Coating film and vacuum chamber wall or internal component using the same

Abstract

The present invention provides a coating film formed on the surface of a vacuum chamber wall or internal component used in the manufacture of a semiconductor or display device, characterized in that the coating film contains a yttrium compound, has resistance to plasma, and contains a predetermined proportion of hydrogen.

Description

[Technical Field]

[0001] The present invention relates to a coating and a vacuum chamber component comprising the coating, and more particularly to a coating having resistance to etching or corrosion in a plasma environment and a vacuum chamber component comprising the coating. [Previous Technology]

[0002] In the manufacture of semiconductors or display devices, processes using plasma are widely used. Plasma is mainly used in deposition and etching processes to form and pattern the metal films, semiconductor films, and insulating films that constitute semiconductor devices.

[0003] As etching gases used in etching processes, halogen-based compounds are mainly used, and specifically, fluorine-containing compounds, chlorine-containing compounds, bromine-containing compounds, etc. can be used. These etching gases are activated into ions, free radicals, etc. in plasma to induce etching.

[0004] In this etching process, in addition to the etching on the substrate, the etching or corrosion of the components inside the vacuum chamber used to form the plasma is also inevitable. The following problems exist: the etching or corrosion of these components may shorten the life of the chamber components and the cleaning cycle, and etching byproducts may fall on the substrate and generate particles or contaminate the etching gas itself.

[0005] To address these issues, materials with plasma resistance (i.e., resistance to plasma etching or corrosion) are being investigated. Needless to say, plasma-resistant materials should possess high etching resistance to etching gases.

[0006] Compounds widely used as plasma-resistant materials include yttrium compounds, zirconium compounds, aluminum compounds, etc., which are mainly formed as oxides in the form of coatings on vacuum chamber components.

[0007] There is relevant prior art literature, Korean Patent Publication No. 2014-0033587. The aforementioned prior art literature discloses a yttrium oxide-zirconia composite oxide with resistance to plasma corrosion, characterized in that the content of yttrium oxide and zirconia is 95~45 wt.%: 5~55 wt.%, and when yttrium oxide and zirconia are sintered, yttrium oxide and zirconia form a solid solution.

[0008] It is believed that various factors of the coating can affect plasma toughness, and the known factors include porosity related to the density of the film, interatomic bonding forces related to the chemical reactivity of the etch active species, and crystallinity related factors such as crystalline or amorphous.

[0009] Recently, due to the narrowing of the linewidth of semiconductor circuits, conventional etching processes using halogen compound plasmas have shown their limitations, and therefore, processes that perform plasma etching by adding hydrogen to existing etching gases are being actively developed.

[0010] This hydrogen etching process clearly reveals the limitations of existing known plasma-resistant materials, and therefore, there is a great need to develop coatings with high plasma resistance for etching processes performed by adding hydrogen to existing halogen-containing gases. [Summary of the Invention]

[0011] Technical Issues

[0012] The first challenge to be solved by the present invention is to provide a coating having improved etch resistance or corrosion resistance to halogen-containing gases or halogen-containing gas-hydrogen mixed plasma.

[0013] The second challenge to be solved by the present invention is to provide a vacuum chamber component including the coating.

[0014] Technical Solution

[0015] In order to achieve the first challenge, the present invention provides a coating film formed on the surface of a vacuum chamber wall or internal component used in the manufacture of a semiconductor or display device, characterized in that the coating film contains a yttrium compound, a plasma-resistant material, and a predetermined concentration of hydrogen atoms.

[0016] According to one embodiment of the present invention, the yttrium compound may be yttrium oxide or yttrium aluminum oxide.

[0017] According to another embodiment of the present invention, it is preferred that yttrium oxide has an atomic ratio of yttrium to oxygen ranging from 1:0.60 to 1:2.5.

[0018] According to another embodiment of the present invention, it is preferred that the yttrium aluminum oxide has an atomic ratio of yttrium to aluminum ranging from 1:0.1 to 1:7.0.

[0019] According to another embodiment of the present invention, it is preferred that the concentration of hydrogen atoms contained in the coating film is 0.2 to 9 mol% (or atomic%).

[0020] According to another embodiment of the present invention, the concentration of hydrogen atoms can be measured by elastic recoil detection analysis.

[0021] According to another embodiment of the present invention, it is preferable that the porosity of the coating is 5% or lower.

[0022] According to another embodiment of the present invention, the coating film may include crystals.

[0023] According to another embodiment of the present invention, it is preferable that the coating has a grain size (average grain diameter) of 70 nanometers or smaller.

[0024] According to another embodiment of the present invention, it is preferable that the hardness of the coating film is 8 GPa or greater.

[0025] According to another embodiment of the present invention, it is preferred that the standard deviation of the standardized hydrogen yield measured by energy elastic recoil detection analysis (ERDA) for coatings under the following measurement conditions is in the range of 0.07 to 1.6. (1) Rutherford Backscattering Spectrometry (RBS) - Incident ion particle: 4He2+ - Incident ion energy: 2.0MeV - Charge of incident ion beam: 10μC - Ion incident angle (angle between the coating normal and the incident ion beam): 5° - Rutherford Backscattering Spectrometry (RBS) detector angle (angle formed with the extension of the incident beam through the sample): 170° - Rutherford Backscattering Spectrometry (RBS) detector scattering solid angle: 3.1 mSr - Standard deviation measurement energy range: 30~700 keV (2) Elastic Recoil Detection Analysis (ERDA) - Incident ion particle: 4He2+ - Incident ion energy: 2.0MeV - Charge of incident ion beam: 10μC - Ion incident angle (angle between the coating normal and the incident ion beam): 75° Elastic Recoil Detection Analysis (ERDA) detector angle (angle formed by the incident beam extension through the sample): 30° - Elastic Recoil Detection Analysis (ERDA) detector scattering solid angle: 2.55 mSr - Standard deviation measurement energy range: 30~700 keV - Method for obtaining standard deviation: Applying a linear regression model

[0026] According to another embodiment of the present invention, elastic recoil detection analysis (ERDA) can be performed after 100 to 700 nanometers have been removed from the surface of the coating by argon ion sputtering.

[0027] According to another embodiment of the present invention, it is preferred that the atomic ratio of yttrium in yttrium oxide is within a standard deviation range of 0.1 to 1.8 under the following analytical conditions: - Analytical method: Energy-dispersive X-ray spectroscopy using a transmission electron microscope - Measurement sites: Nine regions spaced 0.2 micrometers apart in both horizontal and vertical directions on a plane parallel to the surface of the coating film - Calculation of standard deviation: The standard deviation of the atomic ratio of yttrium measured at the above measurement sites

[0028] In order to achieve the second challenge, the present invention provides a vacuum chamber wall or internal component used in the manufacture of semiconductor or display devices, which includes the coating.

[0029] Beneficial effects

[0030] The coating of the present invention has the following effects. (1) The coating of the present invention has high etching resistance or corrosion resistance to plasma, especially in plasma processes composed of a mixture of halogen-containing compounds and hydrogen, or in plasma processes using a sequential mixture of halogen-containing compounds and hydrogen. (2) The concentration of hydrogen atoms in the coating is controlled within a predetermined range to improve plasma resistance. (3) The concentration of hydrogen atoms in the depth direction of the coating is kept constant within a predetermined range, so as to effectively suppress the penetration of hydrogen ions or free radicals inside the plasma into the depth direction of the coating. (4) The porosity is controlled at a low level, thereby inhibiting the rapid movement of etching active species through the pores in the coating, thereby improving etching resistance or corrosion resistance. (5) The atomic ratio of yttrium and its deviation relative to the horizontal direction of the coating are maintained within a certain range, thereby reducing etching or corrosion deviation in areas with non-homogeneous atomic ratios and reducing the possibility of particle generation.

Implementation Method

[0041] The coating of the present invention is a coating formed on the surface of a vacuum chamber wall or internal component used in the manufacture of a semiconductor or display device, characterized in that the coating contains a yttrium compound, is plasma resistant, and contains a predetermined proportion of hydrogen atoms.

[0042] The inventors of this invention have long been studying coatings with high etching resistance to halogenated compounds and hydrogen plasma, while exploring the causes and mechanisms of hydrogen ions or free radicals accelerating the etching or corrosion of coatings, and have discovered important facts that can prevent hydrogen ions or free radicals from accelerating etching or corrosion.

[0043] The coating etching process using plasma with a commonly known etching gas is as follows. The first stage is the reaction between the etching active species (such as halogen-containing ions or free radicals like fluorine, chlorine, and bromine) contained in the plasma and the elements constituting the coating on the surface. At this time, the reactivity is affected by the thermodynamic stability of the reactants constituting the coating and the thermodynamic stability of the products generated on the surface by the reaction, and the reaction rate is affected by the relative difference between the energy of the etching active species and the activation energy required for the reaction, as well as the reaction temperature. The second stage is the vapor pressure of the products generated on the surface by the reaction. If the products of the reaction on the surface have a high vapor pressure, the reaction products evaporate from the surface of the coating, thereby leading to continuous etching of the coating. In addition, in the etching process using reactive ions, positive ions present in the plasma can continuously bombard the coating, thus accelerating the reaction and evaporation.

[0044] Currently known plasma-resistant coatings possess factors that inhibit the etching process. The first stage of the etching process involves factors that inhibit the reaction between etch-active species and compounds on the surface of the coating. Relatedly, the coating characteristics are such that the bonds between atoms within the coating are strong, making it difficult to break these bonds to allow a reaction on the surface, and the thermodynamic energy levels of the reactants and products are set to inhibit the reaction. In this regard, yttrium oxide largely satisfies the above conditions, and additionally, by controlling crystallinity, atomic molar ratio, etc., the development direction of plasma-resistant coatings has been set towards higher plasma resistance.

[0045] The second stage of the etching process for plasma-resistant coatings involves factors that prevent the reaction from continuing while removing the reaction products. To ensure high plasma resistance, the vapor pressure of the substances generated on the surface through the reaction must be low. In fact, it is known that silicon tetrafluoride (SiF4), produced when silicon atoms react with fluorine atoms, has a boiling point of -90°C, while aluminum trifluoride (AlF3) and yttrium oxide (Y2O3), produced when aluminum and yttrium atoms react with fluorine, have very high boiling points of 1,297°C and 1,387°C, respectively.

[0046] Therefore, it is undeniable that the type of compound constituting the coating itself (which is a characteristic of the compound) and its atomic molar ratio are the main factors affecting plasma toughness.

[0047] Even if compounds have the same chemical formula or the same atomic molar ratio, minor factors such as the density and crystallinity of the coating can affect plasma resistance. Since these minor factors are affected by the deposition method and deposition conditions of the coating, one of the current efforts to improve plasma resistance is to find the optimal process conditions and properties.

[0048] The inventors of this invention have attempted to find the reason for the accelerated etching of coatings in plasma containing halogen compounds by adding hydrogen, based on the principle of etching or corrosion in a plasma environment, and have investigated the related factors.

[0049] One characteristic of hydrogen active species (i.e., hydrogen ions or hydrogen radicals) present within plasma is their extremely small atomic size. It is believed that etching or corrosion processes of plasma coatings can be largely attributed to the phenomenon that plasma ion bombardment is applied to regions near the surface of reaction products or intermediate products at a certain depth, and thus, some areas near the surface of the coating disintegrate and peel off to the outside of the surface; rather than the phenomenon that occurs when reaction products evaporate under low pressure. Furthermore, for the disintegration and peeling of the coating to occur effectively, the interatomic bonds of the coating or reaction products must be partially weakened, and it is believed that hydrogen that has penetrated from the surface of the coating to a certain depth by plasma ion bombardment will effectively perform this function.

[0050] In order to prevent etching or corrosion by hydrogen active species as described above, it is necessary to suppress the penetration of hydrogen active species in the thickness direction of the coating film and suppress the weakening of interatomic bonding forces of the coating film by the already penetrated hydrogen active species.

[0051] Based on this reason, the inventors of the present invention have been able to develop a coating that significantly improves resistance to plasma processes containing hydrogen-containing halogen compounds or hydrogen plasma processes and halogen compound plasma processes.

[0052] The plasma-resistant coating of the present invention is characterized in that hydrogen is injected during or after the film formation process and its concentration is controlled within a certain range.

[0053] It is believed that there are several reasons why the hydrogen contained in the coating provides high resistance to etching or corrosion of hydrogen-added plasma.

[0054] The first reason is that hydrogen atoms bond to defect sites on or inside the coating, thereby improving the chemical and physical stability of the film. In the case of yttrium compound coatings deposited by physical vapor deposition or chemical deposition, unstable defect sites may inevitably form on the surface or inside, and dangling bonds (electron pairs that cannot bond with surrounding atoms) may exist at these defect sites. These defect regions are highly reactive and more likely to react with etch-active species; additionally, the defects themselves may weaken the physical strength of the coating.

[0055] Hydrogen injected during or after coating formation can react with electrons at defect sites that are not involved in interatomic bonding, thereby weakening the reactivity of defect sites and improving physical properties. However, the function of these hydrogen atoms can vary depending on the concentration of hydrogen atoms in the coating compound. That is, while an appropriate concentration of hydrogen atoms can act to stabilize defect sites in the coating, a concentration exceeding a certain amount may have the negative effect of disrupting the stable interatomic bonds of the compound constituting the coating, and may also impart brittleness to the coating, resulting in more particles during plasma etching. Furthermore, the negative effects of these hydrogen atoms also mean the destruction of crystallinity. This invention discloses a plasma-resistant coating in which the concentration of hydrogen atoms is controlled within a predetermined range to maximize the positive function of the added hydrogen.

[0056] The second reason is to suppress the penetration of hydrogen-active species of plasma by means of hydrogen contained in the coating. In this regard, it is important that the concentration of hydrogen atoms in the coating does not exceed a certain deviation in the depth direction. Therefore, in the present invention, in a coating having resistance to hydrogen-containing plasma, the depth direction deviation of the concentration of hydrogen atoms is controlled within a predetermined range.

[0057] In addition, one of the factors that keeps the concentration of hydrogen atoms constant within a predetermined range in the depth direction of the coating is to ensure that the atomic ratio of yttrium atoms, one of the elements constituting the yttrium compound coating, remains constant in the horizontal and vertical directions of the coating.

[0058] Embodiments of the present invention will be described below.

[0059] In the plasma-resistant coating of the present invention, the term "plasma resistance" means resistance to etching by plasma or resistance to corrosion caused by collective peeling of particles. Furthermore, plasma defining plasma resistance refers to various plasmas used in semiconductor or display manufacturing processes, and more specifically, plasmas used in etching processes, and particularly plasmas using halogen-containing compounds and hydrogen or both in sequence.

[0060] The plasma-resistant coating of the present invention can be an inorganic oxide, inorganic nitride, or inorganic fluoride, and specifically, it can be a compound containing yttrium, zirconium, titanium, or aluminum, without particular limitation, as long as it is any other material with plasma resistance. Specifically, the coating can be composed of yttrium oxide, yttrium aluminum oxide, zirconium oxide, aluminum oxide, titanium oxide, titanium nitride, aluminum oxynitride, yttrium fluoride, yttrium oxyfluoride, or mixtures thereof. In the case of yttrium aluminum oxide, the atomic ratio of yttrium, oxygen, and aluminum can be varied. Furthermore, the plasma-resistant coating can be formed in the form of a mixture of these various compounds. The coating can be crystalline, amorphous, or nanocrystalline, or it can be a composite phase in which crystalline and amorphous phases are mixed within a predetermined range.

[0061] The hydrogen atoms contained in the plasma-resistant coating of the present invention can be chemically bonded to some atoms of the atoms constituting the coating or exist therein in a physically trapped state, and the concentration of hydrogen atoms can be quantified as the atomic ratio relative to the compound constituting the coating. To quantify this concentration of hydrogen atoms, secondary ion mass spectrometry (SIMS), elastic recoil detection analysis (or energy recoil detection analysis, ERDA) can be used, and other known analytical methods capable of quantitatively detecting hydrogen can also be used.

[0062] The substrate of the plasma-resistant coating of the present invention can be made of materials such as metal, ceramic, semiconductor materials, etc., and the chamber components constituting the substrate can include chamber walls, upper and lower surfaces of the chamber, substrate support, gas spray head, windows, etc., and additionally, their uses and materials are not limited, as long as they constitute the internal components of the chamber used in the plasma process.

[0063] The concentration of hydrogen atoms contained in the plasma-resistant coating of the present invention can be increased or decreased in the depth direction of the coating, and preferably can be uniformly maintained within a certain range in the depth direction of the coating.

[0064] The concentration of hydrogen atoms contained in the plasma-resistant coating of the present invention can exist in different concentrations in the grains and grain boundaries of the coating, and preferably can be uniformly maintained within a certain range in the depth or horizontal direction of the coating.

[0065] The plasma-resistant coating of the present invention can be formed by physical vapor deposition, chemical deposition, electroplating, etc., and the physical vapor deposition method can be any one or a combination of sputtering deposition, reactive sputtering deposition, laser ablation deposition method and electron beam deposition method, and the chemical deposition method can be any one or a combination of chemical vapor deposition, plasma deposition, ion-induced deposition, atomic layer deposition and atmospheric pressure plasma deposition method, and the physical vapor deposition method, chemical deposition method, electroplating method and the like can be performed sequentially to form the film.

[0066] The hydrogen contained in the plasma-resistant coating of the present invention can be injected during the deposition process of the coating, or can be injected through a post-treatment process, such as annealing in a hydrogen atmosphere or hydrogen plasma treatment.

[0067] The plasma resistance of the coating of the present invention can be etching resistance or corrosion resistance to halogen free radicals or halogen ions, etching resistance or corrosion resistance to hydrogen free radicals or hydrogen ions, and etching resistance or corrosion resistance to halogen free radicals or halogen ions accelerated by hydrogen free radicals or hydrogen ions.

[0068] The plasma resistance of the coating of the present invention can be etching resistance or corrosion resistance in a process gas containing halogen compounds and hydrogen, and can be etching resistance or corrosion resistance for a process in which halogen compound plasma process and hydrogen plasma process are performed sequentially.

[0069] The amount of hydrogen atoms contained in the plasma-resistant coating of the present invention can be controlled during the deposition process or post-treatment process of the coating. Specifically, it can be controlled by controlling the amount of hydrogen injected during the deposition process or by controlling the partial pressure of hydrogen inside the deposition chamber. It can also be controlled by controlling the amount of hydrogen injected during the post-treatment process, the partial pressure of hydrogen in the post-treatment atmosphere, the heat treatment temperature, the hydrogen plasma conditions, etc.

[0070] The hydrogen injected into the plasma-resistant coating of the present invention may be in the form of hydrogen molecules or hydrogen-containing compounds, and specifically, the hydrogen-containing compounds may be water, alcohol, hydrocarbon or other hydrogen-containing compounds. Other hydrogen-containing compounds may be compounds in which some halogen atoms in carbon halide are replaced by hydrogen.

[0071] The concentration of hydrogen atoms in the coating of the present invention is preferably 0.2 to 9 mol% (or atomic %). If the concentration of hydrogen atoms is less than 0.2 mol%, the effect of adding hydrogen atoms to improve the etching or corrosion resistance of hydrogen mixed plasma is too low, and if the concentration of hydrogen atoms exceeds 9 mol%, the bond between yttrium and oxygen in the yttrium compound may be excessively broken, leading to accelerated etching or corrosion rate and excessive particle generation due to brittleness. The concentration of hydrogen atoms in the coating is more preferably 0.2 to 8 mol%, and even more preferably 0.3 to 6 mol%.

[0072] The average grain diameter of the coating of the present invention is preferably 70 nanometers or less. This is because when the average grain diameter exceeds 70 nanometers, the relative volume of the grain boundary region becomes too large, and the etching or corrosion rate for the mixed plasma containing halogen compounds and hydrogen may become too fast. The average grain diameter can be measured by X-ray diffraction (XRD).

[0073] The porosity of the coating of the present invention is preferably 5% or lower. This is because if the porosity exceeds 5%, the density of defective portions in the pore region increases, and plasma active species easily penetrate, resulting in an excessively fast etching or corrosion rate for plasmas containing halogen compounds and hydrogen. The porosity of the coating is preferably 3% or lower, and even more preferably 1% or lower.

[0074] The hardness of the coating of the present invention is preferably 8 GPa or greater. This is because the hardness of the coating indicates its resistance to the physical impact of ions in a plasma environment. If the hardness of the coating is less than 8 GPa, the etching or corrosion rate for a mixed plasma containing halogen compounds and hydrogen is too fast.

[0075] If the coating of the present invention is yttrium oxide, the atomic ratio of yttrium to oxygen is preferably in the range of 1:0.6 to 1:2.5. This is because when the atomic ratio is less than 0.6 or more than 2.5, the atomic ratio of oxygen becomes too low or too high, which increases the possibility of defect sites.

[0076] If the coating of the present invention is yttrium aluminum oxide, the atomic ratio of yttrium to aluminum is preferably in the range of 1:0.1 to 1:7.0. This is because if the atomic ratio of yttrium to aluminum is less than 0.1 or more than 7.0, the etching or corrosion rate for the mixed plasma containing halogen compounds and hydrogen is too fast. The atomic ratio of yttrium to aluminum is more preferably 1:0.1 to 1:2.5, and even more preferably 1:0.3 to 1:2.0.

[0077] If the coating of the present invention is yttrium oxide, it is preferable that the atomic ratio of yttrium measured by energy-dispersive X-ray spectroscopy using transmission electron microscopy is within the range of 0.1 to 1.8 under the following analytical conditions. This is because if the standard deviation of the atomic ratio of yttrium is too large, the atomic ratio uniformity of yttrium oxide or yttrium aluminum oxide will be low, resulting in too fast etching or corrosion rates for mixed plasmas containing halogen compounds and hydrogen. The standard deviation of the atomic ratio of yttrium at the measurement sites in the coating and measured by the measurement method described below is preferably within the range of 0.3 to 1.4. (1) Analytical method: Energy-dispersive X-ray spectroscopy using transmission electron microscopy (2) Measurement sites: Nine regions spaced 0.2 micrometers apart in the horizontal and vertical directions on a plane parallel to the surface of the coating (3) Calculation of standard deviation: The standard deviation of the atomic ratio (molar concentration or atomic concentration) of yttrium measured at the above measurement sites

[0078] If the coating of the present invention is yttrium oxide, it is preferable that the atomic ratio of yttrium measured by scanning electron microscopy energy dispersive X-ray spectroscopy is in the range of 0.3 to 1.0 under the following analytical conditions. This is because if the standard deviation of the atomic ratio of yttrium is too large, the atomic ratio uniformity of yttrium oxide or yttrium aluminum oxide will be low, and the etching or corrosion rate for halogen-containing compound and hydrogen mixed plasma will be too fast. The standard deviation of the atomic ratio of yttrium in the coating measured at the measurement site and measured by the measurement method described below is preferably in the range of 0.4 to 0.9. (1) Analytical method: scanning electron microscopy energy dispersive X-ray spectroscopy (2) Measurement site: nine regions spaced 20 micrometers apart in the horizontal and vertical directions on a plane parallel to the surface of the coating (3) Calculation of standard deviation: the standard deviation of the atomic ratio (mole concentration or atomic concentration) of yttrium measured at the above measurement sites

[0079] For the coating of the present invention, it is preferable that, under the following measurement conditions, the standard deviation of the standardized hydrogen yield measured by elastic recoil detection analysis (ERDA) is in the range of 0.07 to 1.6. (1) Lasser Backscattering Spectroscopy (RBS) - Incident ion particles: 4He2+ - Incident ion energy: 2.0MeV - Charge of incident ion beam: 10μC - Ion incident angle (angle between the coating normal and the incident ion beam): 5° - Angle of coating sample (angle between the coating normal and the incident ion beam): 5° - Emission angle (angle between the line perpendicular to the coating surface and the line through which the reflected particles enter the sensor): 5° - Lasser Backscattering Spectroscopy (RBS) detector angle (angle formed with the extension line of the incident beam passing through the sample): 170° - Lasser Backscattering Spectroscopy (RBS) detector scattering solid angle: 3.1 mSr - Standard deviation measurement energy range: 30~700 keV - Method for obtaining standard deviation: Applying a linear regression model - Measurement sensor: PIPS (Passivated Implanted Planar Silicon) detector The sensor can be either a surface detector (SSD) or a surface detector (SSD), which can be weighted by adding a bias voltage V and determined based on the sensor specifications. (2) Elastic Recoil Detection Analysis (ERDA) - Incident Ion Particle: 4He2+ - Incident Ion Energy: 2.0MeV - Charge of Incident Ion Beam: 10μC - Angle of Coating Sample (Angle between the Propagating Ion Beam and the Normal Direction of the Coating): 75° - Ion Incident Angle (Angle between the Normal Direction of the Coating and the Incident Ion Beam): 75° - Elastic Recoil Detection Analysis (ERDA) Detector Angle (Angle formed with the extension line of the incident beam passing through the sample): 30° - Elastic Recoil Detection Analysis (ERDA) Detector Scattering Solid Angle: 2.55 mSr - Standard Deviation Measurement Energy Range: 30~700 keV - Method for Obtaining Standard Deviation: Applying a linear regression model - By installing a 10 μm Mylar foil filter in front of the sensor - Measurement Sensor: PIPS (Passivated Implanted Planar Silicon Detector) or SSD (Silicon Surface Detector), which can be weighted by adding a bias voltage V and determined based on the sensor specifications.

[0080] This is because if the concentration of hydrogen atoms varies too much in the depth direction, hydrogen ions or free radicals in the plasma become more likely to penetrate, resulting in an excessively fast etching or corrosion rate.

[0081] The present invention will be described in more detail below using examples.

[0082] Example 1

[0083] A yttrium oxide (Y2O3) coating containing hydrogen atoms is formed on a substrate using a reactive sputtering method. The substrate is ceramic, and the process pressure and internal temperature of the chamber are controlled to ensure uniform hydrogen concentration. The base pressure of the vacuum chamber is 2 mTorr, and the internal temperature of the chamber is maintained at a constant level below ~200°C.

[0084] Yttrium is used as the target material, and the RF+DC sputtering method is applied. The substrate is attached to the ceramic substrate under the conditions of DC power of 15,000 W and RF power of 800 W, and the deposition is performed while the sample roller is mounted on it and rotates at a high speed of 100 rpm to ensure the uniformity of the sample.

[0085] The oxygen flow rate during the deposition process is 120 sccm, and the hydrogen flow rate is 5 sccm. The deposition thickness of yttrium oxide (Y2O3) containing hydrogen atoms is 10 micrometers.

[0086] Example 2

[0087] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 10 sccm.

[0088] Example 3

[0089] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 30 sccm.

[0090] Example 4

[0091] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 60 sccm.

[0092] Example 5

[0093] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 80 sccm.

[0094] Example 6

[0095] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 100 sccm.

[0096] Example 7

[0097] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 120 sccm.

[0098] Example 8

[0099] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 150 sccm.

[0100] Example 9

[0101] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 200 sccm.

[0102] Comparative Example 1

[0103] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the oxygen flow rate was changed to 150 sccm and the hydrogen flow rate was changed to 0 sccm.

[0104] Comparative Example 2

[0105] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 0 sccm.

[0106] Comparative Example 3

[0107] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the oxygen flow rate was changed to 100 sccm and the hydrogen flow rate was changed to 0 sccm.

[0108] Comparative Example 4

[0109] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the oxygen flow rate was changed to 80 sccm and the hydrogen flow rate was changed to 60 sccm.

[0110] Comparative Example 5

[0111] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the oxygen flow rate was changed to 80 sccm and the hydrogen flow rate was changed to 80 sccm.

[0112] Comparative Example 6

[0113] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 1, except that the oxygen flow rate was changed to 80 sccm and the hydrogen flow rate was changed to 100 sccm.

[0114] Comparative Example 7

[0115] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 4, except that the rotation speed of the roller on which the sample was mounted was changed to 5 rpm.

[0116] Comparative Example 8

[0117] A yttrium oxide (Y2O3) coating containing hydrogen atoms was formed in the same manner as in Example 2, except that the rotation speed of the roller on which the sample was mounted was changed to 5 rpm.

[0118] Table 1 below summarizes the deposition conditions of the coatings according to Examples 1 to 9 and Comparative Examples 1 to 8. [Table 1] Oxygen flow rate (sccm) Hydrogen flow rate (sccm) The rotational speed of the drum (rpm) Example 1 120 5 100 Example 2 120 10 100 Example 3 120 30 100 Example 4 120 60 100 Example 5 120 80 100 Example 6 120 100 100 Example 7 120 120 100 Example 8 120 150 100 Example 9 120 200 100 Comparative Example 1 150 0 100 Comparative Example 2 120 0 100 Comparative Example 3 100 0 100 Comparative Example 4 80 60 100 Comparative Example 5 80 80 100 Comparative Example 6 80 100 100 Comparative Example 7 120 60 5 Comparative Example 8 120 10 5

[0119] Experiment 1 (Confirmation of the presence of hydrogen in the coating)

[0120] Secondary ion mass spectrometry (SIMS) was performed on the yttrium oxide coating prepared according to Example 4. A TOF-SIMS 5 (ION-TOF, Germany) was used as the measurement instrument, and negative mode and depth profiling were applied. A main source (Bi+, accelerating voltage 30 keV, current 1 pA), an etch source (Cs+, accelerating voltage 2 keV, current 100 nA), an analysis area of ​​100 μm x 100 μm, and an etch area of ​​400 μm x 400 μm were used, and a plasma flood gun was employed.

[0121] Figure 1 presents the results of secondary ion mass spectrometry. Referring to Figure 1, hydrogen atoms were detected in the yttrium oxide coating prepared in Example 4. However, due to the limitations of secondary ion mass spectrometry, the atomic ratio of yttrium oxide to other atoms could not be calculated.

[0122] Experiment 2 (Scanning Electron Microscopy Energy Dispersive X-ray Spectroscopy)

[0123] The atomic ratio of yttrium in the coatings manufactured according to Examples 4, 9, Comparative Examples 1, 6 to 8 was measured using scanning electron microscopy energy dispersive X-ray spectroscopy (SEM EDS).

[0124] The measurement sites for energy-dispersive X-ray spectroscopy are nine regions spaced 20 micrometers apart in the horizontal and vertical directions on a plane parallel to the surface of the coating, and Figure 2 shows the analytical regions in a scanning electron microscope image. Then, the atomic ratio and standard deviation of yttrium in the nine analytical regions are calculated.

[0125] The analysis results of Experiment Example 2 are summarized in Table 2 below.

[0126] Referring to Table 2, it can be confirmed that the deviation of the atomic ratio of yttrium decreases rapidly as the rotational speed of the sample-loaded roller increases. However, it is difficult to determine the trend of the deviation of the atomic ratio of yttrium based on the change in hydrogen flow rate. This may be because the analytical area of ​​scanning electron microscopy energy-dispersive X-ray spectroscopy is relatively larger than that of transmission electron microscopy energy-dispersive X-ray spectroscopy, thus making it impossible to significantly distinguish the deviation of the atomic ratio of yttrium in small areas. In addition, the standard deviation of the atomic ratio of yttrium using scanning electron microscopy energy-dispersive X-ray spectroscopy is generally smaller than that using transmission electron microscopy energy-dispersive X-ray spectroscopy, which is believed to be due to the relatively larger analytical area. [Table 2] Atomic ratio of yttrium (atomic %) Standard deviation Area 1 Area 2 Area 3 Area 4 Area 5 Area 6 Area 7 Area 8 Area 9 Example 4 42.36 43.47 42.34 43.52 42.13 42.88 43.11 43.97 43.21 0.62 Actual example 9 44.49 43.68 44.12 44.01 44.09 44.74 44.44 44.02 43.12 0.48 Comparative Example 1 41.79 39.69 40.89 40.66 41.69 41.75 40.57 41.76 42.28 0.82 Comparative Example 6 57.46 58.98 56.65 57.69 56.91 58.79 58.33 59.12 54.54 1.45 Comparative Example 7 51.67 50.45 49.88 46.67 51.59 50.23 49.45 45.25 46.16 2.40 Comparative Example 8 41.16 43.96 41.34 43.62 42.11 43.18 42.92 43.97 44.63 1.22

[0127] Experimental Example 3 (Transmission Electron Microscopy with Energy Dispersive X-ray Spectroscopy)

[0128] The atomic ratio of yttrium to oxygen in the coatings prepared according to Examples 4, 9, Comparative Examples 1, and Comparative Examples 6 to 8 was measured using transmission electron microscopy energy-dispersive X-ray spectroscopy (TEM EDS). The samples used for transmission electron microscopy analysis were prepared to have a thickness that allowed electron transmission using a focused ion beam after polishing with a polishing cloth.

[0129] The measurement sites for energy-dispersive X-ray spectroscopy are nine regions spaced 0.2 micrometers apart in the horizontal and vertical directions in a plane parallel to the surface of the coating, and Figure 3 shows the analytical regions in a transmission electron microscopy image. Then, the standard deviation of the atomic ratio of yttrium or oxygen in the nine analytical regions is calculated.

[0130] The analysis results of Experiment Example 3 are summarized in Table 3 below.

[0131] Referring to Table 3, it can be confirmed that as the amount of hydrogen injected increases, the deviation of the atomic ratio of yttrium increases, and it can also be confirmed that as the rotational speed of the roller carrying the loaded sample increases, the deviation of the atomic ratio of yttrium decreases rapidly.

[0132] These results contain trends not previously observed in scanning electron microscopy and energy-dispersive X-ray spectroscopy, implying that the hydrogen flow rate and sample rotation speed during the reactive sputtering process for coating formation affect the homogeneity of the atomic ratios of the coating. In particular, these trends mean they can be confirmed using analytical methods with small analytical areas and high resolution, such as transmission electron microscopy. In this invention, it has been found that the homogeneity of the atomic ratios in the micro-regions of the coating affects the etch resistance or corrosion resistance to plasma, and in this respect, transmission electron microscopy and energy-dispersive X-ray spectroscopy have been confirmed as an effective analytical method for demonstrating this. [Table 3] Atomic ratio of yttrium (atomic %) Standard deviation Area 1 Area 2 Area 3 Area 4 Area 5 Area 6 Area 7 Area 8 Area 9 Example 4 44.87 44.56 41.68 42.02 41.45 41.05 42.29 43.56 42.01 1.38 Actual example 9 47.05 43.68 42.88 46.11 43.89 45.22 47.71 44.67 43.39 1.69 Comparative Example 1 41.79 39.67 41.89 41.1 39.68 39.76 41.97 42.02 43.51 1.33 Comparative Example 6 53.1 55.3 58.2 58.56 52.34 56.56 60.13 60.45 56.11 2.87 Comparative Example 7 56.78 51.32 46.89 45.22 46.89 50.99 43.04 53.77 57.56 5.12 Comparative Example 8 45.79 43.47 39.88 41.05 38.86 40.76 44.87 47.02 46.71 3.10

[0133] Experiment 4 (Measurement of Porosity)

[0134] The results of measuring the gas adsorption specific surface area (BET) of the coatings manufactured by the Examples and Comparative Examples showed that the porosity was measured to be 0 for all coatings.

[0135] Experiment 5 (Measurement of grain diameter)

[0136] The grain diameter of the coatings manufactured by the experimental and comparative examples was measured by XRD analysis.

[0137] The measurement results are shown in Table 4 below.

[0138] Referring to Table 4, it can be confirmed that the grain diameter changes with the rotational speed of the roller carrying the sample, and the uniformity of the grain diameter increases relatively with the increase of rotational speed. [Table 4] Average grain diameter (nanometer) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 25.34 14.19 9.38 7.65 5.5 5.3 12.99 32.12 69.41 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 62.5 43.51 40.13 75.44 80.73 102.56 185.23 52.31

[0139] Experiment 6 (Measurement of Hardness)

[0140] To check the hardness of the coating, a nano-indenter (NHT3, Anton Paar) was used. As a specific condition, the indentation was 20 mN, and the coating surface was measured approximately 5 times.

[0141] In the embodiment, the hardness of the coating was measured to be greater than 8 GPa, and the measurement results are shown in Figure 18.

[0142] Experiment 7 (Measurement of hydrogen concentration and analysis of elastic recoil detection)

[0143] The hydrogen concentration of the coatings manufactured according to the Examples and Comparative Examples was measured using elastic recoil detection analysis (ERDA). Elastic recoil detection analysis was performed to measure the concentration of hydrogen atoms that could not be quantified by the secondary ion mass spectrometry used in Experimental Example 1.

[0144] The process of measuring the hydrogen concentration of the coating by elastic recoil detection analysis first uses Laserford backscattering spectroscopy (RBS) on the coating sample to obtain the flux of incident ions and the atomic percentage of yttrium and / or oxygen atoms in the coating, and then uses it as correction information for the measurement data of subsequent elastic recoil detection analysis, so as to finally obtain the hydrogen atoms in the coating.

[0145] In the apparatus used for analysis, the ion species was 4He²⁺ (2 protons + 2 neutrons, alpha particles), and a cascade ion accelerator (Pelletron linear accelerator, NEC (National Electrostatics Corp.) model 6SDH-2) was used as the ion accelerator. The incident ion energy was set to 2 MeV, and the size of the ion beam was determined by the shape of the slit through which the ion beam passed, scanning a 1 mm x 4 mm area. The incident ion beam current on the coating was set to 10 μC.

[0146] The ion beam, sample, and detector angle settings used for Elastic Recoil Detection Analysis (ERDA) and Rasford Backscattering Spectroscopy (RBS) are illustrated in detail in Figures 5A and 5B. The specific operation of the analytical equipment is as follows: α particles (4He2+) are accelerated to an energy of 2MeV using a cascade ion accelerator. The backscattered α particles at the normal angle to the sample surface near the coating are measured using Rasford Backscattering Spectroscopy, and the results are shown in Figure 5A.

[0147] Figure 5B shows a schematic diagram of elastic recoil detection analysis, in which α particles are obliquely incident on the sample surface of the coating (grazing angle with the sample surface), and recoil hydrogen atoms are measured.

[0148] The specific measurement conditions for Lasser Backscattering Spectroscopy (RBS) and Elastic Recoil Detection Analysis are as follows. (1) Lasser Backscattering Spectroscopy (RBS) - Incident ion particles: 4He2+ - Incident ion energy: 2.0MeV - Charge of incident ion beam: 10μC - Ion incident angle (angle between the coating normal and the incident ion beam): 5° - Angle of coating sample (angle between the coating normal and the incident ion beam): 5° - Emission angle (angle between the line perpendicular to the coating surface and the line through which the reflected particles enter the sensor): 5° - Detector angle of Lasser Backscattering Spectroscopy (RBS) (angle formed with the extension line of the incident beam passing through the sample): 170° - Scattering solid angle of Lasser Backscattering Spectroscopy (RBS) detector: 3.1 mSr - Standard deviation measurement energy range: 30~700 keV - Method for obtaining standard deviation: Applying a linear regression model - Measurement sensors: PIPS (Plain Injection Planar Silicon Detector) or SSD (Silicon Surface Detector), which can be weighted by adding a bias voltage V and determined based on sensor specifications. (2) Elastic Recoil Detection Analysis (ERDA) - Incident ion particle: 4He2+ - Incident ion energy: 2.0MeV - Charge of incident ion beam: 10μC - Angle of coating sample (angle between the coating normal and the propagating ion beam): 75° - Ion incident angle (angle between the coating normal and the incident ion beam): 75° - Elastic Recoil Detection Analysis (ERDA) detector angle (angle formed with the extension of the incident beam through the sample): 30° - Elastic Recoil Detection Analysis (ERDA) detector scattering solid angle: 2.55 mSr - Standard deviation measurement energy range: 30~700 keV - Method for obtaining standard deviation: Applying a linear regression model - By installing a 10 μm Mylar foil filter in front of the sensor - Measurement sensor: PIPS (Passivated Implanted Planar Silicon Detector) or SSD (Silicon Planar Detector), which can be weighted by adding a bias voltage V and determined based on sensor specifications.

[0149] Sample preparation: A 5 μm thick coating was formed on a silicon substrate, the surface was cleaned with ethanol, and heat-treated in a drying oven at 50°C for 24 hours. Subsequently, because the measurement results could be affected by contamination such as additional oxide films formed on the surface, the coating surface was etched twice by argon sputtering to a maximum value of 600 nm before measurement. In the next step, firstly, Rasford backscattering spectroscopy was performed, and then the same sample was gold-plated to a thickness of 1–2 nm in a vacuum chamber and stored in a vacuum chamber at 10⁻⁶ mbar, with continuous elastic recoil detection analysis and spectroscopy.

[0150] This process is schematically illustrated in Figure 6. Figure 6(A) is a cross-section before argon sputtering, where t1 represents the contaminated thickness during coating storage, and t2 represents the thickness measurable by elastic recoil detection analysis excluding the contaminated area. Figure 6(B) is a cross-section after argon sputtering. During the transfer to the chamber for elastic recoil detection analysis after sputtering, a contaminated layer of thickness t3 may be generated again, and t4 refers to the thickness measurable by elastic recoil detection analysis. To ensure the reproducibility of elastic recoil detection analysis, the thickness of argon sputtering can be from 100 to 700 nanometers.

[0151] Figures 7 to 10 show the results of measuring the number of hydrogen atoms in the coating film by elastic recoil detection analysis. In each figure, Figure 7 shows the results of measuring the concentration of hydrogen atoms in the coating film prepared by Example 2 by elastic recoil detection analysis, Figure 8 shows the results of Example 3, Figure 9 shows the results of Example 4, and Figure 10 shows the results of Comparative Example 6.

[0152] Referring to the diagram, the horizontal axis represents the energy of ions or atoms (recoil particles) present in the measured coating. Specifically, it is the energy emitted by hydrogen atoms or hydrogen ions towards the detector when hydrogen atoms present inside the coating collide with 4He2+ ions (alpha particles). The peak observed in the range of approximately 700–900 keV is caused by hydrogen atoms present relatively close to the surface of the coating, and its intensity is caused by water molecules that contaminate and bind to the surface of the coating. The signal observed in the range of approximately 30–700 keV is due to hydrogen atoms present at a depth deeper than the contaminated area on the surface of the coating. In this case, the normalized yield in the region with relatively low energy intensity becomes smaller than the normalized yield in the region with relatively high energy intensity because energy loss occurs when hydrogen atoms are emitted from inside the coating to the outside. Therefore, the normalized yield observed in the range of approximately 30–700 keV reflects the depth information of the presence of hydrogen atoms contained in the coating. In this context, the normalized yield value refers to the relative number of hydrogen atoms or hydrogen ions emitted per incident helium ion, and the normalized yield value derived from the energy intensity is corrected for measurements obtained by the Rasford backscattering spectroscopy method.

[0153] The concentration of hydrogen atoms present inside the coating can be quantified by the measurement results of the elastic recoil detection analysis of the examples and comparative examples. The range of standardized yield values ​​used at this time is the data of standardized yield in the range of 30~700 keV, excluding information on the contaminated surface of the coating.

[0154] The concentrations of hydrogen atoms in the examples and comparative examples, calculated from the measurement results by elastic recoil detection analysis, are summarized in Table 5 below.

[0155] Referring to Table 5, it can be confirmed that the hydrogen injection rate during the coating manufacturing process is proportional to the amount of hydrogen contained in the coating. [Table 5] Hydrogen atom concentration (mol%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 0.29 0.49 1.24 2.85 3.76 4.14 5.21 7.14 8.96 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 0.14 0.18 0.17 10.1 15.5 20.81 4.03 1.01

[0156] Experiment 8 (obtaining the standard deviation of hydrogen concentration and measurement results analyzed using elastic recoil detection)

[0157] Using the measurement results of Elastic Recoil Detection Analysis (ERDA) in Experiment 7, the standard deviation of hydrogen concentration reflecting information about the thickness direction of the coating was obtained. Although the hydrogen energy measured in Experiment 7 is not linearly inversely proportional to the depth of the coating, the magnitude of the hydrogen energy provides information reflecting the position of the coating in the thickness direction.

[0158] In the measurement results of elastic recoil detection analysis, the hydrogen energy range of 30~700 keV is the range that excludes surface contamination information of the coating. The standard deviation of hydrogen concentration specifically refers to the degree of deviation of the data in the 30~700 keV range based on the value of the linear regression line in the Y-axis direction by +σ, -σ (standard deviation: sigma), and refers to the standard deviation of the concentration of hydrogen atoms distributed in the depth direction of the coating.

[0159] The following describes in detail the process of finding the range of the area covered by the standardized production value.

[0160] First (Process A), from the original complete energy data (range from 0 keV to 2000 keV), data with energy between 30 keV and 700 keV is extracted based on the X-axis data. At this time, the theoretical model of the linear regression model is used. Specifically, it is given in the form of n independent variables Xn and strain Y, in the form Y=β0+β1X1+β2X2+.... The linear independent variables of the given data are specified as n=1, and the ordinary least square (OLS) is , that is, in order to find the value of βn that minimizes the sum of squares of the entire data in Y=β0 +β1X1+β2X2+...+βnXn, the following gradient descent process is used to calculate it. Among them, the variables are as follows: α: learning rate J (cost function) is defined as follows. Using the equation with the minimum value of the previous process, i.e., Ordinary Least Squares (OLS), if the interval of convergence of the value is calculated, a linear graph is obtained (linear graph, Ylinear-regression= mx +b, slope is m, Y-intercept is b).

[0161] Next, based on the data in the range of 30 keV to 700 keV in process A, the sampling standard deviation σ (standard deviation: sigma) is calculated based on the Y-axis value.

[0162] Then, based on the linear regression line in the central part with slope m and Y-intercept, two additional lines can be calculated: the upper boundary line defined by Ylinear-regression+2σ (standard deviation: sigma) (see Figures 11 to 17) and the lower boundary line defined by Ylinear-regression-2σ (standard deviation: sigma) (see Figures 11 to 17).

[0163] At this point, the range of the standardized production value can be specified as the area between the two additional lines: Ylinear-regression+2σ (standard deviation: σ sigma) and Ylinear-regression-2σ (standard deviation: σ sigma).

[0164] Figures 11 to 17 show the range of normalized yields of hydrogen atoms in the energy region of 30 to 700 keV as measured by elastic recoil detection analysis. In each figure, Figure 11 shows the standard deviation of the normalized yield of the coating produced by Example 2, Figure 12 shows the standard deviation of the normalized yield of Example 3, Figure 13 shows the standard deviation of the normalized yield of Example 6, Figure 14 shows the standard deviation of the normalized yield of Comparative Example 2, Figure 15 shows the standard deviation of the normalized yield of Comparative Example 6, Figure 16 shows the standard deviation of the normalized yield of Comparative Example 7, and Figure 17 shows the standard deviation of the normalized yield of Comparative Example 8.

[0165] Table 6 below summarizes the results of the standard deviation of the standardized yield of the coatings manufactured by the Examples and Comparative Examples.

[0166] Referring to Table 6, it can be confirmed that the standard deviation of the results tends to increase with the increase of hydrogen injection volume, and it can also be confirmed that the standard deviation decreases rapidly with the increase of the rotational speed of the roller loaded with the sample. [Table 6] Standard deviation of standardized output Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 0.08 0.095 0.189 0.588 0.764 1.121 1.243 1.376 1.511 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 0.051 0.054 0.052 1.741 1.918 2.767 3.365 0.352

[0167] Experiment 9 (Analysis of plasma toughness characteristics, CF4+O2 etching gas)

[0168] Plasma toughness tests were performed on the coatings manufactured by the Examples and Comparative Examples using CF4+O2 gas. A capacitively coupled plasma (CCP) device was used as the plasma etching apparatus, and the plasma etching conditions were set as follows: power output of 300 W CCP output, process gas of a 2:1 mixture of CF4 and O2 gas, process pressure of 30 mtorr, and plasma etching time of 3 hours to perform the experiment.

[0169] To measure the etching amount, a portion of the coating was masked with Kapton tape before the plasma etching experiment, and the step difference between the masked area and the uncovered area exposed to plasma after the etching experiment was measured using AlphaStep. Specifically, 20mm x 20mm x 2t Al2O3 was typically used as the substrate, and the step difference of the sample under each condition was recorded as the etching amount.

[0170] The results of Experiment 9 are summarized in Table 7 below.

[0171] Referring to Table 7, it can be seen that coatings with controlled hydrogen concentrations within a certain range exhibit excellent plasma resistance characteristics. Furthermore, when the coatings have similar hydrogen concentration ranges, coatings with smaller depth-direction deviations in hydrogen concentration exhibit significantly superior plasma resistance characteristics. [Table 7] Etching depth (nm) Relative etching rate (based on Comparative Example 2) Example 1 320.7 0.78 Example 2 310.3 0.76 Example 3 298.4 0.73 Example 4 279.1 0.68 Example 5 265.4 0.65 Example 6 263.5 0.64 Example 7 276.8 0.67 Example 8 294.1 0.72 Example 9 312.2 0.76 Comparative Example 1 422.1 1.03 Comparative Example 2 410.5 1 Comparative Example 3 433.8 1.06 Comparative Example 4 421.4 1.03 Comparative Example 5 442.5 1.08 Comparative Example 6 469.8 1.14 Comparative Example 7 542.1 1.32 Comparative Example 8 424.3 1.03

[0172] Experiment 10 (Analysis of plasma toughness characteristics, CF4+O2+H2 etching gas)

[0173] Plasma toughness tests were performed on the coatings manufactured by the Examples and Comparative Examples. A capacitively coupled plasma (CCP) device was used as the plasma etching apparatus. As plasma etching conditions, the power output was set to 300 W CCP output, CF4+O2 was injected at a ratio of 2:1 for 30 minutes as the process gas, and then H2+Ar was injected sequentially at a ratio of 3:1 for 2 hours and 30 minutes. The pressure of each process was set to 20 mtorr, and the total plasma etching time was set to 3 hours.

[0174] To measure the etching amount, a portion of the coating was masked with Kapton tape before the plasma etching experiment, and the step difference between the masked area and the unmasked area after plasma irradiation was measured using AlphaStep. Specifically, 20mm x 20mm x 2t Al2O3 was typically used as the substrate, and the step difference of the sample under each condition was recorded as the etching amount.

[0175] The results of Experiment 10 are summarized in Table 8 below.

[0176] Referring to Table 8, it can be seen that the trend of the plasma toughness of the coating is similar to that in Experimental Example 9. However, in the experimental example where the roller with the sample was rotated, the improvement in plasma toughness tended to be more significant than the improvement in halogen-containing etching gas. [Table 8] Etching depth (nm) Relative etching rate (based on Comparative Example 2) Example 1 173.2 0.78 Example 2 160.6 0.73 Example 3 156.2 0.71 Example 4 148.5 0.67 Example 5 141.4 0.64 Example 6 139.8 0.63 Example 7 154.4 0.70 Example 8 167.6 0.76 Example 9 185.7 0.84 Comparative Example 1 231.6 1.05 Comparative Example 2 220.7 1 Comparative Example 3 228.4 1.03 Comparative Example 4 238.4 1.08 Comparative Example 5 251.3 1.14 Comparative Example 6 268.6 1.22 Comparative Example 7 491.3 2.23 Comparative Example 8 224.2 1.02 [Simplified Explanation of the Diagram]

[0031] Figure 1 shows the results of secondary ion mass spectrometry (SIMS) for a coating according to one embodiment of the present invention.

[0032] Figure 2 shows a scanning electron microscope (SEM) image of the coating according to one embodiment of the present invention and a measurement area of ​​energy dispersive X-ray spectroscopy (EDS).

[0033] Figure 3 shows a transmission electron microscopy (TEM) image of the coating according to one embodiment of the present invention and a measurement area by energy dispersive X-ray spectroscopy (EDS).

[0034] Figure 4 is a photograph of an analytical apparatus for elastic recoil detection analysis (ERDA) used to analyze a coating according to one embodiment of the present invention.

[0035] Figure 5A illustrates the sample and detector setup for performing Rasherford backscattering spectroscopy (RBS).

[0036] Figure 5B illustrates the sample and detector setup for performing elastic recoil detection analysis.

[0037] Figure 6 is a diagram illustrating the process of removing contaminants from the surface of the coating during the application of elastic recoil detection analysis.

[0038] Figures 7 to 10 show the results of the measurement of the amount of hydrogen atoms in the coating by elastic recoil detection analysis.

[0039] Figures 11 to 17 show the standard deviation of the normalized yield of hydrogen atoms measured by elastic recoil detection analysis.

[0040] Figure 18 shows the measurement results of the hardness of the coating.

Claims

1. A coating formed on the surface of a vacuum chamber wall or internal component used in the manufacture of a semiconductor or display device, wherein the coating contains a yttrium compound, is resistant to plasma, and contains a predetermined concentration of hydrogen atoms.

2. The coating as claimed in claim 1, wherein the yttrium compound is yttrium oxide or yttrium aluminum oxide.

3. The coating of claim 2, wherein the yttrium oxide has an atomic ratio of yttrium to oxygen in the range of 1:0.6 to 1:2.

5.

4. The coating of claim 2, wherein the yttrium aluminum oxide has an atomic ratio of yttrium to aluminum in the range of 1:0.1 to 1:7.

0.

5. The coating as claimed in claim 1, wherein the concentration of hydrogen atoms contained in the coating is 0.2 to 9 atoms.

6. The coating as requested in item 5, wherein the concentration of hydrogen atoms is measured by elastic recoil detection analysis.

7. The coating as requested in item 1, wherein the porosity of the coating is less than 5%.

8. The coating as claimed in claim 1, wherein the coating includes crystals.

9. The coating as claimed in claim 1, wherein the average grain diameter of the coating is 70 nanometers or less.

10. The coating as claimed in claim 1, wherein the hardness of the coating is 8 GPa or greater.

11. For the coating as requested in item 1, wherein the standard deviation of the normalized hydrogen yield measured by energy elastic recoil detection analysis of the coating is in the range of 0.07 to 1.6 under the following measurement conditions: (1) Rasford backscattering spectroscopy (RBS) - Incident ion particle: 4He2+ - Incident ion energy: 2.0 MeV - Charge of incident ion beam: 10 μC - Ion incident angle (angle between the coating normal and the incident ion beam): 5° - Rasford backscattering spectroscopy (RBS) detector angle (angle formed with the extension of the incident beam through the sample): 170° - Rasford backscattering spectroscopy (RBS) detector scattering solid angle: 3.1 mSr - Standard deviation measurement energy range: 30~700 keV (2) Elastic recoil detection analysis (ERDA) - Incident ion particle: 4He2+ - Incident ion energy: 2.0 MeV - Incident ion beam charge: 10 μC - Ion incident angle (angle between the coating normal and the incident ion beam): 75° - Elastic recoil detection analysis (ERDA) detector angle (angle formed with the extension of the incident beam through the sample): 30° - Elastic recoil detection analysis (ERDA) detector scattering solid angle: 2.55 mSr - Standard deviation measurement energy range: 30~700 keV - Method for obtaining standard deviation: application of linear regression model.

12. The coating of claim 11, wherein elastic recoil detection analysis is performed after the coating is removed from the surface to a thickness of 100 to 700 nanometers by argon ion sputtering.

13. The coating as claimed in claim 3, wherein the atomic ratio of yttrium in the yttrium oxide is within a standard deviation range of 0.1 to 1.8 under the following analytical conditions: - Analytical method: Energy dispersive X-ray spectroscopy using a transmission electron microscope - Measurement sites: Nine regions spaced 0.2 micrometers apart in the horizontal and vertical directions on a plane parallel to the surface of the coating - Calculation of standard deviation: The standard deviation of the ratio of yttrium atoms measured at the above measurement sites.

14. A vacuum chamber wall or internal component used in the manufacture of a semiconductor or display device, comprising a coating as claimed in any one of claims 1 to 13.