Plasma-resistant laminate, method for manufacturing the same, and plasma processing apparatus

Abstract

To provide a capacitive probe-type plasma sensor including a plasma-resistant laminate.SOLUTION: A plasma-resistant laminate 1 comprises a substrate 2, a membrane electrode 3 formed on the substrate 2, and a dielectric layer 4 formed on the membrane electrode 3. The dielectric layer 4 is a polycrystalline dielectric layer and includes columnar particles longer in a thickness direction. The membrane electrode 3 is formed of active metal, or a constituent element of the substrate or the dielectric layer, or lamination of these elements.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a plasma-resistant laminate, a manufacturing method thereof, and a plasma processing apparatus. [Background technology]

[0002] 2. Description of the Related Art In the field of semiconductor manufacturing, plasma processing methods using plasma discharge on a processing target such as a semiconductor substrate are widely used for the purpose of plasma CVD (chemical vapor deposition), ashing, etching, sputtering, and other surface treatments.

[0003] In a plasma processing step in which plasma treatment is performed, there is a problem that when a high voltage or a high frequency voltage from a high frequency power source is applied, abnormal discharge occurs, etc., and the characteristics of electronic elements of the processed object are deteriorated due to poor stability of the plasma. In order to deal with such problems, it is required to accurately detect the plasma state in the plasma processing chamber.

[0004] Known plasma measuring instruments for detecting the plasma state include the Langmuir probe, which inserts an exposed tip of a probe-shaped electrode into the plasma and measures plasma states such as space potential from the current-voltage characteristics obtained by applying a voltage, and the capacitive probe, which covers the electrode with an insulator and measures plasma states such as space potential from the electrostatic capacitance.

[0005] Conventionally proposed plasma measuring instruments include those disclosed in, for example, Patent Documents 1 to 3. That is, Patent Document 1 proposes a plasma monitoring device using a window-type probe. Patent Document 2 proposes a plasma processing device equipped with a signal detection unit that detects a precursor signal that catches the occurrence of abnormal plasma discharge in advance, and a control unit that controls the ESC leakage current based on the precursor signal.

[0006] Patent Document 3 proposes that in a plasma processing apparatus, a probe base is installed on the side wall of a processing chamber, pulsed bias power is applied to this base, and the voltage change of a capacitor is analyzed to monitor the condition of the inner wall of the processing chamber and the internal state of the plasma in real time, and the processing method of the plasma processing apparatus is controlled from the data values. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2003-318115 A [Patent Document 2] JP 2007-73309 A [Patent Document 3] JP 2011-228386 A Summary of the Invention

[0008] The plasma-resistant laminate of the present disclosure comprises a substrate, a film electrode located on the substrate, and a dielectric layer located on the film electrode, the dielectric layer being a polycrystalline dielectric layer and including columnar particles that are long in the thickness direction, and the film electrode being made of an active metal or a constituent element of the substrate or the dielectric layer, or a laminate thereof.

[0009] The method for manufacturing the plasma-resistant laminate of the present disclosure includes the steps of polishing the surface of a substrate to an arithmetic mean height (Sa) of 0.01 μm or less, forming a film electrode on the substrate, and forming a dielectric layer by repeatedly depositing and oxidizing a metal material.

[0010] The plasma processing apparatus of the present disclosure has a capacitive probe type plasma sensor including the above-mentioned plasma-resistant laminate attached inside a plasma processing chamber. [Brief description of the drawings]

[0011] [Figure 1] 1 is a schematic cross-sectional view showing a plasma-resistant laminate according to an embodiment of the present disclosure. [Diagram 2]FIG. 2 is a schematic diagram showing a sputtering apparatus for producing a plasma-resistant laminate. [Figure 3A] 1 is a laser microscope photograph (magnification: 1200 times) of a substrate on which a film is formed using sapphire. [Figure 3B] For comparison, a laser microscope photograph (magnification: 1200 times) of a substrate on which a film was formed using alumina is shown. [Figure 4A] 1 is a scanning electron microscope (SEM) photograph showing the interface between the film electrode and the dielectric layer in the center. [Figure 4B] 1 is a scanning electron microscope (SEM) photograph showing an interface between a film electrode and a dielectric layer in the outer periphery. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] A plasma-resistant laminate according to an embodiment of the present disclosure will be described below. Fig. 1 is a schematic cross-sectional view showing a plasma-resistant laminate 1 according to this embodiment. This plasma-resistant laminate 1 functions as a capacitive probe type plasma sensor.

[0013] As shown in FIG. 1, the plasma-resistant laminate 1 includes a substrate 2, a membrane electrode 3 formed on the substrate 2, and a dielectric layer 4 formed on the membrane electrode 3.

[0014] The substrate 2 includes sapphire, and the dielectric layer 4 includes an oxide including yttrium. Sapphire has excellent plasma resistance and mechanical strength. In addition, yttria (Y2O3), which is an oxide of yttrium, has even better plasma resistance than sapphire.

[0015] Furthermore, because sapphire is a single crystal, its surface can be processed smoothly, making it possible to form thin film electrodes 3 and dielectric layers 4 with few defects such as voids. As a result, the capacitance calculated from (area x dielectric constant / thickness) can be increased.

[0016] Average linear thermal expansion coefficient at 40℃~400℃ (10 -6 / K) is 7.2 for the yttria constituting the dielectric layer 4, whereas the sapphire constituting the substrate 2 is 7.7 in the direction parallel to the c-axis and 7.0 in the direction perpendicular to the c-axis. Therefore, the difference in thermal expansion between the dielectric layer 4 and the substrate 2 is small, and peeling or cracks due to thermal stress are unlikely to occur.

[0017] The film electrode 3 is made of an active metal, or a constituent element of the substrate 2 or the dielectric layer 4, or a laminate thereof. An active metal is a metal that is more likely to bond with oxygen atoms of the oxide constituting the substrate 2 than inactive metals such as copper, silver, and gold, and has a higher adhesive strength. Representative active metals are alkaline earth metals, rare earth metals, metals of groups 4 to 6 of the periodic table, and metals of groups 13 to 14 of the periodic table. In particular, titanium, zirconium, hafnium, vanadium, and chromium have a high adhesive strength with sapphire, and their thermal expansion coefficients are relatively small compared to sapphire as metals. Yttrium is a constituent element of yttria constituting the dielectric layer 4, and the dielectric layer 4 can be formed continuously by oxidizing the surface of yttrium, so that the adhesive strength with the dielectric layer 4 can be improved. Aluminum is a constituent element of sapphire constituting the substrate 2, and the adhesive strength with the substrate 2 can be improved by utilizing the diffusion of aluminum atoms by heat treatment. It is particularly preferred that the membrane electrode 3 be a laminate of an active metal formed on the substrate 2 and yttrium formed on the active metal, since this provides high adhesion to both the substrate 2 and the dielectric layer 4.

[0018] The membrane electrode 3 has a thickness of 0.5 μm or more and 5 μm or less, and the dielectric layer 4 has a thickness of 0.5 μm or more and 5 μm or less from the surface of the membrane electrode 3 and an area of ​​1000 mm 2 It is preferable that the capacitance is 1 nF or more. Since the film electrode 3 is thin in this way, it can be covered with a thin dielectric layer 4, and the capacitance (area x dielectric constant / thickness) can be increased. Specifically, the plasma-resistant laminate of this embodiment preferably has a capacitance of 1 nF or more.

[0019] It is preferable that the surface of the substrate 2 is a c-plane of sapphire. Since the substrate 2 is thicker than the film electrode 3 and the dielectric layer 4, the deformation and stress of the substrate 2 have a large effect on the deformation and stress of the plasma-resistant laminate 1. The c-plane has the advantage that it has little deformation when the temperature changes because it has no anisotropy in the thermal expansion coefficient or Young's modulus.

[0020] Depending on the formation method, the dielectric layer 4 has a compressive stress in a direction perpendicular to the thickness direction. The direction perpendicular to the thickness direction is a direction parallel to the surface of the dielectric layer 4. For example, as described later, in the post-oxidation sputtering method, the oxide film (dielectric layer 4) is formed by repeatedly depositing and oxidizing a metal (yttrium), so that the interatomic distance increases during oxidation. At that time, it is considered that a compressive stress occurs in the dielectric layer 4 because the direction perpendicular to the thickness direction is restrained by the base 2.

[0021] The stress in the direction perpendicular to the thickness direction of the dielectric layer 4 can be measured using an X-ray diffraction device. Stresses in two directions parallel to the surface and perpendicular to each other are evaluated at multiple points (for example, five points) in the plane, and the average values ​​are taken as σ11 and σ22. Since the dielectric layer 4 is thin, cracks are likely to occur when tensile stress is applied in the direction perpendicular to the thickness direction. Therefore, it is preferable that σ1, which is the average value of stress σ11 and stress σ22, is compressive stress. In this case, it is particularly preferable that both σ11 and σ22 are compressive stress. Since distortion is likely to occur when the difference between σ11 and σ22 is large, it is preferable that σ22 / σ11 is 0.5 to 2, preferably 0.8 to 1.2.

[0022] The average value σ1 of the stresses σ11 and σ22 may be 200 MPa or more and 1000 MPa or less. When σ1 is 200 MPa or more, the hardness is maintained and the occurrence of particles, cracks, etc. can be reduced. On the other hand, when σ1 is too large, deformation and cracks are likely to occur and the bonding strength is also likely to decrease, so σ1 is preferably 1000 MPa or less.

[0023] As described above, the thermal expansion coefficient of sapphire is larger than that of yttria in the direction parallel to the c-axis, and smaller than that of yttria in the direction perpendicular to the c-axis. Therefore, it is possible to adjust σ1 by selecting the crystal orientation of the sapphire used as the substrate 2. For example, when σ1 is a compressive stress as in the embodiment of the present invention, it is preferable to use sapphire with a surface perpendicular to the c-axis (c-plane) of the substrate 2 facing the dielectric 4 and to use the substrate 2 in a lower temperature environment than when the dielectric layer 4 is formed, because the difference in thermal expansion between the substrate 2 and the dielectric layer 4 alleviates σ1 (σ1 does not become too large). In addition, for example, when the shape of the substrate 2 is rectangular and has a long (long side) direction and a short (short side) direction, causing a difference between σ11 and σ22, the surface of the substrate 2 facing the dielectric 4 may be sapphire with a surface parallel to the c-axis (a-plane, m-plane, etc.), and the orientation of the sapphire may be selected so that the direction that is likely to cause large compressive stress (for example, the long side of the rectangle) is perpendicular to the c-axis. Perpendicular to or parallel to the c-axis does not need to be completely perpendicular or parallel, and may be within ±15°, for example.

[0024] Also, the dielectric layer 4 is preferably formed of columnar grains long in the thickness direction. It is particularly preferable that the length of the grains in the thickness direction is almost the same as the thickness of the dielectric layer 4. The average grain size on the surface of the dielectric layer 4 is preferably 0.01 μm to 0.5 μm, and the average aspect ratio (major axis / minor axis) of the grains is preferably 2 or more. If the average grain size is 0.01 μm or more on the surface of the dielectric layer 4 that is most exposed to plasma, the ratio of grain boundaries is reduced, and plasma resistance is improved. Also, columnar grains long in the thickness direction reduce the number of grain boundaries that cross the electric field direction, and measurement accuracy is improved. This provides high dielectric performance and plasma resistance. The dielectric layer 4 made of columnar grains can be formed, for example, using a post-oxidation sputtering device. The average particle size of the particles can be determined by obtaining a surface observation image of an area of, for example, 9 x 12 μm using a scanning electron microscope (SEM) or the like, drawing six straight lines of the same length, for example, 6 μm, radially from an arbitrary point as the center, and dividing the total length of these six straight lines by the total number of crystals present on these lines.

[0025] Furthermore, the dielectric layer 4 may have elongated pores whose length in the thickness direction is longer than the length in the direction perpendicular to the thickness direction when a cross section cut along the thickness direction is observed. In the case where the dielectric layer 4 has elongated pores, the area ratio of the pores when the dielectric layer 4 is viewed in the thickness direction can be reduced, and the decrease in capacitance due to the pores can be reduced to improve the measurement accuracy. Furthermore, the capacitance in the thickness direction of the dielectric layer 4 can be appropriately maintained to improve the measurement accuracy, while the stress generated in the dielectric layer 4 can be effectively relaxed by the pores. The dielectric layer 4 having elongated pores in the thickness direction can be formed by repeating the film formation several times using, for example, a post-oxidation sputtering device. The area ratio of the pores in the cross section cut along the thickness direction of the dielectric layer 4 having elongated pores may be 0.05 area % to 8 area %.

[0026] Light of various wavelengths is generated in the plasma generating section. Light of wavelengths of 400 nm or less is called ultraviolet light, and light of wavelengths of 700 nm or more is called infrared light. When infrared light is absorbed by a substance, it causes heat generation (increase in lattice vibration). When the dielectric layer 4 is heated, there is a concern that the characteristics of the element using the dielectric layer 4 will change due to changes in resistivity caused by thermal generation of carriers (electrons). Ultraviolet light causes deterioration of various substances such as polymers. When the dielectric layer 4 absorbs ultraviolet light, a part of the ultraviolet light is changed to light of other wavelengths, and the reflection and transmission of the ultraviolet light is reduced, so that the influence of the ultraviolet light on the surrounding members is reduced compared to when the reflectance of the ultraviolet light is high. Therefore, it is preferable that the reflectance of the dielectric layer 4 for light of wavelengths of 400 nm or less is 50% or less, preferably 30% or more. It is also preferable that the reflectance of the dielectric layer 4 for light of wavelengths of 700 nm or more is 50% or more, preferably 60% or more. If the reflectance of light with a wavelength of 400 nm or less is 50% or less, preferably 30% or more, the reflectance of ultraviolet light is low, so that deterioration of other parts exposed to plasma light inside and outside the device, particularly organic parts that are at risk of deterioration due to ultraviolet light, can be reduced. If the reflectance of light with a wavelength of 700 nm or more is 50% or more, preferably 60% or more, the reflectance of infrared light is high, so that the temperature rise of the film surface is suppressed and the change in element sensitivity due to plasma exposure is reduced.

[0027] As shown in FIG. 1, the substrate 2 is formed on the surface of the support layer 5. For example, alumina ceramics can be used as the support layer 5. Alumina ceramics is the same material as sapphire, so the difference in physical properties such as thermal expansion coefficient is small, and it can be produced more inexpensively than sapphire. For example, an epoxy adhesive or a silicone adhesive can be used to bond the substrate 2 and the support layer 5, or direct bonding by diffusion bonding or the like can be used. A power supply terminal 7 for power supply and measurement is provided on the support layer 5. The support layer 5 may be provided as necessary, and the substrate 2 and the support layer 5 may be integrally formed using sapphire.

[0028] The substrate 2 has a plurality of via electrodes 6 electrically connected to the membrane electrodes 3. The via electrodes 6 can be formed by applying copper plating or the like to through holes provided in the substrate 2. The diameter of the via electrodes 6 is preferably 30 μm or more and 200 μm or less.

[0029] If there is a step between the via electrode 6 and the base 2, there is a risk of the electrical connection with the film electrode 3 being impaired (disconnected). Therefore, in this embodiment, it is preferable to adjust the step between the via electrode 6 and the base 2 to 1.0 μm or less, preferably 0.2 μm or less, by surface polishing. This makes it possible to maintain the surface smoothness and the film thickness distribution of the dielectric layer 4 with extremely high precision without variation.

[0030] The membrane electrode 3 is electrically connected to a power supply terminal 7 of the support layer 5 through a via electrode 6. This allows the membrane electrode 3 to function as a probe for plasma measurement, and to measure the space potential that indicates the plasma state.

[0031] Next, a method for producing the plasma-resistant laminate of the present disclosure will be described. The plasma-resistant laminate of the present disclosure can be produced by the steps exemplified below. <Process for polishing the substrate 2> The surface of the substrate 2 containing sapphire is polished so that the arithmetic mean height (Sa) is 0.1 μm or less, preferably 10 nm or less. The substrate 2 has the above-mentioned multiple via electrodes 6 formed thereon in advance. The polishing may be performed by, for example, lapping using diamond abrasive grains and a surface plate, and chemical mechanical polishing (CMP) using colloidal silica abrasive grains and an alkaline slurry.

[0032] Arithmetic mean height (Sa) is a parameter of surface quality defined in ISO25178-6:2010, and is a parameter that extends the arithmetic mean roughness Ra of lines to surfaces. Specifically, arithmetic mean height (Sa) represents the average of the absolute values ​​of the differences in height of each point on the target surface relative to the average surface of the target surface. Sa represents the average of the absolute values ​​of the differences in height of each point on the target surface relative to the average surface of the target surface.

[0033] The substrate 2 includes single crystal sapphire. The surface of the substrate 2 is preferably a c-plane of sapphire in order to reduce the difference in thermal expansion with the dielectric layer 4. The thickness of the substrate 2 is designed so that the plasma-resistant laminate 1 satisfies the mechanical strength requirements, and for example, if the diameter of the substrate 2 is about 50 mm (2 inches), the thickness should be 100 μm or more.

[0034] <Step of forming the membrane electrode 3 and the dielectric layer 4> It is preferable to form a membrane electrode 3 having a thickness of 5 μm or less on a substrate 2, and then form a dielectric layer 4 having a thickness of 5 μm or less on the surface of the membrane electrode 3. The membrane electrode 3 is made of an active metal such as titanium or yttrium, or a constituent element of the substrate 2 or the dielectric layer 4, but the following description will be given taking an example in which yttrium is used.

[0035] A method for forming the film electrode 3 and the dielectric layer 4 will be described with reference to Fig. 2. Fig. 2 is a schematic diagram showing a sputtering apparatus 20, which includes a chamber 15, a gas supply source 13 connected to the inside of the chamber 15, an anode 14 and a cathode 12 located within the chamber 15, and a target 11 connected to the cathode 12 side.

[0036] The film electrode 3 and the dielectric layer 4 can be formed continuously by a sputtering device 20 capable of sputtering and plasma processing. First, the substrate 2 obtained by the above-mentioned method is placed on the anode 14 side in the chamber 15. A target 11 of metal yttrium with a purity of 4N (99.99%) or more is placed on the cathode 12 side on the opposite side in the chamber 15. In this state, the chamber 15 is depressurized by the exhaust pump, and argon and oxygen are supplied as gas G from the gas supply source 13. For example, the pressure of the argon gas is 0.1 Pa or more and 2 Pa or less, and the pressure of the oxygen gas is 1 Pa or more and 5 Pa or less. Here, in order to obtain a dielectric layer 4 in which the average value σ1 of the stresses σ11 and σ22 in two directions perpendicular to the thickness direction and perpendicular to each other is 200 MPa or more and 1000 MPa or less, the pressure of the argon gas may be 0.1 Pa or more and 1 Pa or less, and the pressure of the oxygen gas may be 1 Pa or more and 5 Pa or less.

[0037] Next, in an argon-rich atmosphere, an electric field is applied between the anode 14 and the cathode 12 by the power source, and plasma P is generated and sputtered to form a metal yttrium film on the surface of the substrate 2, forming a film electrode 3 having a thickness of 5 μm or less. The power supplied from the power source may be either high-frequency power or direct current power. When forming a film electrode 3 in which multiple metals such as titanium and yttrium are laminated, multiple targets 11 may be placed in the sputtering device 20, and the metal to be formed may be switched by switching the targets 11.

[0038] After forming the film electrode 3, the dielectric layer 4 is formed by a post-oxidation sputtering method. That is, the formation of a metal yttrium film by sputtering and the oxidation by oxygen plasma are repeated on the surface of the film electrode 3 to form an yttria film that becomes the dielectric layer 4. The thickness of each yttrium film is approximately 1 nm or less. Then, the formation of the yttrium film and the oxidation process are alternately performed to stack the dielectric layers 4 so that the total thickness of the dielectric layers 4 is 5 μm or less, thereby obtaining a dielectric layer 4 containing yttria and having a thickness of 5 μm or less. In this way, the plasma-resistant laminate 1 of the present disclosure can be obtained. If the surface of the film electrode 3 is yttrium, the connection portion with the dielectric layer 4 can be formed by oxidizing the film electrode 3, so that a highly adhesive and stable dielectric layer 4 can be obtained. The interface between such an yttrium layer and yttrium oxide is unclear, and there is a region where the oxygen ratio increases continuously.

[0039] There are two types of sputtering apparatus 20 for alternately performing the sputtering step of forming a metal yttrium film and the oxidation step: one in which the sputtering region and the oxidation region are separated by a space and the substrate 2 moves between the two regions, and the other in which the sputtering and oxidation are separated by time and sputtering and oxidation are alternately performed in the same region. Figure 2 shows the latter type.

[0040] In the former type, a sputtering region and an oxidation region are set up inside the device, and the substrate 2 moves between these regions. Each region is surrounded by a partition, and in the sputtering region, the Ar partial pressure is increased, and ions are accelerated by a magnetic field (or electric field) to collide with the target. On the other hand, in the oxidation region, the oxygen partial pressure is increased.

[0041] In the latter type, the substrate 2 remains in the same place, and the gas species supplied to the chamber 15 is switched to repeat metal film formation and oxidation.

[0042] In either case, in the sputtering region (during sputtering), argon-rich plasma is irradiated onto the target to perform sputtering, and in the oxidation region (during oxidation), oxygen-rich plasma is irradiated onto the substrate 2 and the film of the dielectric layer 4 to perform oxidation.

[0043] 1, the dielectric layer 4 is formed so as to cover the front and side surfaces of the membrane electrode 3. The membrane electrode 3 is not exposed in this manner in order to protect the membrane electrode 3 from plasma.

[0044] Fig. 3A shows a laser microscope photograph (magnification: 1200x) of the surface of the dielectric layer 4 formed on the sapphire substrate 2. For comparison, Fig. 3B shows a laser microscope photograph (magnification: 1200x) of the surface of the dielectric layer 4 formed on an alumina ceramic substrate in a similar manner. The arithmetic mean height Sa of the sapphire substrate 2 after polishing was 10 nm or less, and the arithmetic mean height Sa of the alumina substrate was 30 nm or less.

[0045] Voids, scratches, etc. appear on the surface of dielectric layer 4 of the alumina substrate shown in FIG. 3B, whereas no voids, scratches, etc. are observed on the surface of dielectric layer 4 of the sapphire substrate 2 shown in FIG. 3A.

[0046] In addition, the surface of the dielectric layer 4 on the alumina substrate had an arithmetic mean height (Sa) of 0.199 μm, whereas the surface of the dielectric layer 4 on the sapphire substrate 2 had an arithmetic mean height (Sa) of 0.032 μm, and the surface was smooth. Therefore, by using the sapphire substrate 2, it is possible to form a thin film electrode 3 and a dielectric layer 4 without voids or the like.

[0047] 4A and 4B are scanning electron microscope (SEM) photographs showing an example of a laminated state of the formed film electrode 3 and dielectric layer 4, showing the interface portion at the center and the outer periphery, respectively. The plasma-resistant laminate 1 shown in Fig. 4A and 4B is formed by forming a dielectric layer 4 made of yttria (Y2O3) with a thickness of about 2 µm on a film electrode 3 made of yttrium (Y) with a thickness of about 2 µm on a substrate 2 made of sapphire.

[0048] 4A and 4B show that the membrane electrode 3 and the dielectric layer 4 are laminated uniformly over the entire surface. In addition, an amorphous intermediate layer exists between the membrane electrode 3 made of yttrium and the dielectric layer 4 made of yttria. The intermediate layer has a composition intermediate between yttria and yttrium, and contributes to improving the adhesion between the membrane electrode 3 and the dielectric layer 4.

[0049] The support layer 5 may be bonded to the substrate 2 in advance of the sputtering, or may be bonded after the sputtering is completed.

[0050] The plasma-resistant laminate 1 of the present disclosure is used as a capacitive probe type plasma sensor. That is, in a plasma processing apparatus that performs plasma processing on a processing target such as a semiconductor substrate by using plasma discharge, such as plasma CVD, ashing, etching, sputtering, etc., one or more of the plasma sensors are attached to a wall surface inside a plasma processing chamber. Other applications of the plasma-resistant laminate 1 include electrostatic chucks, etc.

[0051] The plasma-resistant laminate 1 of this embodiment has excellent plasma resistance because the base 2 contains sapphire and the dielectric layer 4 contains an oxide of yttrium (yttria). In addition, the difference in thermal expansion between sapphire and yttria is small, so peeling or cracks due to thermal stress are unlikely to occur. Furthermore, sapphire also has excellent mechanical strength. Therefore, the plasma-resistant laminate 1 of this embodiment can be suitably used in a plasma measuring device in a plasma processing apparatus.

[0052] Although the embodiments of the present disclosure have been described above, the plasma-resistant laminate of the present disclosure is not limited to the above embodiments, and various modifications and improvements are possible within the scope of the present disclosure. For example, the base 2 may contain additives or oxygen defects for adjusting the light transmittance of sapphire, or additives or defects that absorb harmful light such as ultraviolet light, etc., within a range that does not impair its characteristics. Furthermore, the dielectric layer 4 may contain other oxides such as aluminum in addition to yttrium, or may contain composite oxides such as yttrium aluminum garnet, within a range that does not impair its characteristics. [Explanation of symbols]

[0053] 1. Plasma-resistant laminate 2 Base 3 Membrane electrode 4 Dielectric Layer 5 Support layer 6 Via electrode 7 Power supply terminal 11. Target 12 Cathode 13 Gas supply source 14 Anode 15 Chamber 20 Sputtering equipment

Claims

1. A plasma-resistant laminate comprising a substrate, a membrane electrode located on the substrate, and a dielectric layer located on the membrane electrode, The dielectric layer is a polycrystalline dielectric layer and contains columnar grains that are long in a thickness direction, The membrane electrode is a plasma-resistant laminate made of an active metal, or a constituent element of the substrate or the dielectric layer, or a laminate thereof.

2. The plasma-resistant laminate according to claim 1 , wherein the columnar grains include an oxide containing yttrium.

3. 3. The plasma-resistant laminate according to claim 1, wherein the film electrode is a laminate of the active metal on the substrate and yttrium on the active metal.

4. The membrane electrode has a thickness of 5 μm or less, and the dielectric layer has a thickness of 5 μm or less from the surface of the membrane electrode and an area of ​​1000 mm ２ The plasma-resistant laminate according to claim 1 or 2.

5. 3. The plasma-resistant laminate according to claim 1, having a capacitance of 1 nF or more.

6. The plasma-resistant laminate according to claim 1 , wherein the membrane electrode is made of titanium, yttrium, or a laminate thereof.

7. 7. The plasma-resistant laminate according to claim 6, wherein said film electrode is formed by laminating yttrium on titanium formed on said substrate.

8. 3. The plasma-resistant laminate according to claim 1, wherein stresses σ11 and σ22 in two directions perpendicular to a thickness direction of the dielectric layer and perpendicular to each other are both compressive stresses, and σ22 / σ11 is 0.5 or more and 2 or less.

9. The plasma-resistant laminate according to claim 8, wherein the σ22 / σ11 is 0.8 or more and 1.2 or less.

10. 9. The plasma-resistant laminate according to claim 8, wherein an average value σ1 of stresses σ11 and σ22 in two directions perpendicular to a thickness direction of the dielectric layer and perpendicular to each other is a compressive stress of 200 MPa or more and 1000 MPa or less.

11. 3. The plasma-resistant laminate according to claim 1, wherein the substrate is a single crystal.

12. 3. The plasma-resistant laminate according to claim 1, wherein the dielectric layer has a compressive stress in a direction perpendicular to a thickness direction, and the substrate surface is a c-plane of sapphire.

13. The plasma-resistant laminate according to claim 11, wherein the dielectric layer has a compressive stress in a direction perpendicular to the thickness direction, the shape of the substrate has a long direction and a short direction, and the long direction is parallel to the c-axis of sapphire.

14. 3. The plasma-resistant laminate according to claim 1, wherein the substrate has a via electrode electrically connected to the membrane electrode, and a step between the via electrode and the substrate is 1.0 [mu]m or less.

15. A method for producing the plasma-resistant laminate according to claim 1 or 2, comprising the steps of: a step of polishing the surface of the substrate so that the arithmetic mean height (Sa) is 10 nm or less; forming the membrane electrode on the substrate; forming the dielectric layer by repeatedly depositing a metal material and oxidizing it; A method for producing a plasma-resistant laminate, comprising the steps of:

16. The method for producing a plasma-resistant laminate according to claim 15, wherein the film electrode has a thickness of 5 μm or less, and the dielectric layer has a thickness of 5 μm or less.

17. 3. A plasma processing apparatus comprising: a plasma sensor including the plasma-resistant laminate according to claim 1 or 2, the plasma sensor being attached in a plasma processing chamber.

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