerant supplied to the refrigerant flow path 24 is returned to the cooling device via a pipe 26b. As described above, the refrigerant is supplied to the refrigerant flow path 24 in a circulating manner. By controlling the temperature of the refrigerant, the temperature of the wafer W supported by the electrostatic chuck ESC can be controlled.

[0057] A gas supply passage 28 is provided in the plasma processing device 10. The gas supply passage 28 supplies a heat transfer gas such as He gas from a heat transfer gas supply mechanism to between the upper surface of the electrostatic chuck ESC and the back surface of the wafer W.

[0058] The plasma processing apparatus 10 is provided with a temperature adjustment section HT that adjusts the temperature of the wafer W. The temperature adjustment section HT is built in the electrostatic chuck ESC. The temperature adjustment section HT is connected to a heater power source HP. The temperature adjustment section HT is supplied with electric power from the heater power source HP, whereby the temperature of the electrostatic chuck ESC is adjusted, and thus the temperature of the wafer W placed on the electrostatic chuck ESC can be adjusted. Further, the temperature adjustment section HT can also be embedded in the second plate 18b.

[0059] The temperature adjustment section HT includes a plurality of heating elements that generate heat, and a plurality of temperature sensors that respectively detect the temperature of the surroundings of the plurality of heating elements. The plurality of heating elements are respectively arranged as shown in Figure 3 each of the plurality of regions ER of the main surface FW of the wafer W when the wafer W is placed in alignment on the electrostatic chuck ESC. The control section Cnt recognizes the heating elements and the temperature sensors corresponding to each of the plurality of regions ER of the main surface FW of the wafer W in association with the regions ER when the wafer W is placed in alignment on the electrostatic chuck ESC. The control section Cnt can recognize the regions ER and the heating elements and the temperature sensors corresponding to the regions ER by using, for example, numerals or letters, etc., for each of the plurality of regions (each of the plurality of regions ER). The control section Cnt detects the temperature of one region ER by the temperature sensor arranged at a position corresponding to the one region ER, and adjusts the temperature of the one region ER by the heating element arranged at a position corresponding to the one region ER. Further, when the wafer W is placed on the electrostatic chuck ESC, the temperature detected by one temperature sensor is the same as the temperature of the region ER on the wafer W above the temperature sensor, and the temperature adjustment of the region ER is described later in Figure 4 (a) of FIG. 10, the temperature of the region ER in the main surface FW of the wafer W is the same as the temperature of the mask MK and the etched layer EL positioned in the region ER, more specifically.

[0060] The plasma processing apparatus 10 has an upper electrode 30. The upper electrode 30 is arranged in opposition to the placement table PD above the placement table PD. The lower electrode LE and the upper electrode 30 are arranged substantially in parallel to each other, and constitute a parallel plate electrode. A processing space Sp for plasma processing of the wafer W is provided between the upper electrode 30 and the lower electrode LE.

[0061] The upper electrode 30 is supported at the upper portion of the processing container 12 by an insulating shielding member 32. The insulating shielding member 32 is composed of an insulating material, for example, capable of containing oxygen like quartz. The upper electrode 30 can include an electrode plate 34 and an electrode support 36. The electrode plate 34 faces the processing space Sp, and a plurality of gas discharge holes 34a are provided in the electrode plate 34. The electrode plate 34 contains silicon (hereinafter sometimes referred to as silicon element) in one embodiment. In another embodiment, the electrode plate 34 can contain silicon oxide.

[0062] The electrode support 36 is a member that supports the electrode plate 34 in a detachable manner, and is composed of, for example, an electrically conductive material such as aluminum. The electrode support 36 can have a water-cooling configuration. A gas diffusion chamber 36a is provided inside the electrode support 36. A plurality of gas flow-through holes 36b that communicate with the gas discharge holes 34a extend downward from the gas diffusion chamber 36a.

[0063] The plasma processing apparatus 10 includes a first high-frequency power supply 62 and a second high-frequency power supply 64. The first high-frequency power supply 62 is a power supply that generates first high-frequency electric power for generating plasma, and generates high-frequency electric power of a frequency of 27 to 100 [MHz], and in one example, generates high-frequency electric power of 60 [MHz]. In addition, the first high-frequency power supply 62 has a pulse mode, and can be controlled at a frequency of 0.1 to 50 [kHz] and a duty (duty ratio) of 5 to 100%. The first high-frequency power supply 62 is connected to the upper electrode 30 via a matcher 66. The matcher 66 is a circuit for matching the output impedance of the first high-frequency power supply 62 to the input impedance of the load side (lower electrode LE side). Further, the first high-frequency power supply 62 can be connected to the lower electrode LE via the matcher 66.

[0064] The second high-frequency power supply 64 is a power supply that generates second high-frequency electric power, i.e., high-frequency bias electric power, for introducing ions into the wafer W, and generates high-frequency bias electric power of a frequency in the range of 400 [kHz] to 40.68 [MHz], and in one example, generates high-frequency bias electric power of a frequency of 13.56 [MHz]. In addition, the second high-frequency power supply 64 has a pulse mode, and can be controlled at a frequency of 0.1 to 50 [kHz] and a duty (duty ratio) of 5 to 100%. The second high-frequency power supply 64 is connected to the lower electrode LE via a matcher 68. The matcher 68 is a circuit for matching the output impedance of the second high-frequency power supply 64 to the input impedance of the load side (lower electrode LE side).

[0065] The plasma processing apparatus 10 also includes a power supply 70. The power supply 70 is connected to the upper electrode 30. The power supply 70 applies a voltage to the upper electrode 30 to introduce positive ions present in the processing space Sp into the electrode plate 34. In one example, the power supply 70 is a DC power supply that generates a negative DC voltage. When such a voltage is applied from the power supply 70 to the upper electrode 30, the positive ions present in the processing space Sp collide with the electrode plate 34. This releases secondary electrons and / or silicon from the electrode plate 34.

[0066] An exhaust plate 48 is provided on the bottom side of the processing container 12, between the support portion 14 and the side wall of the processing container 12. The exhaust plate 48 is constructed, for example, by coating aluminum with a ceramic such as Y2O3. An exhaust port 12e is provided below the exhaust plate 48 and on the processing container 12. An exhaust device 50 is connected to the exhaust port 12e via an exhaust pipe 52. The exhaust device 50 has a vacuum pump such as a turbomolecular pump, which can reduce the pressure of the space inside the processing container 12 to the desired vacuum level. In addition, a wafer W loading / unloading outlet 12g is provided on the side wall of the processing container 12, which can be opened and closed using a gate valve 54.

[0067] Gas source group 40 has multiple gas sources. These multiple gas sources can include gas sources containing organic groups such as aminosilanes and fluorocarbons (C). x F y This refers to various gas sources, including gas sources for gases (where x and y are integers from 1 to 10), gas sources for gases containing oxygen atoms (such as oxygen), and gas sources for inert gases. As an aminosilane gas containing an organic group, a gas with a molecular structure having a relatively small number of amino groups can be used; for example, a monoaminosilane (H3-Si-R, where R is a substituted amino group containing an organic group) can be used. The aforementioned aminosilane gas containing an organic group (the gas included in the second gas G1 described later) can include aminosilanes containing 1 to 3 silicon atoms, or aminosilanes containing 1 to 3 amino groups. The aminosilane containing 1 to 3 silicon atoms can be silane (monoaminosilane) containing 1 to 3 amino groups, silane (dimethylsilane) containing 1 to 3 amino groups, or silane (propane) containing 1 to 3 amino groups. Furthermore, the aforementioned aminosilane can have substituted amino groups. Moreover, the aforementioned amino groups can be substituted by any of methyl, ethyl, propyl, and butyl groups. Furthermore, the aforementioned methyl, ethyl, propyl, or butyl groups can be replaced by halogens. Any fluorocarbon gas, such as CF4, C4F6, or C4F8, can be used as the fluorocarbon gas (the gas included in the first gas described later). Any gas, such as nitrogen, Ar, or He, can be used as the inert gas.

[0068] The valve group 42 includes a plurality of valves, and the flow controller group 44 includes a plurality of flow controllers such as mass flow controllers. The plurality of gas sources of the gas source group 40 are respectively connected to the gas supply pipe 38 and the gas supply pipe 82 via the corresponding valves of the valve group 42 and the corresponding flow controllers of the flow controller group 44. Thus, the plasma processing apparatus 10 is capable of supplying the gas from one or more gas sources selected from the plurality of gas sources of the gas source group 40 into the processing vessel 12 at independently adjusted flow rates.

[0069] In the plasma processing apparatus 10, as described later, the amino silane-based gas containing an organic group is supplied, and therefore the plasma processing apparatus 10 has a post-mixing configuration in which the piping for supplying the amino silane-based gas containing an organic group is separated from the piping for supplying other processing gas (e.g., oxygen). The reactivity of the amino silane-based gas containing an organic group is relatively high, and therefore, in the case where the supply of the amino silane-based gas containing an organic group and the supply of other processing gas are performed by the same piping, the components of the amino silane-based gas containing an organic group adsorbed in the piping react with the components of other processing gas, and there are cases where the reaction products generated by the reaction are deposited in the piping. The reaction products deposited in the piping are difficult to remove by cleaning or the like, and become a cause of particles and a cause of abnormal discharge in the case where the position of the piping is close to the plasma region. Therefore, it is necessary to perform the supply of the amino silane-based gas containing an organic group and the supply of other processing gas by different piping respectively. By the post-mixing configuration of the plasma processing apparatus 10, the supply of the amino silane-based gas containing an organic group and the supply of other processing gas can be performed by different piping respectively.

[0070] The post-mixing configuration of the plasma processing apparatus 10 has at least two piping (the gas supply pipe 38, the gas supply pipe 82). The gas supply pipe 38 and the gas supply pipe 82 are both connected to the gas source group 40 via the valve group 42 and the flow controller group 44.

[0071] A gas introduction port 36c (a first gas introduction port) is provided in the processing container 12. The gas introduction port 36c is provided above the wafer W placed on the stage PD in the processing container 12. The gas introduction port 36c is connected to one end of a gas supply pipe 38. The other end of the gas supply pipe 38 is connected to the valve group 42. The gas introduction port 36c is provided in the electrode support 36. The gas introduction port 36c introduces the first gas (a gas containing a fluorocarbon compound, described later), the backflow prevention gas (a gas containing an inert gas or the like, described later), the third gas (a gas containing an oxygen atom, described later), and the purge gas (a gas containing an inert gas or the like, described later) to the gas diffusion chamber 36a. The gas supplied from the gas introduction port 36c to the processing space Sp via the gas diffusion chamber 36a is supplied to the space region between the wafer W and the upper electrode 30 on the wafer W.

[0072] A gas introduction port 52a (a second gas introduction port) is provided in the processing container 12. The gas introduction port 52a is provided laterally to the wafer W placed on the stage PD in the processing container 12. The gas introduction port 52a is connected to one end of a gas supply pipe 82. The other end of the gas supply pipe 82 is connected to the valve group 42. The gas introduction port 52a is provided in the side wall of the processing container 12. The gas introduction port 52a introduces the second gas G1 (a gas containing an aminosilane containing an organic group, described later) and the backflow prevention gas (a gas containing an inert gas or the like, described later) to the processing space Sp. The gas supplied from the gas introduction port 52a to the processing space Sp is supplied to the space region between the wafer W and the upper electrode 30 on the wafer W.

[0073] The gas supply pipe 38 connected to the gas introduction port 36c and the gas supply pipe 82 connected to the gas introduction port 52a do not intersect each other. In other words, the supply path of the first gas and the third gas containing the gas introduction port 36c and the gas supply pipe 38 and the supply path of the second gas G1 containing the gas introduction port 52a and the gas supply pipe 82 do not intersect each other.

[0074] In the plasma processing apparatus 10, a deposit shield 46 is detachably provided along the inner wall of the processing container 12. The deposit shield 46 is also provided to the outer periphery of the support portion 14. The deposit shield 46 is configured by covering Y2O3 or the like ceramic on aluminum material, and prevents etching by-products (deposits) from adhering to the components of the processing container 12. The deposit shield can be configured by an oxygen-containing material such as quartz in addition to Y2O3.

[0075] The control portion Cnt is a computer including a processor, a storage portion, an input device, a display device, and the like, and controls the entire plasma processing apparatus 10. Figure 2The illustrated plasma processing apparatus 10. The control section Cnt is connected to the valve group 42, the flow controller group 44, the exhaust apparatus 50, the 1st high-frequency power supply 62, the matcher 66, the 2nd high-frequency power supply 64, the matcher 68, the power supply 70, the heater power supply HP, the refrigeration mechanism, and the like in the plasma processing apparatus 10.

[0076] The control section Cnt operates in accordance with a computer program for controlling the sections of the plasma processing apparatus 10 in each step of the method MT (a program based on the input processing recipe), and issues control signals. The sections of the plasma processing apparatus 10 are controlled by the control signals from the control section Cnt. The control section Cnt specifically controls the selection and flow rate of the gas supplied from the gas source group 40, the exhaust of the exhaust apparatus 50, the power supply from the 1st high-frequency power supply 62 and the 2nd high-frequency power supply 64, the voltage application from the power supply 70, the power supply of the heater power supply HP, the refrigerant flow rate and refrigerant temperature from the refrigeration mechanism, and the like in the plasma processing apparatus 10. Figure 2 The control section Cnt operates in accordance with a computer program for controlling the sections of the plasma processing apparatus 10 in each step of the method MT (a program based on the input processing recipe), and issues control signals. The sections of the plasma processing apparatus 10 are controlled by the control signals from the control section Cnt. The control section Cnt specifically controls the selection and flow rate of the gas supplied from the gas source group 40, the exhaust of the exhaust apparatus 50, the power supply from the 1st high-frequency power supply 62 and the 2nd high-frequency power supply 64, the voltage application from the power supply 70, the power supply of the heater power supply HP, the refrigerant flow rate and refrigerant temperature from the refrigeration mechanism, and the like in the plasma processing apparatus 10.

[0077] Again, reference is made to Figure 1 The method MT is described in detail. Hereinafter, an example of using the plasma processing apparatus 10 in the implementation of the method MT is described. In the following description, reference is made to Figure 4 , Figure 5 and Figure 6 . Figure 4 (a), (b), and (c) of Figure 4 (a) of Figure 1 is a cross-sectional view of the state of the processed body before the implementation of the step illustrated in Figure 4 (b) of Figure 1 is a cross-sectional view of the state of the processed body after the implementation of the etching illustrated in Figure 4 (c) of Figure 1 is a cross-sectional view of the state of the processed body after the implementation of the plurality of processes illustrated in Figure 5 is a view of the state of the supply of the gas and the supply of the high-frequency power in the implementation of each step of the method illustrated in Figure 1 is a view of the state of the supply of the gas and the supply of the high-frequency power in the implementation of each step of the method illustrated in Figure 6 (a), (b), and (c) of Figure 6 (a) of Figure 1 is a view schematically showing the state of the processed body before the implementation of the process illustrated in Figure 6 (b) ofFigure 1 The diagram shows the state of the processed entity during the implementation of the process. Figure 6 (c) is a schematic representation Figure 1 A diagram showing the state of the processed entity after the implementation of the process.

[0078] like Figure 1 As shown, method MT includes step ST1, process SQ1, and step ST3. Before step ST1 of method MT is implemented, the wafer W, which is to be processed, is first prepared. The prepared wafer W is as follows: Figure 4 As shown in (a), there is an etched layer EL and a mask MK. The mask MK is disposed on the main surface ELa of the etched layer EL. An opening OP is formed in the mask MK to the main surface ELa of the etched layer EL. The opening OP can be an opening such as a slot or a cavity. The main surface ELa of the etched layer EL is partially exposed through the opening OP. The mask MK includes a side surface MKa and a front surface MKb. The side surface MKa includes the surface OPa inside the opening OP. The front surface MKb includes the main surface FW of the wafer W.

[0079] The etchable layer EL is a layer composed of materials that can be selectively etched relative to the mask MK, such as a hydrophilic insulating layer containing silicon. More specifically, the etchable layer EL can contain silicon oxide (SiO2). The etchable layer EL can also contain other materials such as silicon nitride (Si3N4) and polycrystalline silicon.

[0080] A photomask MK is applied to the main surface ELa of the layer being etched, EL. The photomask MK is a photoresist mask containing a photoresist material such as ArF, formed by patterning the photoresist layer using photolithography. The photomask MK partially covers the main surface ELa of the layer being etched, EL. An opening OP defines the pattern shape of the photomask MK. The pattern shape of the photomask MK can be, for example, a line or spatial pattern. Furthermore, the photomask MK may have a pattern that provides a circular opening when viewed from above. Alternatively, the photomask MK may have a pattern that provides an elliptical opening when viewed from above.

[0081] Before implementing step ST1, prepare the above. Figure 4 The wafer W shown in (a) is housed in the processing container 12 of the plasma processing apparatus 10 and is mounted on the stage PD, aligned with the stage PD. The control unit Cnt... Figure 1In the implementation of method MT (at least in the implementation of step ST2a included in method MT), the temperature of each of the multiple regions ER of wafer W is detected by temperature sensors of temperature adjustment units HT located at locations corresponding to each of the multiple regions ER of wafer W. The temperature of each region ER is adjusted by heating elements of the temperature adjustment units HT located at locations corresponding to each region ER. Through temperature adjustment performed by the temperature adjustment units HT using the control unit Cnt, the temperature of wafer W becomes uniform across all the multiple regions ER.

[0082] In step ST1, Figure 4 The etchable layer EL of the wafer W shown in (a) is etched. Step ST1 is a step of anisotropically etching the etchable layer EL via the opening OP. In step ST1, a plasma of a first gas is generated in the processing space Sp of the processing container 12 of the plasma processing apparatus 10 that houses the wafer W. In step ST1, a gas source selected from a plurality of gas sources chosen from the gas source group 40, such as... Figure 5 As indicated by reference numeral FG1 in the attached diagram, the first gas is supplied to the processing space Sp of the processing container 12 via the gas supply pipe 38 from the gas inlet 36c, and, as Figure 5 As shown by reference numeral FG2 in the attached diagram, anti-backflow gas is supplied to the processing space Sp of the processing container 12 via gas supply pipe 82 and gas inlet 52a. The first gas can be appropriately selected according to the material constituting the etched layer EL. The first gas contains carbon atoms and fluorine atoms. For example, in the case where the etched layer EL is a silicon oxide film, the processing gas can contain a fluorocarbon gas. In order to prevent the first gas supplied to the processing space Sp and plasma ions of the first gas from entering the gas supply pipe 82 via gas inlet 52a, anti-backflow gas is supplied to the processing space Sp from gas inlet 52a. The anti-backflow gas can, for example, contain an inert gas. In addition, as Figure 5 The attached figure, labeled FG3, indicates that high-frequency power is supplied from the first high-frequency power source 62. Additionally, as... Figure 5 As indicated by reference numeral FG4 in the attached diagram, high-frequency bias power is supplied from the second high-frequency power supply 64. Furthermore, by activating the exhaust device 50, the pressure within the processing space Sp can be set to a predetermined pressure. This generates plasma. The active species in the generated plasma etch the area exposed from the mask MK through the opening OP in the entire region of the main surface ELa of the etched layer EL. Through step ST1, as... Figure 4 As shown in (b), the pattern of the mask MK (the pattern defined by the opening OP) is transferred to the etched layer EL.

[0083] Through the etching performed in step ST1, the etched layer EL is etched, and the inside of the opening OP reaches the interior of the etched layer EL. For example...Figure 4 In the etching performed in step ST1, the reaction product containing the component included in the first gas is deposited on the portion of the front surface MKb of the mask MK and the portion of the side surface MKa of the mask MK located in the opening OP, and the deposition portion NC of the reaction product is attached to the opening OP. That is, the opening OP has a necking portion in which the opening is narrowed due to the deposition of the reaction product (attachment of the deposition portion NC). The plasma ions generated in step ST1 are incident on the wafer W perpendicularly (anisotropically) with respect to the main surface FW of the wafer W, but when the deposition portion NC is attached, the plasma ions are incident on the deposition portion NC and collide with the deposition portion NC, and thus the traveling direction of the plasma ions is bent and the anisotropy of the plasma ions is lost. Therefore, the plasma ions collide with the inner surface OPa of the opening OP (including the side surface of the opening OP located in the side surface MKa of the mask MK, the side surface of the opening OP located in the side surface ELb of the etched layer EL, and the bottom surface of the opening OP located in the bottom surface ELc inside the etched layer EL, hereinafter the same) and form a bowing shape on the inner surface OPa of the opening OP.

[0084] In order to simultaneously perform the removal of the deposition portion NC attached to the opening OP by the execution of step ST1 and the filling of the bowing shape formed on the inner surface OPa of the opening OP by the execution of step ST1, the flow SQ1 and step ST3 are executed multiple times after step ST1. The flow SQ1 and step ST3 are steps of forming the film BF on the inner surface OPa of the opening OP after the execution of step ST1 of etching the etched layer EL.

[0085] The flow SQ1 is executed after step ST1. The flow SQ1 includes step T2a (first step), step ST2b (second step), step ST2c (third step), and step ST2d (fourth step). The method MT can repeatedly perform the flow SQ1 multiple times. By the flow SQ1 and step ST3, the flow SQ1 is repeatedly performed multiple times, and the film BF is formed on the inner surface OPa of the opening OP. From the start of the flow SQ1 to the series of steps described below as “YES” in step ST3, the steps of simultaneously performing the removal of the deposition portion NC attached to the opening OP by step ST1 and the filling of the bowing shape formed on the side surface MKa and the side surface ELb, and the steps of repairing the shape inside the opening OP, and more specifically the shape of the inner surface OPa of the opening OP, to a desired shape. The filling of the bowing shape formed on the side surface MKa and the side surface ELb is performed by forming the film BF on the portion of the bowing shape formed on the inner surface OPa of the opening OP. The film BF is a silicon oxide film containing silicon oxide (SiO2).

[0086] Step ST2a, as follows Figure 5 As indicated by reference numeral FG2 in the attached drawing, the second gas G1 is supplied from the gas inlet 52a through the gas supply pipe 82 into the processing space Sp of the processing container 12, and, as Figure 5 As indicated by reference numeral FG1 in the attached drawing, anti-backflow gas is supplied to the processing space Sp of the processing container 12 via gas supply pipe 38 from gas inlet 36c. The second gas G1 comprises an aminosilane gas containing organic groups. In step ST2a, the second gas G1 is supplied to the processing space Sp of the processing container 12 from a gas source selected from a plurality of gas sources chosen from gas source group 40. The second gas G1, as an aminosilane gas containing organic groups, can, for example, be a monoaminosilane (H3-Si-R (R being amino)). In step ST2a, as... Figure 5 The accompanying reference numerals FG3 and FG4 indicate plasma in which the second gas G1 is not generated. The molecules of the second gas G1 (monoaminosilane) adhere to the surface OPa inside the opening OP (specifically, the portion of surface OPa without the adhering accumulation NC) through chemical bond-based chemisorption, and plasma is not used in step ST2a. Furthermore, the second gas G1 can be any gas other than monoaminosilane, as long as it is a gas capable of adhering to the surface OPa (specifically, the portion of surface OPa without the adhering accumulation NC) through chemical bonds and contains silicon. To prevent the second gas G1 supplied to the processing space Sp from entering the gas supply pipe 38 via the gas inlet 36c, an anti-backflow gas is supplied to the processing space Sp from the gas inlet 36c. The anti-backflow gas may, for example, contain an inert gas.

[0087] The reason for choosing monoaminosilanes as the second gas, G1, is that monoaminosilanes have relatively high electronegativity and a polar molecular structure, making them relatively easy to chemically adsorb. For example... Figure 6 (a) and Figure 6 As shown in (b), the molecules of the second gas G1 adhere to the surface OPa inside the opening OP (specifically, the part of surface OPa that is exposed without the deposited portion NC). Figure 6The layer Ly1 formed by the adsorption of the second gas G1 to the surface OPa of the opening OP (also the same for the surface OPa shown in (a) to (c)) becomes a state close to a monomolecular layer (a single layer) because the adsorption is chemisorption. The smaller the amino group (R) of the monoamino silane, the smaller the molecular structure of the molecule adsorbed to the surface OPa of the inner side of the opening OP, so that the steric hindrance caused by the size of the molecule can be reduced, and thus the molecules of the second gas G1 can be uniformly adsorbed to the surface OPa of the inner side of the opening OP, and the layer Ly1 can be formed with a uniform film thickness with respect to the surface OPa of the inner side of the opening OP. For example, the monoamino silane (H3-Si-R) included in the second gas G1 reacts with the hydrophilic OH group of the surface OPa of the inner side of the opening OP, thereby forming a reaction precursor H3-Si-O, and thus it can be considered that the layer Ly1 as a monomolecular layer of H3-Si-O can be formed. Therefore, the layer Ly1 of the reaction precursor can be formed conformally with respect to the surface OPa of the inner side of the opening OP. Further, the accumulation portion NC of the opening OP to which the adsorption is made contains a hydrophobic compound including a carbon atom and a fluorine atom, so that the layer Ly1 is not formed in the accumulation portion NC, but, as described later, the accumulation portion NC is physically removed by the multiple implementation of the flow SQ1, and the surface OPa of the inner side of the opening OP exposed after the removal of the accumulation portion NC can form the layer Ly1.

[0088] Further, the amino silane-based gas included in the second gas G1 can include an amino silane including 1 to 3 silicon atoms in addition to the monoamino silane, and the amino silane-based gas included in the second gas G1 can include an amino silane including 1 to 3 amino groups.

[0089] In step ST2a, etching is performed on the etching layer EL via the openings OP while adjusting so that the temperature of the wafer W becomes uniform in the plurality of regions ER of the wafer W. That is, in the implementation of step ST2a, the control section Cnt continues the temperature adjustment of the wafer W with the temperature adjustment section HT so that the temperature of the wafer W (particularly, the mask MK and the etching layer EL of the wafer W) becomes uniform in all of the plurality of regions ER. The degree of chemical attachment (chemisorption) of the molecules of the second gas G1 (e.g., monoaminosilane) to the hydrophilic surface OPa on the inner side of the openings OP depends on the temperature of the surface OPa. Specifically, in the case where the molecules of the second gas G1 (e.g., monoaminosilane) are chemisorbed to the hydrophilic surface OPa on the inner side of the openings OP, as indicated by the Arrhenius equation that represents the correlation between the reaction rate of a chemical reaction and temperature, the higher the temperature of the surface OPa, the more the reaction rate of chemisorption increases, and thus the number of the molecules of the second gas G1 chemisorbed to the surface OPa also increases. Therefore, the higher the temperature of the surface OPa, the greater the film thickness of the layer Ly2 formed on the surface OPa, and the film thickness of the film BF formed on the surface OPa also increases by the multiple implementation of the process SQ1. Therefore, in order to form the film BF having the same film thickness in all of the plurality of regions ER of the wafer W, at least in the implementation of step ST2a, the temperature adjustment of the wafer W (particularly, the mask MK and the etching layer EL of the wafer W) needs to be continued so that the temperature of the wafer W (particularly, the mask MK and the etching layer EL of the wafer W) becomes uniform in all of the plurality of regions ER.

[0090] In step ST2b following step ST2a, the processing space Sp of the processing container 12 is purged. Specifically, the second gas G1 supplied in step ST2a is exhausted. For example, in step ST2b, an inert gas such as nitrogen gas as a purge gas can be supplied into the processing space Sp of the processing container 12 via the gas supply pipe 38 and the gas introduction port 36c. That is, the purge in step ST2b can be any of a gas purge in which an inert gas is circulated in the processing space Sp or a purge based on evacuation. In step ST2b, the molecules excessively attached to the surface OPa on the inner side of the openings OP can also be removed. By the above, the layer Ly1 of the reaction precursor becomes a very thin monomolecular layer.

[0091] In step ST2c following step ST2b, the plasma P1 of the third gas is generated in the processing container 12. In step ST2c, the plasma P1 of the third gas is generated from a gas source selected from the plurality of gas sources of the gas source group 40, such as Figure 5As indicated by reference numeral FG1 in the attached diagram, a third gas containing oxygen atoms is supplied from the gas inlet 36c through the gas supply pipe 38 into the processing space Sp of the processing container 12, and, as shown in the attached diagram... Figure 5 As shown by reference numeral FG2 in the attached diagram, anti-backflow gas is supplied to the processing space Sp of the processing container 12 via gas supply pipe 82 and gas inlet 52a. The third gas is a gas containing oxygen atoms, such as oxygen. The anti-backflow gas is used to prevent the third gas supplied to the processing space Sp from entering the gas supply pipe 82 via gas inlet 52a, and is supplied to the processing space Sp from gas inlet 52a. The anti-backflow gas may, for example, contain an inert gas. Moreover, as... Figure 5 As indicated by reference numeral FG3 in the attached diagram, high-frequency power is supplied from the first high-frequency power source 62. In this case, as... Figure 5 As indicated by reference numeral FG4 in the attached diagram, bias power from the second high-frequency power supply 64 can also be applied. Furthermore, plasma can be generated using only the second high-frequency power supply 64 without using the first high-frequency power supply 62. By activating the exhaust device 50, the pressure within the processing space Sp is set to a predetermined pressure.

[0092] As described above, the molecules (molecules constituting the monolayer of layer Ly1) of the surface OPa attached to the inside of the opening OP by the implementation of step ST2a contain silicon-hydrogen bonds. The bond energy between silicon and hydrogen is lower than that between silicon and oxygen. Therefore, as Figure 6 As shown in (b), when plasma P1 containing a third gas containing oxygen atoms is generated, active species of oxygen, such as oxygen free radicals, are generated. The hydrogen molecules in the monolayer constituting layer Ly1 are replaced by oxygen, as... Figure 6 As shown in (c), the layer Ly2, which serves as a silicon oxide film (SiO2 film), is formed as a monolayer.

[0093] In step ST2d following step ST2c, the processing space Sp of the processing container 12 is purged. Specifically, the third gas supplied in step ST2c is exhausted. For example, in step ST2d, an inert gas such as nitrogen can be supplied to the processing space Sp as the purging gas through the gas supply pipe 38 and the gas inlet 36c. That is, the purging in step ST2d can be either a purging of the inert gas that circulates within the processing space Sp or a purging based on vacuum.

[0094] In the flow SQ1 described above, in the step ST2b, purging is performed, and in the step ST2c following the step ST2b, hydrogen of the molecules constituting the layer Ly1 is replaced with oxygen. Therefore, similarly to the ALD (Atomic Layer Deposition) method, by one execution of the flow SQ1, a layer Ly2 of the silicon oxide film is formed conformally in a thin and uniform film thickness in the portion (including the portion of the arc shape) in which the accumulation portion NC is not attached in the surface OPa inside the opening OP. In the present specification, the ALD refers to atomic layer deposition in which accumulation is performed layer by layer per 1 atomic layer.

[0095] Since the accumulation portion NC includes the hydrophobic compound including the carbon atom and the fluorine atom, the layer Ly1 is not formed in the accumulation portion NC. By one execution of the flow SQ1, one or a plurality of atomic layers of the accumulation portion NC is removed from the surface of the accumulation portion NC.

[0096] In the step ST3 following the flow SQ1, it is determined whether or not the execution of the flow SQ1 is ended. Specifically, in the step ST3, it is determined whether or not the number of times of execution of the flow SQ1 reaches a number of times set in advance. The number of times of execution of the flow SQ1 is determined by the film thickness of the film BF indicated in (c) of Figure 4 More specifically, the product of the film thickness of the silicon oxide film (the layer Ly2) formed by one execution of the flow SQ1 and the number of times of execution of the flow SQ1 can substantially determine the thickness of the film BF formed in the portion (including the portion of the arc shape) in which the accumulation portion NC is not attached in the surface OPa inside the opening OP. Therefore, the number of times of execution of the flow SQ1 is set in accordance with the desired thickness of the film BF formed in the portion (including the portion of the arc shape) in which the accumulation portion NC is not attached in the surface OPa inside the opening OP.

[0097] In the portion to which the deposited portion NC in the surface OPa on the inner side of the opening OP is attached, the deposited portion NC is removed by the implementation of the flow SQ1 after the first time or a plurality of times including the first time, and the film BF is formed only by the implementation of the flow SQ1 after the side surface MKa and the side surface ELb are exposed. When the deposited portion NC having a hydrophobic surface (including a compound containing a carbon atom and a fluorine atom) is removed by the implementation of the flow SQ1 after the first time or a plurality of times including the first time, and the side surface MKa and the side surface ELb as a hydrophilic surface (including an OH group) are exposed, the monosilane (H3-Si-R) included in the second gas G1 reacts with the hydrophilic OH group of the surface OPa on the inner side of the opening OP by the implementation of the step ST2a of the flow SQ1 after the removal of the deposited portion NC, thereby forming a reaction precursor H3-Si-O, and thus a monolayer of the layer Ly1 as H3-Si-O is formed. As described above, the number of times of the implementation of the flow SQ1 until the film BF is formed in the portion to which the deposited portion NC in the surface OPa on the inner side of the opening OP is attached is smaller than the number of times of the implementation of the flow SQ1, and thus the film thickness of the film BF formed in the portion to which the deposited portion NC in the surface OPa on the inner side of the opening OP is attached is thinner than the film thickness of the film BF formed in the portion (including the portion in the arch shape) to which the deposited portion NC is not attached in the surface OPa on the inner side of the opening OP.

[0098] In a case where it is determined in the step ST3 that the number of times of the implementation of the flow SQ1 has not reached the number of times set in advance (step ST3: No), the implementation of the flow SQ1 is repeatedly performed again. On the other hand, in a case where it is determined in the step ST3 that the number of times of the implementation of the flow SQ1 has reached the number of times set in advance (step ST3: Yes), the implementation of the flow SQ1 is ended. By repeating the number of times of the implementation of the flow SQ1 by the number of times set in advance (step ST3: Yes), as shown in (c) of FIG. 1, the deposited portion NC can be removed and the film BF of the silicon oxide film can be formed on the surface OPa on the inner side of the opening OP. Figure 4

[0099] ​The film BF formed in the portion where the deposited portion NC is not attached in the surface OPa on the inner side of the opening OP is mainly formed in the portion of the arc shape (recess in the opening OP). The film thickness of the film BF formed in the portion where the deposited portion NC is not attached (including the portion of the arc shape) in the surface OPa on the inner side of the opening OP is thicker than the film thickness of the film BF formed in the portion where the deposited portion NC is attached in the surface OPa on the inner side of the opening OP. Therefore, the implementation of the flow SQ1 is repeated in the step ST3 until the number of times of implementation of the flow SQ1 reaches the number of times set in advance, whereby the arc shape is filled with the film BF, and the deposited portion NC attached to the opening OP is removed, so that the flatness of the surface OPa on the inner side of the opening OP can be sufficiently recovered by the method MT.

[0100] The method MT includes the flow SQ2 and the step ST4. The flow SQ2 includes the above-described step ST1, the flow SQ1, and the step ST3. The method MT implements the flow SQ2 once or more. In the step ST4 following the flow SQ2 (following the step ST3: Yes), it is determined whether or not to end the implementation of the flow SQ2. Specifically, in the step ST4, it is determined whether or not the number of times of implementation of the flow SQ2 reaches the number of times set in advance. In the case where it is determined in the step ST4 that the number of times of implementation of the flow SQ2 does not reach the number of times set in advance (step ST4: No), the implementation of the flow SQ2 is repeated again. On the other hand, in the case where it is determined in the step ST4 that the number of times of implementation of the flow SQ2 reaches the number of times set in advance (step ST4: Yes), the implementation of the flow SQ2 is ended. As described above, by repeatedly implementing the flow SQ2, the depth on the inner side of the opening OP can be adjusted to the desired depth while maintaining the flatness and the shape of the surface on the inner side of the opening OP.

[0101] By the etching performed in the step ST1, the deposited portion NC as a reaction product due to the first gas is attached to the opening OP, and there is a case where the portion where the deposited portion NC is not attached (the portion exposed by the etched layer EL) in the surface OPa on the inner side of the opening OP forms the arc shape (recess). According to the method MT of the embodiment described above, by the flow SQ1 and the step ST3 implemented after the implementation of the step ST1, the deposited portion NC attached to the opening OP can be removed, and by forming the film BF in the portion where the arc shape is formed, the arc shape can be moderated.

[0102] In addition, in the step ST2a in which the second gas is used, a chemical reaction can be used without generating plasma, and therefore the thickness of the film BF formed by the flow SQ1 including the step ST2a and the step ST3 increases as the temperature of the wafer W (particularly, the etching layer EL) to be etched increases. Therefore, according to the method MT, the thickness of the film BF formed in the flow SQ1 and the step ST3 becomes uniform in the plurality of regions ER of the wafer W.

[0103] In addition, the second gas including the amino silane-based gas containing an organic group having relatively high reactivity used in the step ST2a is introduced into the gas introduction port 52a in the processing container 12, and the first gas including the carbon atom and the fluorine atom used in the step ST1 and the third gas including the oxygen atom used in the step ST2c are introduced into the gas introduction port 36c in the processing container, and the gas supply pipe 38 connected to the gas introduction port 36c and the gas supply pipe 82 connected to the gas introduction port 52a are not crossed with each other, and therefore the reaction product generated in the gas supply pipe (the gas introduction port 36c and the gas introduction port 52a) by the second gas including the amino silane-based gas containing an organic group having relatively high reactivity and the first gas and the third gas can be reduced. In addition, by using the backflow prevention gas, the backflow of any one of the first gas, the second gas, and the third gas in the gas supply pipe (the gas introduction port 36c or the gas introduction port 52a) in which none of the first gas, the second gas, and the third gas flows can be prevented.

[0104] In addition, the etching of the etching layer EL which is a hydrophilic insulating layer containing silicon using the first gas including the fluorocarbon-based gas can be performed in the step ST1, and the formation of the reaction precursor of silicon using the second gas including the monoamino silane can be performed in the step ST2a.

[0105] As described above, according to the first embodiment, the bow shape of the side surface of the recess generated by etching can be moderated.

[0106] (Second Embodiment)

[0107] Hereinafter, the second embodiment will be described with reference to Figures 7-11 will be described. Figure 7is a flowchart showing a method MT of processing a wafer W of an embodiment. The method MT includes steps ST1a, ST5, which are implemented in this order. The method MT can include ST1b after ST1a. In the second embodiment, the surface of the wafer W includes a surface SFa of a first region La of the wafer W and a surface SFb of a second region Lb of the wafer W. In an embodiment, a first film M1 is formed on the surface SFa of the first region La of the wafer W. The film is formed on the surface SFb of the second region Lb by ALD.

[0108] The control section Cnt of the plasma processing apparatus 10 controls each section of the plasma processing apparatus 10, and implements the method MT.

[0109] Figure 8 (a) of FIG. 8, Figure 8 (b) of FIG. 8 schematically shows a state of the wafer W after implementation of each step of the method MT shown in FIG. 8. Figure 7 TM1 shown in (a) of FIG. 8 shows a state of the wafer at the time of starting the step ST5. Figure 8 TM2 shown in (b) of FIG. 8 shows a state of the wafer at the time of ending the step ST5 (in particular, shows the time of ending the removal of the first film M1). Figure 8 TM3 shown in (a) of FIG. 8 shows a state of the wafer at the time of starting the step ST1b. Figure 9 TM4 shown in (b) of FIG. 8 shows a state of the wafer at the time of ending the step ST1b. Figure 9 (b) to Figure 11 as well in FIG. 9).

[0110] Figure 9 (a) of FIG. 10, Figure 9 (b) of FIG. 10 schematically shows the removal of the first film M1 and the formation of the second film M2 based on the method MT shown in FIG. 10. Figure 7 (a) of FIG. 10 schematically shows the removal of the first film M1 and the formation of the second film M2 on the first region La. Figure 9 (b) of FIG. 10 schematically shows the formation of the second film M2 on the second region Lb. Figure 9 (a) of FIG. 11 shows a case of a change in film thickness of the first film M1 and a change in film thickness of the second film M2 based on the method MT shown in FIG. 11. Figure 10 (b) of FIG. 11 shows another case of a change in film thickness based on the method MT. Figure 7 The vertical axis of FIG. 11 shows the film thickness of the first film M1. Figure 11 The vertical axis of FIG. 12 shows the film thickness of the second film M2. Figure 10 The horizontal axis of each of FIGS. 11 and 12 shows time from the start of processing. Figure 11 Figure 10 Figure 11 The method MT shown in FIG. 13 is explained. The step ST1a is to selectively form the first film M1 on the wafer W.

[0111] The method MT shown in FIG. 14 is explained. The step ST1b is to remove the first film M1 from the second region Lb of the wafer W. Figure 7 TM1 shown in (a) of FIG. 14 shows a state of the wafer at the time of starting the step ST1b. Figure 8 ​​Step (a) of the above. Specifically, in step ST1a, the first membrane M1 is as follows: Figure 8 As shown in (a), SFa is formed on the surface of the first region La of wafer W, while SFb is not formed on the surface of the second region Lb of wafer W (as shown in (a)). Figure 10 (corresponding to the situation shown), or it can be formed as a film thinner than the first film M1 formed on the surface SFa (with) Figure 11 (As shown in the example). Furthermore, step ST1a includes a process for preparing wafer W, which includes a first region La formed of a first material and a second region Lb formed of a second material different from the first material. The first and second materials will be described later.

[0112] In step ST1a, the first film M1 is formed using the fourth gas. The first film M1 can be formed using plasma-enhanced chemical vapor deposition (PECVD), thermal CVD, or the like using the fourth gas. Other examples include forming the first film M1 by etching with active species of the fourth gas. If the first material of the first region La contains, for example, any of silicon, organic matter, or metal, and the second material of the second region Lb contains, for example, silicon and oxygen, the fourth gas can be a fluorocarbon gas. If the first material of the first region La contains, for example, any of silicon, organic matter, or metal, and the second material of the second region Lb contains, for example, silicon and nitrogen, the fourth gas can be a fluorinated hydrocarbon gas. As described above, the fourth gas is a gas with packing properties.

[0113] For example, when Lb in the second region is SiO2, plasma etching is performed using a gas such as C4F6, thereby forming a first film M1 on the first region La. On the other hand, for example, when Lb in the second region is SiN, plasma etching is performed using a gas such as CH3F, thereby forming a first film M1 on the first region La.

[0114] The following describes an example of forming the first film M1 by plasma etching. According to this example, the difference in film thickness between the first film M1 formed on the first region La and the first film M1 formed on the second region Lb can be further increased. Step ST1a includes steps 5 and 6. Steps 5 and 6 are performed in the plasma processing apparatus 10. Step ST1a forms the first film M1 on the first region La by etching the second region Lb using plasma of the fourth gas in steps 5 and 6.

[0115] First, plasma of the fourth gas is generated in the processing container 12 in which the wafer W is housed, and a film is deposited on the surface SFa of the first region La and the surface SFb of the second region Lb (fifth step). The fifth step includes a step of adjusting the pressure by supplying the fourth gas into the processing container 12. Next, the first high-frequency power source 62 is operated and high-frequency power is applied to generate plasma of the fourth gas. In the fifth step, no high-frequency power for introducing ions to the wafer W is applied or power that does not cause etching is applied. Thus, a film is formed on the surface SFa of the first region La and the surface SFb of the second region Lb.

[0116] Next, the second region Lb is removed in the sixth step. In the sixth step, an inert gas is supplied into the processing container 12. The first high-frequency power source 62 is operated and high-frequency power is applied to generate plasma of the inert gas. The second high-frequency power source 64 can be operated and high-frequency power can be applied in the sixth step. Thus, ions of the inert gas are introduced to the film deposited by the fifth step, and the deposited film and a part of the second region Lb react to remove a part of the second region Lb. In this etching, one atomic layer to ten atomic layers of the second region Lb are etched in each cycle including the fifth step and the sixth step (referred to as ALE). On the other hand, the deposited film and the first region La are difficult to form a reaction product with high volatility, and thus the first region La is difficult to be removed compared to the second region Lb. Therefore, the first film Ml is formed on the first region La. The fifth step and the sixth step are repeated until the etching amount of the second region Lb becomes a predetermined amount. After the etching, no film or almost no film remains on the second region Lb. This etching method can improve the selectivity of the deposition amount of the first film Ml. Here, ALE is shown as one example of forming the first film in the etching, but the second region Lb can be etched and the first film Ml can be formed on the first region La by another method.

[0117] In one embodiment, the first region La has a first material including any of silicon, an organic substance, and a metal. Specifically, the first material of the first region La can include, for example, any one of Si, SiGe, Ge, SiN, SiC, an organic film, a metal (W, Ti, or the like), SiON, SiOC, or a combination of two or more thereof. The second region Lb includes a second material different from the first material constituting the first region La, and can include silicon and oxygen. Specifically, the second region Lb has a second material including SiO2, SiON, SiOC, or the like. The fourth gas can be a fluorocarbon-based gas such as C4F6, C4F8, or the like. The fourth gas can also include an inert gas. The inert gas used in the sixth step includes a noble gas such as argon.

[0118] In addition, in another embodiment, the first region La can contain any of silicon, an organic substance, and a metal, and the second region Lb can contain silicon and nitrogen. Specifically, the first region La can include, for example, any of Si, SiO2, SiC, an organic film, a metal (W, Ti, or the like), SiON, SiOC, and the like, and the second region Lb can include any of SiN, SiON, and the like. In this embodiment, the fourth gas can be a fluorocarbon gas. The fourth gas can also include an inert gas. The inert gas used in the sixth step can include a noble gas such as argon.

[0119] Referring again to Figure 7 Step ST5 is a step of forming a second film M2 on the second region Lb by ALD while removing the first film Ml. As described above, step ST5 forms the second film M2 on the surface of the wafer W selectively by the ALD method Figure 8 (b) of FIG. 1. Step ST5 includes a plasma treatment that is repeatedly performed to remove the first film Ml on the first region La.

[0120] In step ST5 of forming the second film M2, the total of the implementation times of step ST2c can be adjusted in accordance with a target value of the film thickness of the second film M2 that is set in advance.

[0121] Step ST5 includes flow SQl and step ST3. Flow SQl includes step ST2a, step ST2b, step ST2c, and optionally step ST2d. Flow SQl optionally includes step ST2e after step ST2d. Step ST2e is a step of generating a plasma of an inert gas. Thus, step ST2e densifies the second film M2 formed by step ST2a, step ST2b, step ST2c, and step ST2d. In addition, the film thickness of the first film Ml can be adjusted by step ST2e. The respective implementation times of step ST2c and step ST2e can be adjusted.

[0122] The step STIa and the step ST5 can be continuously performed without breaking the vacuum using the same plasma processing apparatus 10. In other embodiments, the step STIa and the step ST5 can be performed using different plasma processing apparatuses from each other. In the case where the step STIa and the step ST5 are performed using different plasma processing apparatuses, in the step STIa, the first film Ml is selectively formed using one plasma processing apparatus. Also, in the step ST5, using a different plasma processing apparatus 10 from the one plasma processing apparatus, the second film M2 is selectively formed on the exposed surface of the wafer W on which the first film Ml is selectively provided, by the ALD method. During the formation of the second film M2 by repeating the flow SQl, the first film Ml on the first region La is removed. Specifically, the plasma of the modification gas in the step ST2c, or the plasma of the inert gas selectively performed in the step ST2e removes the first film Ml on the first region La. The amount of removal of the first film can be controlled by adjusting the time of the step ST2, the value of the first or second high frequency power in the step ST2c.

[0123] The second gas G1 (precursor gas) used in the step ST2a is a gas that adsorbs on the region of the wafer W on which the first film Ml is not formed to form an adsorption layer (indicated by the layer Ly1) (the first film Ml hinders the adsorption of the second gas). The second gas G1 can be an aminosilane-based gas, a silicon-containing gas, a titanium-containing gas, a hafnium-containing gas, a tantalum-containing gas, a zirconium-containing gas, a gas containing an organic substance. The third gas used in the step ST2c is a gas that modifies the adsorption layer, for example, an oxygen-containing gas, a nitrogen-containing gas, a hydrogen-containing gas. Figure 6

[0124] Specifically, the third gas can use O2 gas, CO2 gas, NO gas, SO2 gas, N2 gas, H2 gas, NH3 gas, and the like. In addition, the third gas can also use ozone gas (O3 gas), and in the step ST2c, plasma can not be generated.

[0125] Figure 8 (a) of the above (b) to Figure 8 (a) of the above (b) to Figure 11 indicates the processing performed in the step ST5. As Figure 8 (a) and Figure 10 indicates the processing performed in the step ST5. As

[0126] Figure 10 ​The line segment LP1 and the line segment LP2 indicate a change in the film thickness of the first film M1 formed on the surface SFa of the first region La. Figure 10 The line segment LP3 indicates a change in the film thickness of the second film M2 formed on the surface SFb of the second region Lb. Figure 10 The line segment LP4 indicates a change in the film thickness of the second film M2 formed on the surface SFa when the step ST5 of forming the second film M2 is continued after the first film M1 is removed from the surface SFa of the first region La.

[0127] On the surface SFb of the second region Lb, as Figure 8 (a) of FIG. 1A and Figure 10 indicated by the step 1a, the first film M1 is not formed, or as Figure 8 (a) of FIG. 1A and Figure 11 indicated by the step 1a, the first film M1 formed on the surface SFa can be thinner than the first film M1.

[0128] Figure 11 The line segment LP1a and the line segment LP2a indicate a change in the film thickness of the first film M1 formed on the surface SFb of the second region Lb.

[0129] As Figure 9 (a) of FIG. 1A, Figure 9 (b) of FIG. 1A, Figure 10 , Figure 11 indicated, the step ST5 is started at the time TM1, and the step ST5 is repeatedly performed to remove the first film M1 (the line segment LP2 of FIG. 1A, the line segment LP2 of FIG. 2A, and the line segment LP2a of FIG. 3A) in stages. On the other hand, the step ST5 is repeatedly performed to form the second film M2 on the surface SFb of the second region Lb on which the first film M1 is not formed or on the surface SFb of the second region Lb from which the first film M1 is removed (the line segment LP3 of FIG. 1A, the line segment LP3 of FIG. 2A, and the line segment LP3 of FIG. 3A) by one atomic layer at a time. Figure 10 the line segment LP2 of FIG. 1A, Figure 11 the line segment LP2 of FIG. 2A, and the line segment LP2a of FIG. 3A). On the other hand, the step ST5 is repeatedly performed to form the second film M2 on the surface SFb of the second region Lb on which the first film M1 is not formed or on the surface SFb of the second region Lb from which the first film M1 is removed (the line segment LP3 of FIG. 1A, the line segment LP3 of FIG. 2A, and the line segment LP3 of FIG. 3A) by one atomic layer at a time. Figure 10 Figure 11 The line segment LP3 of FIG. 1A,

[0130] In one embodiment, the step ST5 can be continued from the time TM1 to a time TM2 at which the first film M1 on the surface SFa of the first region La is completely removed. Figure 9 (a) of FIG. 1A and Figure 9 (b) of FIG. 1A illustrate a case in which the step ST5 is repeatedly performed three times. That is, Figure 9 (a) of FIG. 1A and Figure 9 (b) of FIG. 1A illustrate a case in which the first film M1 on the first region La is completely removed by repeatedly performing the step ST5 three times.

[0131] ​At the moment when step ST5 is initially implemented in time TM1, the surface SFb of region Lb in the second region is exposed, while the surface SFa of region La in the first region is covered by the first film M1 and is not exposed. By the initial implementation of step ST5 in time TM1, a portion of the first film M1 covering region La in the first region is removed. A second film M2 with one atomic layer is formed on the exposed region Lb in the second region.

[0132] Next, through the second implementation of step ST5, a portion of the first film M1 on the first region La is further removed, and a second atomic layer is further formed on the second film M2 on the second region Lb, making the second film M2 a two-atom-layer film. Then, through the third implementation of step ST5, the first film M1 on the first region La is completely removed, and a second atomic layer is further formed on the second film M2 on the second region Lb, making the second film M2 a three-atom-layer film. As described above, at the moment TM2 when step ST5 has been repeated three times, the first film M1 on the first region La is completely removed, the surface SFa of the first region La is exposed, and a three-atom-layer second film M2 is formed on the second region Lb.

[0133] like Figure 9 of (a), Figure 9 (b) Figure 10 , Figure 11 As shown, step ST5 can continue from time TM1 until time TM2 when the first film M1 on the surface SFa of the first region La is completely removed. However, it is not limited to this. In another embodiment, it can continue until a predetermined film thickness of the first film M1 or a predetermined film thickness of the second film M2 is reached. For example, even after time TM2 when the first film M1 on the surface SFa is completely removed, step ST5 can continue. In this case, as... Figure 9 of (a), Figure 9 After time T2 in (b), such as Figure 10 , Figure 11 As shown in line segment LP4, in each implementation of step ST5, a second film M2 is formed sequentially on the (exposed) surface SFa of the first region La by one atomic layer, and on the second region Lb, the second film M2 is also added layer by layer by one atomic layer.

[0134] Figure 9 of (a), Figure 9 Example (b) illustrates the case where step ST5 is repeated 3 times (cycle) after time TM2. Step ST5 is repeated 3 times after time TM2, thereby forming a second film M2 with 3 atomic layers on the first region La and a second film M2 with 6 atomic layers on the second region Lb.

[0135] In one mode, the first film Ml having different film thicknesses is formed in each region on the wafer W, and the second film M2 having different thicknesses is formed in correspondence with the regions by repeatedly performing the ALD cycle. That is, the second film M2 can also be formed in a plurality of film thicknesses according to the plurality of film thicknesses of the first film Ml.

[0136] Embodiments 1 to 3 below show a plurality of specific examples of processing conditions that can be used in the step STla, the step ST2a, and the step ST2c.

[0137] (Embodiment 1)

[0138] • Material of the first region La: SiN

[0139] • Material of the second region Lb: SiO2

[0140] <Step STla>

[0141] • Pressure in the processing space Sp: 20 [mTorr]

[0142] • Electric power of the first high-frequency power source 62: 500 [W]

[0143] • Electric power of the second high-frequency power source 64: 0 [W]

[0144] • First gas flow rate: C4F6 gas (15 [sccm]) / Ar gas (350 [sccm]) / O2 gas (20 [sccm])

[0145] • Temperature of the wafer W: 200 [°C]

[0146] • Implementation time: 10 [seconds]

[0147] The first film Ml formed in this embodiment 1 is a fluorocarbon film.

[0148] <Step ST2a>

[0149] • Pressure in the processing space Sp: 100 [mTorr]

[0150] • Electric power of the first high-frequency power source 62: 0 [W]

[0151] • Electric power of the second high-frequency power source 64: 0 [W]

[0152] • First gas flow rate: Aminosilane gas (50 [sccm])

[0153] • Temperature of the wafer W: 80 [°C]

[0154] • Implementation time: 15 [seconds]

[0155] <Step ST2c>

[0156] • Pressure in the processing space Sp: 200 [mTorr]

[0157] • Power of the 1st high-frequency power source 62: 500 [W] (60 [MHz])

[0158] • Power of the 2nd high-frequency power source 64: 300 [W] (10 [kHz])

[0159] • 1st gas flow rate: CO2 gas (300 [sccm])

[0160] • Implementation time: 5 [seconds]

[0161] (Example 2)

[0162] • Material of the 1st region La: SiN

[0163] • Material of the 2nd region Lb: SiO2

[0164] <Step ST1a>

[0165] • The implementation used the etching processing of the 5th step and the 6th step described above.

[0166] • Number of repetitions of the 5th step and the 6th step: 2 times

[0167] The 1st film M1 formed in this Example 2 is a fluorocarbon film.

[0168] <5th Step>

[0169] • Pressure in the processing space Sp: 30 [mTorr]

[0170] • Power of the 1st high-frequency power source 62: 100 [W]

[0171] • Power of the 2nd high-frequency power source 64: 0 [W]

[0172] • Voltage of the direct-current power source 70: -300 [V]

[0173] • 4th gas flow rate: C4F6 gas (16 [sccm]) / Ar gas (1000 [sccm]) / O2 gas (10 [sccm])

[0174] • Implementation time: 3 [seconds]

[0175] <7th Step>

[0176] • Pressure in the processing space Sp: 30 [mTorr]

[0177] • Power of the 1st high-frequency power source 62: 500 [W]

[0178] • Power of the 2nd high frequency power source 64: 0 [W]

[0179] • Voltage of the DC power source 70: -300 [V]

[0180] • 4th gas flow rate: C4F6 gas (0 [sccm]) / Ar gas (1000 [sccm]) / O2 gas (0 [sccm])

[0181] • Implementation time: 5 [sec]

[0182] <Step ST2a>

[0183] • Pressure in the processing space Sp: 100 [mTorr]

[0184] • Power of the 1st high frequency power source 62: 0 [W]

[0185] • Power of the 2nd high frequency power source 64: 0 [W]

[0186] • 1st gas flow rate: Aminosilane gas (50 [sccm])

[0187] • Temperature of the wafer W: 80 [°C]

[0188] • Implementation time: 15 [sec]

[0189] <Step ST2c>

[0190] • Pressure in the processing space Sp: 200 [mTorr]

[0191] • Power of the 1st high frequency power source 62 (frequency: 60 [MHz]): 500 [W]

[0192] • Power of the 2nd high frequency power source 64 (frequency: 10 [kHz]): 300 [W]

[0193] • 1st gas flow rate: CO2 gas (300 [sccm])

[0194] • Implementation time: 5 [sec]

[0195] (Example 3)

[0196] • Material of the 1st region La: SiN

[0197] • Material of the 2nd region Lb: SiO2

[0198] <Step ST1a>

[0199] • The etching treatment of the 5th step and the 6th step described above was implemented.

[0200] • Number of repetitions of the 5th step to the 8th step: 2 times

[0201] The first film M1 formed in this embodiment 3 is a fluorocarbon film.

[0202] <Step 5>

[0203] • Pressure in the processing space Sp: 30 [mTorr]

[0204] • Electric power of the first high-frequency power source 62: 100 [W]

[0205] • Electric power of the second high-frequency power source 64: 0 [W]

[0206] • Voltage of the direct-current power source 70: -300 [V] (This condition can be omitted)

[0207] • Fourth gas: C4F6 gas (16 [sccm]) / Ar gas (1000 [sccm]) / O2 gas (10 [sccm])

[0208] • Implementation time: 3 [seconds]

[0209] <Step 7>

[0210] • Pressure in the processing space Sp: 30 [mTorr]

[0211] • Electric power of the first high-frequency power source 62: 500 [W]

[0212] • Electric power of the second high-frequency power source 64: 0 [W]

[0213] • Voltage of the direct-current power source 70: -300 [V]

[0214] • Fourth gas: C4F6 gas (0 [sccm]) / Ar gas (1000 [sccm]) / O2 gas (0 [sccm])

[0215] • Implementation time: 5 [seconds]

[0216] <Step ST2a>

[0217] • Pressure in the processing space Sp: 100 [mTorr]

[0218] • Electric power of the first high-frequency power source 62: 0 [W]

[0219] • Electric power of the second high-frequency power source 64: 0 [W]

[0220] • First gas: Aminosilane gas (50 [sccm])

[0221] • Temperature of the wafer W: 80 [°C]

[0222] • Implementation time: 15 [seconds]

[0223] <Step ST2c>

[0224] • Pressure in the processing space Sp: 200 [Torr]

[0225] • Power of the 1st high-frequency power source 62 (frequency 60 [MHz]): 500 [W]

[0226] • Power of the 2nd high-frequency power source 64 (frequency 10 [kHz]): 300 [W]

[0227] • 1st gas: CO2 gas (300 [sccm])

[0228] • Implementation time: 2 [seconds]

[0229] The implementation time of Step ST2c in the above-described Example 2 and Example 3 is different. The implementation time of Step ST2c in Example 3 (2 [seconds]) is 2 / 5 times the implementation time of Step ST2c in Example 2 (5 [seconds]). In this case, the removal rate of the 1st film Ml of the surface SFa of the 1st region La in Example 3 is about 2 / 5 times the removal rate in Example 2.

[0230] Further, after the implementation of Step STla and before the implementation of Step ST5, the surface of the wafer W can be cleaned (Step STlb). Step STlb is implemented in the case where the 1st film Ml is formed on the 2nd region Lb, and the 1st film Ml can be removed from the 2nd region Lb. The 2nd film M2 is not formed on the 2nd region Lb from the start of the ALD Step ST5 until the 1st film Ml on the 2nd region Lb is completely removed, and the 2nd film M2 is formed from the time when the 1st film Ml is removed from the 2nd region Lb. Therefore, by implementing the cleaning of Step STlb, the formation of the 2nd film M2 can start from the start of Step ST5. Therefore, the number of times of implementation of Step ST5 required for the 2nd film M2 to reach the desired film thickness can be reduced.

[0231] Hereinafter, the principles of the present application are illustrated and described in suitable embodiments, but the present application can be changed in configuration and details without departing from the principles thereof, and it should be known to those skilled in the art. The present application is not limited to the specific configurations disclosed in the present embodiments. Therefore, all modifications and changes requested in the scope of the patent application and the scope according to the spirit thereof are claimed.

[0232] Other aspects of the embodiments include the following Notes 1 to 4.

[0233] (Note 1)

[0234] A method of processing a processed object, including a step of selectively providing a first film on a surface of the processed object, and a step of forming a second film on the surface of the processed object by ALD (atomic layer deposition) while removing the first film.

[0235] (Addendum 2)

[0236] A method of processing a processed object, including a step of selectively forming a first film on a first region of the processed object, a step of forming a first ALD film on a second region of the processed object where the first film is not formed by ALD (atomic layer deposition), and a step of forming a second ALD film on the first region after the first film on the first region is removed by repeatedly performing ALD.

[0237] (Addendum 3)

[0238] According to the method of Addendum 2, the first ALD film has a film thickness thicker than a film thickness of the second ALD film.

[0239] (Addendum 4)

[0240] A method of processing a processed object, including a step of preparing the processed object including a first region formed of a first material and a second region formed of a second material different from the first material, a step of etching the first region with a first plasma to form a first film on the second region, and a step of forming a second film on the first region by atomic layer deposition while removing the first film.

Claims

1. An apparatus for processing a processed object having a first region and a second region different from the first region, the apparatus comprising: at least one vessel; a plasma generating section for generating plasma in the at least one vessel; and a controller configured to execute a process a for forming a first film on the first region and a process b for forming a second film on the second region, the process b including: a process i for forming an adsorption layer on the processed object by exposing the processed object to a precursor; a process ii for modifying the adsorption layer by generating plasma from a modifying gas to form the second film on the second region while removing the first film on the first region; and a process iii for repeating the process i and the process ii, the second film being formed on the first region after the first film on the first region is removed by repeating the process i and the process ii.

2. The apparatus according to claim 1, wherein: the at least one vessel includes a first vessel, and the process a and the process b are performed in the first vessel.

3. The apparatus according to claim 1 or 2, wherein: the at least one vessel includes a first vessel and a second vessel, the process a is performed in the first vessel, and the process b is performed in the second vessel.

4. The apparatus according to claim 1 or 2, wherein: the controller further performs a process c for repeating the process a and the process b.

5. The apparatus according to claim 1 or 2, wherein: the process b includes a process for adjusting a temperature of each region of the processed object separately.

6. The apparatus according to claim 1 or 2, wherein: the process a is performed by PECVD.

7. The apparatus according to claim 1 or 2, wherein: the process a is performed by thermal CVD.

8. An apparatus for processing a processed object having a first region and a second region, the apparatus comprising: the first region containing a first substance, the second region containing a second substance different from the first substance; at least one vessel; a plasma generating section for generating plasma in the at least one vessel; and a controller configured to execute: a process a for etching the first region from a first gas to form a first film on the second region; and a process b for removing the first film formed on the second region while forming a second film on the first region.

9. The apparatus according to claim 8, wherein: the process b includes: a process i for forming an adsorption layer on the processed object by exposing the processed object to a precursor; and a process ii for modifying the adsorption layer by generating plasma from a modifying gas.

10. The apparatus according to claim 8 or 9, wherein: the first region is an etched layer, and the second region is a mask.

11. The apparatus according to claim 8 or 9, wherein: ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ The apparatus comprises: ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ The first gas contains carbon and fluorine, and the first film contains carbon and fluorine.

12. An apparatus for processing a processed object, characterized by comprising: Comprising: at least one container; and a controller, the controller controls to execute process a and process b, the process a selectively forms a first film on a first region of the processed body, the process b forms a second film on a second region of the processed body different from the first region and removes the first film, wherein the process b includes: process i, forming an adsorption layer on the processed body by exposing the processed body to a precursor; process ii, forming the second film by modifying the adsorption layer on the second region by generating plasma from a modifying gas while removing the first film on the first region; and process iii, repeating the process i and the process ii, by repeating the process i and the process ii, the second film is formed on the first region after removing the first film on the first region.

13. The apparatus according to any one of claims 1, 2, 8, 9, 12, wherein: the controller further executes a process of forming the second film on the first region.

14. A processing device, characterized by Comprising: a first container that forms a first film on a first region of a processed body by plasma CVD; and a second container that removes the first film and forms a second film on a second region of the processed body different from the first region, the process of forming the second film includes: process i, forming an adsorption layer on the processed body by exposing the processed body to a precursor; process ii, forming the second film by modifying the adsorption layer on the second region by generating plasma from a modifying gas while removing the first film on the first region; and process iii, repeating the process i and the process ii, by repeating the process i and the process ii, the second film is formed on the first region after removing the first film on the first region.

15. An apparatus for processing a processed object, characterized by comprising: Comprising: at least one container; a plasma generation section that generates plasma in the at least one container; and a controller, the controller is configured to execute processes a to c, wherein process a provides a processed body having a mask and an etched layer, the mask having an opening, a recess connected to the opening is formed in the etched layer, and a first film is formed on a side wall of the mask, process b forms a second film on the recess, process c etches a bottom of the recess, the process b includes: process i, forming an adsorption layer on the recess by exposing the processed body to a precursor; process ii, forming the second film by modifying the adsorption layer on the side wall of the mask by generating plasma from a modifying gas while removing the first film; and process iii, repeating the process i and the process ii.

Images