Film, article, and plasma processing device

Abstract

Provided is a technique for suppressing the generation of dust caused by plasma processing. A film comprising a carbon-containing metal oxyfluoride is provided. The carbon-containing metal oxyfluoride in the film is represented by MaObFcCd, where: M represents a metal atom; a, b, c, and d represent atomic ratios; and the relationships 0 < a < 1, 0 < b < 1, 0 < c < 1, 0 < d < 1, and a + b + c + d = 1 are satisfied.

Description

Film, article and plasma treatment device

[0001] Exemplary embodiments of the present disclosure relate to films, articles, and plasma processing apparatuses.

[0002] Patent Document 1 discloses a technique for coating the inside of a chamber for processing plasma.

[0003] Special table 2019-515139 publication

[0004] The present disclosure provides a technique for suppressing dust generation caused by plasma processing.

[0005] In one exemplary embodiment of the present disclosure, there is provided a film comprising a carbon-containing metal oxyfluoride, wherein the carbon-containing metal oxyfluoride is ａ O ｂ F ｃ C ｄ wherein M represents a metal atom, a, b, c, and d represent atomic ratios, and satisfy 0<a<1, 0<b<1, 0<c<1, 0<d<1, and a+b+c+d=1.

[0006] According to one exemplary embodiment of the present disclosure, a technique for suppressing dust generation due to plasma processing can be provided.

[0007] It is a diagram for explaining an example of the configuration of a plasma processing system. It is a diagram for explaining an example of the configuration of a capacitively coupled plasma processing apparatus. It is a diagram showing an example of the cross-sectional structure of a component CP. It is a diagram showing the measurement results of the number of dust particles generated after plasma processing. It is a diagram showing the composition of a carbon-containing metal oxyfluoride before and after plasma processing.

[0008] Hereinafter, each embodiment of the present disclosure will be described.

[0009] In one exemplary embodiment, a film comprising a carbon-containing metal oxyfluoride, the carbon-containing metal oxyfluoride being ａ O ｂ F ｃ C ｄwherein M represents a metal atom, and a, b, c, and d represent atomic ratios, and satisfy 0<a<1, 0<b<1, 0<c<1, 0<d<1, and a+b+c+d=1.

[0010] In one exemplary embodiment, the a is 0.10 or more and 0.40 or less, the b is 0.10 or more and 0.45 or less, the c is 0.05 or more and 0.60 or less, and the d is 0.05 or more and 0.55 or less.

[0011] In one exemplary embodiment, the a is 0.15 or more and 0.36 or less, the b is 0.10 or more and 0.35 or less, the c is 0.15 or more and 0.50 or less, and the d is 0.05 or more and 0.30 or less.

[0012] In one exemplary embodiment, the membrane has a porosity of less than 5%.

[0013] In one exemplary embodiment, M is at least one selected from the group consisting of Y, Al, Er, Yb, La, and Gd.

[0014] In one exemplary embodiment, the film is obtained by at least one method selected from the group consisting of thermal spraying, sputtering PVD, chemical vapor deposition CVD, ion plating, ion-assisted deposition and aerosol deposition.

[0015] In one exemplary embodiment, the thickness of the film is 1 μm or more and 300 μm or less.

[0016] In one exemplary embodiment, an article constituting a part of a plasma processing apparatus includes a substrate and a film disposed on the substrate and including a carbon-containing metal oxyfluoride, the carbon-containing metal oxyfluoride being selected from the group consisting of M ａ O ｂ F ｃ C ｄ wherein M represents a metal atom, a, b, c, and d represent atomic ratios, and satisfy 0<a<1, 0<b<1, 0<c<1, 0<d<1, and a+b+c+d=1.

[0017] In one exemplary embodiment, the substrate is a solid aluminum material, an aluminum material surface-treated with anodized aluminum, Al ２ O ３ Alumina sintered body, YAG sintered body, Y ２ O ３ The material contains at least one selected from the group consisting of sintered bodies.

[0018] In one exemplary embodiment, the substrate has an average surface roughness Ra of less than 0.5 μm.

[0019] In one exemplary embodiment, the film of the article constitutes a plasma-exposed surface in a chamber of the plasma processing apparatus.

[0020] In one exemplary embodiment, a plasma processing apparatus is provided that includes the above-described article.

[0021] In one exemplary embodiment, there is provided a plasma processing apparatus comprising: a chamber; and a plasma generating unit configured to generate plasma in the chamber, wherein at least a portion of a portion in the chamber that is exposed to the plasma is formed of the film according to any one of claims 1 to 7.

[0022] Hereinafter, each embodiment of the present disclosure will be described in detail with reference to the drawings. In each drawing, the same or similar elements are designated by the same reference numerals, and redundant explanations will be omitted. Unless otherwise specified, the positional relationships, such as up, down, left, and right, will be described based on the positional relationships shown in the drawings. The dimensional ratios in the drawings do not represent actual ratios, and the actual ratios are not limited to the ratios shown in the drawings.

[0023] <Configuration Example of Plasma Processing System> FIG. 1 is a diagram illustrating a configuration example of a plasma processing system. In one embodiment, the plasma processing system includes a plasma processing apparatus 1 and a control unit 2. The plasma processing system is an example of a substrate processing system, and the plasma processing apparatus 1 is an example of a substrate processing apparatus. The plasma processing apparatus 1 includes a plasma processing chamber 10, a substrate support 11, and a plasma generation unit 12. The plasma processing chamber 10 has a plasma processing space. The plasma processing chamber 10 also has at least one gas supply port for supplying at least one processing gas to the plasma processing space and at least one gas exhaust port for exhausting gas from the plasma processing space. The gas supply port is connected to a gas supply unit 20 (described later), and the gas exhaust port is connected to an exhaust system 40 (described later). The substrate support 11 is disposed in the plasma processing space and has a substrate support surface for supporting a substrate.

[0024] The plasma generating unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma generated in the plasma processing space may be capacitively coupled plasma (CCP), inductively coupled plasma (ICP), electron-cyclotron-resonance plasma (ECR plasma), helicon wave plasma (HWP), surface wave plasma (SWP), or the like. Various types of plasma generators may be used, including alternating current (AC) plasma generators and direct current (DC) plasma generators. In one embodiment, the AC signal (AC power) used in the AC plasma generator has a frequency in the range of 100 kHz to 10 GHz. Thus, AC signals include radio frequency (RF) signals and microwave signals. In one embodiment, the RF signal has a frequency in the range of 100 kHz to 150 MHz.

[0025] The control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform various processes described in this disclosure. The control unit 2 may be configured to control each element of the plasma processing apparatus 1 to perform various processes described herein. In one embodiment, part or all of the control unit 2 may be included in the plasma processing apparatus 1. The control unit 2 may include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. The control unit 2 may be implemented by, for example, a computer 2a. The processing unit 2a1 may be configured to read a program from the storage unit 2a2 and execute the read program to perform various control operations. This program may be stored in the storage unit 2a2 in advance or may be acquired via a medium when needed. The acquired program is stored in the storage unit 2a2 and read from the storage unit 2a2 by the processing unit 2a1 for execution. The medium may be various storage media readable by the computer 2a or a communication line connected to the communication interface 2a3. The processing unit 2a1 may be a CPU (Central Processing Unit). The storage unit 2a2 may include a random access memory (RAM), a read-only memory (ROM), a hard disk drive (HDD), a solid state drive (SSD), or a combination thereof. The communication interface 2a3 may communicate with the plasma processing apparatus 1 via a communication line such as a local area network (LAN).

[0026] The following describes a configuration example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1. Fig. 2 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0027] The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply 20, a power supply 30, and an exhaust system 40. The plasma processing apparatus 1 also includes a substrate support 11 and a gas inlet. The gas inlet is configured to introduce at least one process gas into the plasma processing chamber 10. The gas inlet includes a showerhead 13. The substrate support 11 is disposed within the plasma processing chamber 10. The showerhead 13 is disposed above the substrate support 11. In one embodiment, the showerhead 13 forms at least a portion of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the showerhead 13, a sidewall 10a of the plasma processing chamber 10, and the substrate support 11. The plasma processing chamber 10 is grounded. The showerhead 13 and the substrate support 11 are electrically insulated from the housing of the plasma processing chamber 10.

[0028] The substrate support 11 includes a main body 111 and a ring assembly 112. The main body 111 has a central region 111a for supporting a substrate W and an annular region 111b for supporting the ring assembly 112. A wafer is an example of a substrate W. The annular region 111b of the main body 111 surrounds the central region 111a of the main body 111 in a plan view. The substrate W is disposed on the central region 111a of the main body 111, and the ring assembly 112 is disposed on the annular region 111b of the main body 111 so as to surround the substrate W on the central region 111a of the main body 111. Therefore, the central region 111a is also called a substrate support surface for supporting the substrate W, and the annular region 111b is also called a ring support surface for supporting the ring assembly 112.

[0029] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive member. The conductive member of the base 1110 can function as a lower electrode. The electrostatic chuck 1111 is disposed on the base 1110. The electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic electrode 1111b disposed within the ceramic member 1111a. The ceramic member 1111a has a central region 111a. In one embodiment, the ceramic member 1111a also has an annular region 111b. Note that the annular region 111b may also be provided by another member surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member. In this case, the ring assembly 112 may be disposed on the annular electrostatic chuck or the annular insulating member, or may be disposed on both the electrostatic chuck 1111 and the annular insulating member. Furthermore, at least one RF / DC electrode coupled to an RF power supply 31 and / or a DC power supply 32, which will be described later, may be disposed within the ceramic member 1111a. In this case, the at least one RF / DC electrode functions as a lower electrode. When a bias RF signal and / or a DC signal, which will be described later, is supplied to the at least one RF / DC electrode, the RF / DC electrode is also called a bias electrode. Note that the conductive member of the base 1110 and the at least one RF / DC electrode may function as multiple lower electrodes. Furthermore, the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support 11 includes at least one lower electrode.

[0030] The ring assembly 112 includes one or more annular members. In one embodiment, the one or more annular members include one or more edge rings and at least one cover ring. The edge rings are formed of a conductive or insulating material, and the cover rings are formed of an insulating material.

[0031] The substrate support 11 may also include a temperature adjustment module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature. The temperature adjustment module may include a heater, a heat transfer medium, a flow passage 1110a, or a combination thereof. A heat transfer fluid such as brine or a gas flows through the flow passage 1110a. In one embodiment, the flow passage 1110a is formed in the base 1110, and one or more heaters are disposed in the ceramic member 1111a of the electrostatic chuck 1111. The substrate support 11 may also include a heat transfer gas supply configured to supply a heat transfer gas to a gap between the backside of the substrate W and the central region 111a.

[0032] The showerhead 13 is configured to introduce at least one process gas from the gas supply unit 20 into the plasma processing space 10s. The showerhead 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and multiple gas inlets 13c. The process gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s from the multiple gas inlets 13c. The showerhead 13 also includes at least one upper electrode. In addition to the showerhead 13, the gas inlet may also include one or more side gas injectors (SGIs) attached to one or more openings formed in the sidewall 10a.

[0033] The gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22. In one embodiment, the gas supply unit 20 is configured to supply at least one process gas from a corresponding gas source 21 to the showerhead 13 via a corresponding flow controller 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Additionally, the gas supply unit 20 may include at least one flow modulation device that modulates or pulses the flow rate of the at least one process gas.

[0034] The power supply 30 includes an RF power supply 31 coupled to the plasma processing chamber 10 via at least one impedance matching circuit. The RF power supply 31 is configured to supply at least one RF signal (RF power) to at least one lower electrode and / or at least one upper electrode. This generates a plasma from at least one processing gas supplied to the plasma processing space 10s. Therefore, the RF power supply 31 can function as at least a part of the plasma generation unit 12. Furthermore, by supplying a bias RF signal to the at least one lower electrode, a bias potential is generated on the substrate W, thereby attracting ion components in the formed plasma to the substrate W.

[0035] In one embodiment, the RF power supply 31 includes a first RF generating unit 31a and a second RF generating unit 31b. The first RF generating unit 31a is coupled to at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit and is configured to generate a source RF signal (source RF power) for plasma generation. In one embodiment, the source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generating unit 31a may be configured to generate multiple source RF signals having different frequencies. The generated one or more source RF signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0036] The second RF generator 31b is coupled to at least one lower electrode via at least one impedance matching circuit and is configured to generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100 kHz to 60 MHz. In one embodiment, the second RF generator 31b may be configured to generate multiple bias RF signals having different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. In various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0037] The power supply 30 may also include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generator 32a and a second DC generator 32b. In one embodiment, the first DC generator 32a is connected to the at least one lower electrode and configured to generate a first DC signal. The generated first DC signal is applied to the at least one lower electrode. In one embodiment, the second DC generator 32b is connected to the at least one upper electrode and configured to generate a second DC signal. The generated second DC signal is applied to the at least one upper electrode.

[0038] In various embodiments, the first and second DC signals may be pulsed. In this case, a sequence of voltage pulses is applied to at least one lower electrode and / or at least one upper electrode. The voltage pulses may have a rectangular, trapezoidal, triangular, or combination thereof pulse waveform. In one embodiment, a waveform generator for generating the sequence of voltage pulses from the DC signal is connected between the first DC generator 32a, at least one lower electrode, and the pore. Thus, the first DC generator 32a and the waveform generator constitute a voltage pulse generator. When the second DC generator 32b and the waveform generator constitute a voltage pulse generator, the voltage pulse generator is connected to at least one upper electrode. The voltage pulses may have positive or negative polarity. Furthermore, the sequence of voltage pulses may include one or more positive voltage pulses and one or more negative voltage pulses within one period. The first and second DC generating units 32a and 32b may be provided in addition to the RF power supply 31, or the first DC generating unit 32a may be provided instead of the second RF generating unit 31b.

[0039] The exhaust system 40 may be connected to, for example, a gas exhaust port 10e provided at the bottom of the plasma processing chamber 10. The exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure in the plasma processing space 10s is regulated by the pressure regulating valve. The vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.

[0040] In one embodiment, at least some of the components of the plasma processing chamber 10 may include a film (hereinafter also referred to as "film C") containing the following carbon-containing metal oxyfluoride: ａ O ｂ F ｃ C ｄ where M represents a metal atom, and a, b, c, and d represent atomic ratios, and satisfy the relationships 0<a<1, 0<b<1, 0<c<1, 0<d<1, and a+b+c+d=1.

[0041] In one embodiment, the film C may be disposed on a substrate, such as a component in the plasma processing chamber 10. That is, an article (hereinafter simply referred to as "article") including a substrate and the film C may constitute a part of a plasma processing apparatus. In other words, in one embodiment, the plasma processing apparatus may include such an article. In one example, the film C in such an article may constitute a plasma-exposed surface (a surface exposed to the plasma processing space 10s) in the plasma processing chamber 10. That is, in one embodiment, the plasma processing apparatus may include a chamber and a plasma generating unit configured to generate plasma in the chamber, and at least a portion of a portion in the chamber exposed to the plasma may be constituted by the film C. Below, a specific example of applying the film C or the article to a plasma processing apparatus will be described with reference to FIG. 3 .

[0042] 3 is a diagram showing an example of a cross-sectional structure of a component CP of the plasma processing apparatus 1. In one example, the component CP may be one or more of the shower head 13, the edge ring of the ring assembly 112, the sidewall 10a, the shield member of the sidewall 10a, and the baffle plate, or a part of such a component.

[0043] 3, the component CP may have a first layer CP1 and a second layer CP2 on the first layer CP1. The second layer CP2 is a portion exposed to plasma generated in the plasma processing space 10s. That is, the second layer CP2 has a plasma-exposed surface. The second layer CP2 is ａ O ｂ F ｃ C ｄ (wherein M represents a metal atom, and a, b, c, and d represent atomic ratios, and satisfy 0<a<1, 0<b<1, 0<c<1, 0<d<1, and a+b+c+d=1).

[0044] The second layer CP2 may be configured as a coating on the first layer CP1. For example, the second layer CP2 may be obtained by at least one method selected from the group consisting of thermal spraying, sputtering physical vapor deposition (sputtering PVD), chemical vapor deposition (CVD), ion plating, ion-assisted deposition, and aerosol deposition. As an example, the second layer CP2 may be formed by a method having the composition M ａ O ｂ F ｃ C ｄ The metal source, oxygen source, fluorine source, and carbon source may be used so as to obtain the above-mentioned method.

[0045] The first layer CP1 is a base material of the component CP and may be appropriately selected depending on the type of the component CP. For example, the first layer CP1 may be made of a solid aluminum material, an aluminum material surface-treated with anodized aluminum, or an Al ２ O ３ Alumina sintered body, YAG sintered body, Y ２ O ３ The first layer CP1 may include at least one material selected from the group consisting of sintered bodies. Alternatively, the first layer CP1 may be a silicon-containing material such as silicon or silicon carbide. The first layer CP1 may be configured by laminating multiple materials. In one embodiment, the average surface roughness Ra of the substrate may be less than 0.5 μm.

[0046] <Example of Plasma Processing Method> The plasma processing performed using the plasma processing apparatus 1 (hereinafter also referred to as "this processing method") includes an etching process that uses plasma to etch a film on the substrate W. In one embodiment, the plasma processing is performed by the control unit 2.

[0047] First, the substrate W is carried into the chamber 10 by the transport arm, placed on the substrate support 11 by the lifter, and held by suction on the substrate support 11 as shown in FIG.

[0048] Next, a processing gas is supplied to the shower head 13 by the gas supply unit 20, and then supplied from the shower head 13 to the plasma processing space 10s. The processing gas supplied at this time includes a gas that generates activated species necessary for etching the substrate W. In one embodiment, the processing gas includes a fluorocarbon gas and / or a hydrofluorocarbon gas. In one embodiment, the processing gas may include an oxygen-containing gas. In one embodiment, the processing gas may include an inert gas such as a noble gas or nitrogen gas.

[0049] In one embodiment, a source RF signal for plasma generation is supplied to the lower electrode and / or the upper electrode. A bias signal for ion attraction may be supplied to the lower electrode. At this time, the atmosphere in the plasma processing space 10s may be exhausted through the gas exhaust port 10e, and the pressure in the plasma processing space 10s may be reduced to a predetermined pressure. As a result, plasma is generated in the plasma processing space 10s, and the substrate W is etched.

[0050] As described above, when the film C is disposed in the component CP of the plasma processing chamber 10 in the plasma processing apparatus 1, dust generation tends to be suppressed even after plasma processing by the present processing method. The reason for this is not entirely clear, but the inventors speculate that the carbon contained in the film C influences this tendency. In one embodiment, from the viewpoint of suppressing dust generation, the composition or physical properties of the film C can be adjusted as follows.

[0051] In one embodiment, the a may be 0.10 or more and 0.40 or less, the b may be 0.10 or more and 0.45 or less, the c may be 0.05 or more and 0.60 or less, and the d may be 0.05 or more and 0.55 or less. Also, in one embodiment, the a may be 0.15 or more and 0.36 or less, the b may be 0.10 or more and 0.35 or less, the c may be 0.15 or more and 0.50 or less, and the d may be 0.05 or more and 0.30 or less. The values ​​of a to d can be measured based on the method described in the Examples below. The values ​​of a to d can be adjusted to the above-mentioned ranges, for example, by appropriately changing the amounts of the metal source, oxygen source, fluorine source, and carbon source used during the production of the film C.

[0052] In one embodiment, the metal atom may be at least one selected from the group consisting of Y, Al, Er, Yb, La, and Gd. In one embodiment, the metal atom may be at least one selected from the group consisting of Y, Al, Er, and Yb, or may be Y.

[0053] In one embodiment, the porosity of the film C may be less than 5%. The porosity can be measured based on the method described in the Examples below. The porosity can be adjusted to less than 5% by, for example, appropriately adjusting the particle size of the raw material powder, the film formation rate, the film formation temperature, etc. The porosity can be calculated as the area ratio of the pores to the other parts by observing the cross section of the film with a scanning electron microscope.

[0054] In one embodiment, the thickness of the film C may be 1 μm or more and 300 μm or less.

[0055] <Example> Next, a description will be given of an example in which process stability was evaluated using the plasma processing apparatus 1. The present disclosure is not limited to the following example.

[0056] Example A: An apparatus having a configuration similar to that of the plasma processing apparatus 1 shown in FIG. 2 was prepared, which had a shower head 13 including the component CP shown in FIG. 3, with the component CP comprising an Al base material as a first layer CP1 and a second layer CP2 formed on the base material. Here, the second layer CP2 was formed as follows. That is, in order to adjust the ratio of each element after film formation, raw material powders containing yttrium, oxygen, fluorine, and carbon were prepared, and the mixing ratios of these were appropriately adjusted. Using these raw materials, a second layer CP2 having a thickness of 10 μm and a porosity of more than 0% and not more than 2% was formed on the base material. To confirm the composition of the obtained second layer CP2, it was subjected to energy dispersive X-ray analysis (EDX). As a result of this analysis, the second layer CP2 contained Y. ０．３５５ O ０．１１８ F ０．４７６ C ０．０５１ It was found that the film was composed of a carbon-containing metal oxyfluoride represented by the following formula: In the following examples and reference examples, the composition of the second layer CP2 was confirmed by the same EDX.

[0057] (Examples B to D) Plasma processing apparatuses of Examples B to D were prepared in the same manner as Example A, except that the amounts of the raw material powders were changed so that the second layer CP2 had the composition shown in Table 1. The second layer CP2 of Examples B to D was prepared in the same manner as Example A, except that the amounts of the raw material powders were changed so that the second layer CP2 had the composition shown in Table 1. ０．３３６ O ０．１８８ F ０．３８６ C ０．０９０ , Y ０．２００ O ０．２８８ F ０．２９２ C ０．２２０ and Y ０．２９２ O ０．２６７ F ０．１４９ C ０．２９２ It was found that the film was composed of a carbon-containing metal oxyfluoride represented by the formula:

[0058] Reference Example 1: Y in which the second layer CP2 was formed by a conventionally known method ２ O ３ A plasma processing apparatus of Reference Example 1 was prepared in the same manner as in Example A, except for the above change.

[0059] Reference Example 2: The second layer CP2 was formed by a conventional method using YF ３A plasma processing apparatus of Reference Example 1 was prepared in the same manner as in Example A, except for the above change.

[0060] (Number of generated dust particles) In order to evaluate the influence of the second layer CP2 of each example on process stability, plasma processing was performed as follows. That is, in the plasma processing apparatus of Examples A to D, Reference Example 1, or Reference Example 2, plasma processing was performed using Ar gas, with the second layer CP2 on the upper top plate in the chamber being the plasma-exposed surface. Dust particles generated on the plasma-exposed surface of the second layer CP2 by this processing were collected on the substrate W, and the number of particles was counted. The results are shown in FIG.

[0061] (Composition after plasma treatment) The compositional change when the second layer CP2 of each example was subjected to plasma treatment was confirmed as follows. Note that the measurement samples for the second layer CP2 had the same area in all examples. First, in the plasma treatment apparatuses of Examples A to D, plasma treatment was performed on the second layer CP2 on the upper top plate in the chamber using a CF-based gas, oxygen, and Ar gas. To confirm the composition of the second layer CP2 of each example after plasma treatment, EDX similar to that described above was performed, and the results are shown in FIG. 5.

[0062] 5, when the plasma processing apparatuses of Examples A to D were used, the number of dust particles was smaller than that of Reference Examples 1 and 2. In Examples A to D, carbon was contained in Film C, and it is believed that this carbon suppressed dust generation. On the other hand, in Reference Examples 1 and 2, the number of dust particles was higher because carbon was not contained in the film.

[0063] In the plasma processing apparatuses of Reference Examples 1 and 2, the second layer CP2 on the upper ceiling plate in the chamber was subjected to plasma processing using a CF -based gas, oxygen, and Ar gas, and the results were analyzed by EDX in the same manner as above. As a result, the presence of elements not contained in the film before processing was confirmed, and in Reference Example 1, the atomic ratio of fluorine increased by 26.1%, and in Reference Example 2, the atomic ratio of oxygen increased by 35.1%. In contrast, as shown in Figure 5, when the plasma processing apparatuses of Examples A to D were used, after plasma processing, fluctuations of less than ±0.12 were observed in all atomic ratios, and the compositional fluctuations were evaluated to be small. When films with small compositional fluctuations such as those of Examples A to D are applied to a plasma processing apparatus, process fluctuations are less likely to occur, and as a result, process stability can be improved.

[0064] Embodiments of the present disclosure further include the following aspects.

[0065] (Supplementary Note 1) A film containing a carbon-containing metal oxyfluoride, wherein the carbon-containing metal oxyfluoride is ａ O ｂ F ｃ C ｄ wherein M represents a metal atom, and a, b, c, and d represent atomic ratios, and satisfy 0<a<1, 0<b<1, 0<c<1, 0<d<1, and a+b+c+d=1.

[0066] (Appendix 2) The film according to appendix 1, wherein a is 0.10 or more and 0.40 or less, b is 0.10 or more and 0.45 or less, c is 0.05 or more and 0.60 or less, and d is 0.05 or more and 0.55 or less.

[0067] (Appendix 3) The film according to appendix 1 or 2, wherein a is 0.15 or more and 0.36 or less, b is 0.10 or more and 0.35 or less, c is 0.15 or more and 0.50 or less, and d is 0.05 or more and 0.30 or less.

[0068] (Appendix 4) The membrane according to any one of Appendices 1 to 3, wherein the membrane has a porosity of less than 5%.

[0069] (Appendix 5) The film according to any one of Appendices 1 to 4, wherein M is at least one selected from the group consisting of Y, Al, Er, Yb, La, and Gd.

[0070] (Appendix 6) The film according to any one of appendices 1 to 5, wherein the film is obtained by at least one method selected from the group consisting of thermal spraying, sputtering physical vapor deposition, chemical vapor deposition, ion plating, ion-assisted deposition, and aerosol deposition.

[0071] (Supplementary Note 7) The film according to any one of Supplementary Notes 1 to 6, wherein the film has a thickness of 1 μm or more and 300 μm or less.

[0072] (Supplementary Note 8) An article constituting a part of a plasma processing apparatus, comprising: a substrate; and a film disposed on the substrate and containing a carbon-containing metal oxyfluoride, wherein the carbon-containing metal oxyfluoride is selected from the group consisting of M ａ O ｂ F ｃ C ｄ wherein M represents a metal atom, and a, b, c, and d represent atomic ratios, and satisfy 0<a<1, 0<b<1, 0<c<1, 0<d<1, and a+b+c+d=1.

[0073] (Appendix 9) The substrate is a solid aluminum material, an aluminum material surface-treated with anodized aluminum, Al ２ O ３ Alumina sintered body, YAG sintered body, Y ２ O ３ 9. The article of claim 8, comprising at least one selected from the group consisting of sintered bodies.

[0074] (Appendix 10) The article according to appendix 8 or 9, wherein the substrate has a surface average roughness Ra of less than 0.5 μm.

[0075] (Supplementary Note 11) The article according to any one of Supplementary Note 8 to Supplementary Note 10, wherein the film of the article constitutes a plasma-exposed surface in a chamber of the plasma processing apparatus.

[0076] (Supplementary Note 12) A plasma processing apparatus comprising the article according to any one of Supplementary Notes 8 to 11.

[0077] (Supplementary Note 13) A plasma processing apparatus comprising: a chamber; and a plasma generating unit configured to generate plasma in the chamber, wherein at least a portion of a portion in the chamber that is exposed to the plasma is formed of the film according to any one of Supplementary Note 1 to Supplementary Note 13.

[0078] The above embodiments are described for the purpose of explanation and are not intended to limit the scope of the present disclosure. Various modifications can be made to the above embodiments without departing from the scope and spirit of the present disclosure. For example, some components in one embodiment can be added to other embodiments. Also, some components in one embodiment can be replaced with corresponding components in other embodiments.

[0079] REFERENCE SIGNS LIST 1: Plasma processing apparatus, 2: Control unit, 10: Plasma processing chamber, 10a: Side wall, 10s: Plasma processing space, 11: Substrate support, 112: Ring assembly, 13: Shower head, 13a: Gas supply port, 20: Gas supply unit, 31a: First RF generating unit, 31b: Second RF generating unit, 32a: First DC generating unit, CP: Component, CP1: First layer, CP2: Second layer, W: Substrate

Claims

1. A film comprising a carbon-containing metal oxyfluoride, wherein the carbon-containing metal oxyfluoride is M ａ O ｂ F ｃ C ｄ wherein M represents a metal atom, and a, b, c, and d represent atomic ratios, and satisfy 0<a<1, 0<b<1, 0<c<1, 0<d<1, and a+b+c+d=1.

2. The membrane according to claim 1, wherein a is 0.10 or more and 0.40 or less, b is 0.10 or more and 0.45 or less, c is 0.05 or more and 0.60 or less, and d is 0.05 or more and 0.55 or less.

3. The membrane according to claim 1, wherein a is 0.15 or more and 0.36 or less, b is 0.10 or more and 0.35 or less, c is 0.15 or more and 0.50 or less, and d is 0.05 or more and 0.30 or less.

4. The membrane of claim 1, wherein the membrane has a porosity of less than 5%.

5. The film of claim 1, wherein M is at least one selected from the group consisting of Y, Al, Er, Yb, La, and Gd.

6. The film of claim 1, wherein the film is obtained by at least one method selected from the group consisting of thermal spraying, sputtering physical vapor deposition, chemical vapor deposition, ion plating, ion-assisted deposition, and aerosol deposition.

7. The film according to claim 1, wherein the film has a thickness of 1 μm or more and 300 μm or less.

8. An article constituting a part of a plasma processing apparatus, comprising: a substrate; and a film disposed on the substrate and containing a carbon-containing metal oxyfluoride, wherein the carbon-containing metal oxyfluoride is M ａ O ｂ F ｃ C ｄ wherein M represents a metal atom, and a, b, c, and d represent atomic ratios, and satisfy 0<a<1, 0<b<1, 0<c<1, 0<d<1, and a+b+c+d=1.

9. The substrate is solid aluminum, aluminum with anodized surface treatment, Al ２ O ３ Alumina sintered body, YAG sintered body, Y ２ O ３ The article of claim 8 , comprising at least one selected from the group consisting of sintered bodies.

10. The article according to claim 8, wherein the substrate has an average surface roughness Ra of less than 0.5 μm.

11. The article of claim 8, wherein the film of the article comprises a plasma-exposed surface in a chamber of the plasma processing apparatus.

12. A plasma processing apparatus comprising the article according to any one of claims 8 to 11.

13. A plasma processing apparatus comprising: a chamber; and a plasma generating unit configured to generate plasma within the chamber, wherein at least a portion of a portion within the chamber that is exposed to the plasma is formed of the film according to any one of claims 1 to 7.

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