Coating film and vacuum chamber component comprising same

Abstract

The coating film of the present invention is formed on the surface of a vacuum chamber wall or internal component used for manufacturing semiconductors or display devices, wherein the coating film contains an yttrium compound, has resistance to plasma, and contains hydrogen in a predetermined ratio.

Description

Coating film and vacuum chamber components containing the same

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

[0002] Plasma-based processes are widely used in the manufacturing of semiconductors and display devices. Plasma is primarily used in deposition and etching processes to form and pattern the metal, semiconductor, and insulating films that make up semiconductor devices.

[0003] Halogen compounds are mainly used as etching gases in the etching process, and specifically, fluorine compounds, chlorine compounds, and bromine compounds can be used. These etching gases are activated into ions and radicals in the plasma to induce etching.

[0004] In addition to etching the substrate, these etching processes inevitably involve etching or corrosion of components within the vacuum chamber used to generate plasma. This etching or corrosion of components shortens the lifespan and cleaning cycle of chamber components, and etch byproducts can fall onto the substrate, generating particles or contaminating the etching gas itself.

[0005] To address these issues, materials with plasma resistance, i.e., resistance to plasma etching or corrosion, are being studied. It goes without saying that plasma-resistant materials must also exhibit high etching resistance to etching gases.

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

[0007] A related prior art document is Korean Patent Publication No. 2014-0033587. The prior art document discloses an yttria-zirconia composite oxide having corrosion resistance to plasma, characterized in that the yttria and zirconia contents are 95 to 45 wt%: 5 to 55 wt%, and the yttria and zirconia form a solid solution when sintered.

[0008] It is thought that various factors of the coating film affect the plasma resistance, and the currently known factors include porosity related to the density of the film, interatomic bonding force related to chemical reactivity with etching active species, and crystallinity-related factors such as crystalline or amorphous.

[0009] Recently, as the line width of semiconductor circuits has become narrower, the conventional etching process using halogen compound plasma is showing its limitations, and active development is being conducted on a process that performs plasma etching by adding hydrogen gas together with the existing etching gas.

[0010] This hydrogen-added etching process clearly reveals the limitations of existing known plasma-resistant materials, and therefore, there is a great need to develop a coating film with high plasma resistance for the etching process performed by adding hydrogen together with existing halo gases.

[0011] The first problem to be solved by the present invention is to provide a coating film having improved etching resistance or corrosion resistance against a halogen-based gas or a mixed plasma of a halogen-based gas and hydrogen gas.

[0012] The second problem to be solved by the present invention is to provide a vacuum chamber component including the coating film.

[0013] In order to achieve the first object, the present invention provides a coating film formed on the surface of a wall or internal component of a vacuum chamber used in the manufacture of semiconductors or display devices, wherein the coating film comprises an yttrium compound, has resistance to plasma, and is characterized in that it contains hydrogen atoms in a predetermined concentration.

[0014] According to one embodiment of the present invention, the yttrium compound may be yttrium oxide or yttrium aluminum oxide.

[0015] According to another embodiment of the present invention, it is preferable that the yttrium oxide has an atomic ratio of yttrium and oxygen in the range of 1:0.60 to 1:2.5.

[0016] According to another embodiment of the present invention, it is preferable that the yttrium aluminum oxide has an atomic ratio of yttrium and aluminum in the range of 1:0.1 to 1:7.0.

[0017] According to another embodiment of the present invention, the concentration of hydrogen atoms included in the coating film is preferably 0.2 to 9 mol% (or atomic%).

[0018] According to another embodiment of the present invention, the concentration of the hydrogen atoms can be measured by Elastic Recoil Detection Analysis.

[0019] According to another embodiment of the present invention, the porosity of the coating film is preferably 5% or less.

[0020] According to another embodiment of the present invention, the coating film may include a crystalline substance.

[0021] According to another embodiment of the present invention, it is preferable that the coating film has a grain size (average diameter of grains) of 70 nanometers or less.

[0022] According to another embodiment of the present invention, the hardness of the coating film is preferably 8 GPa or more.

[0023] According to another embodiment of the present invention, it is preferable that the standard deviation of the standardized yield of hydrogen measured by Elastic Recoil Detection Analysis (ERDA) under the following measurement conditions for the coating film is in the range of 0.07 to 1.6.

[0024] (1) Rutherford backscattering spectroscopy (RBS)

[0025] - Incident ion particles: 4 He 2+

[0026] - Incident ion energy: 2.0 MeV

[0027] - Incident ion beam charge: 10μC

[0028] - Ion incidence angle (angle between the normal direction of the coating film and the incident ion beam): 5°

[0029] - Rutherford backscattering spectroscopy (RBS) detector angle (angle formed by the incident beam with the extension line penetrating the sample): 170°

[0030] - Rutherford backscattering spectroscopy (RBS) detector scattering solid angle: 3.1 mSr

[0031] - Standard deviation measurement energy range: 30~700 keV

[0032]

[0033] (2) Elastic Resonance Analysis (ERDA)

[0034] - Incident ion particles: 4 He 2+

[0035] - Incident ion energy: 2.0 MeV

[0036] - Incident ion beam charge: 10μC

[0037] - Ion incidence angle (angle between the normal direction of the coating film and the incident ion beam): 75°

[0038] - Detector angle of elastic refractive index (ERDA) (angle formed by the incident beam with the extension line penetrating the sample): 30°

[0039] - Detector scattering solid angle of elastic spectroscopy (ERDA): 2.55 mSr

[0040] - Standard deviation measurement energy range: 30~700 keV

[0041] - Method for deriving standard deviation: Applying a linear regression model

[0042]

[0043] According to another embodiment of the present invention, the elastic recoil detection analysis (ERDA) may be performed by removing 100 to 700 nanometers from the surface of the coating film by argon ion sputtering.

[0044] According to another embodiment of the present invention, the yttrium atomic ratio of the yttrium oxide is preferably in the range of a standard deviation of 0.1 to 1.8 under the following analysis conditions.

[0045] - Analysis method: Transmission electron microscope energy dispersive spectroscopy

[0046] - Measurement area: 9 areas spaced 0.2 micrometers apart in the horizontal and vertical directions on a plane parallel to the surface of the coating film

[0047] - Standard deviation calculation: Standard deviation of the yttrium atomic ratio measured at the above measurement site

[0048] In order to achieve the second object, the present invention provides a vacuum chamber wall or internal component used in the manufacture of a semiconductor or display device, including the coating film.

[0049] The coating film of the present invention has the following effects.

[0050] (1) It has high etching resistance or corrosion resistance against plasma, and in particular, it has high etching resistance or corrosion resistance in a plasma process consisting of a mixed gas of a halogen compound and hydrogen or a sequential plasma process using a halogen compound and hydrogen.

[0051] (2) The hydrogen atom concentration of the coating film is controlled within a predetermined range to improve plasma resistance.

[0052] (3) The concentration of hydrogen atoms in the depth direction of the coating film is maintained at a constant level within a predetermined range, so that hydrogen ions or radicals inside the plasma can be effectively suppressed from penetrating in the depth direction of the coating film.

[0053] (4) The porosity is controlled to a low level, thereby suppressing rapid movement of etching active species through the pores within the coating film, thereby improving etching resistance or corrosion resistance.

[0054] (5) By maintaining the yttrium atomic ratio and its deviation in the horizontal direction of the coating film within a certain range, the deviation of etching or corrosion in areas where the atomic ratio is not homogeneous is reduced and the possibility of particle generation is lowered.

[0055] Figure 1 shows the results of secondary ion mass spectrometry (SIMS) for a coating film according to one embodiment of the present invention.

[0056] FIG. 2 shows a scanning electron microscope (SEM) image and an energy dispersive X-ray spectroscopy (EDS) measurement area of ​​a coating film according to one embodiment of the present invention.

[0057] FIG. 3 shows a transmission electron microscope (TEM) image and an energy dispersive X-ray spectroscopy (EDS) measurement area of ​​a coating film according to one embodiment of the present invention.

[0058] FIG. 4 is a photograph of an analysis device used for Elastic Recoil Detection Analysis (ERDA) for analyzing a coating film according to one embodiment of the present invention.

[0059] Figure 5a illustrates the sample and detector setup positions for performing Rutherford Backscattering Spectrometry (RBS).

[0060] Figure 5b illustrates the sample and detector setup positions for performing elastic recoil detection.

[0061] Figure 6 is a drawing for explaining the process of removing surface contamination of a coating film during the process of applying the elasticity measurement method.

[0062] Figures 7 to 10 show the results of measuring the amount of hydrogen atoms contained in a coating film using an elastic semiconductivity measurement method.

[0063] Figures 11 to 17 show the standard deviation of the standardized yield of hydrogen atoms measured by the elastic semiconductivity measurement method.

[0064] Figure 18 shows the results of hardness measurement for the coating film.

[0065] The coating film of the present invention is a coating film formed on the surface of a wall or internal component of a vacuum chamber used in the manufacture of semiconductor or display devices, and is characterized in that the coating film contains an yttrium compound, has resistance to plasma, and contains hydrogen atoms in a predetermined ratio.

[0066] The inventors of the present invention have been conducting research for a long time on a coating film having high etching resistance to halogen compounds and hydrogen gas plasma, and have explored the cause and mechanism by which hydrogen ions or radicals accelerate etching or corrosion of the coating film, and have discovered an important fact that can prevent acceleration of etching or corrosion by hydrogen ions or radicals.

[0067] The etching process of a coating film using a plasma of a generally known etchant gas is as follows. The first step is that the etching active species contained in the plasma, such as halogen ions or radicals such as fluorine, chlorine, and bromine, react with the elements constituting the coating film on the surface. At this time, the reactivity is affected by the thermodynamic stability of the reactants constituting the coating film and the thermodynamic stability of the products created by the surface reaction. 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 step is the vapor pressure of the products created through the surface reaction. If the products of the surface reaction have a high vapor pressure, the reaction products will evaporate from the surface of the coating film, continuously etching the coating film. Additionally, in the reactive ion etching process, the positive ions present in the plasma can accelerate this reaction and evaporation by continuously colliding with the coating film.

[0068] Currently known plasma-resistant coatings contain factors that inhibit the etching process. Factors involved in the first stage of the etching process inhibit the reaction between etching-active species and surface compounds of the coating. The characteristics of these coatings are that the bonds between internal atoms within the coating are strong, making it difficult to cleave the interatomic bonds for surface reactions. Furthermore, the thermodynamic energy levels of the reactants and products are set to inhibit the reaction. From this perspective, yttrium oxide satisfies the above conditions to a significant degree, and the development direction of plasma-resistant coatings has been set to achieve higher plasma resistance by further controlling crystallinity, atomic molar ratio, etc.

[0069] In plasma-resistant coatings, the factors involved in the second stage of the etching process are those that impede the continuation of the reaction while removing the reaction products. For the coating to have high plasma resistance, the vapor pressure of the substance produced through the surface reaction must be low. In fact, the boiling point of silicon tetrafluoride (SiF4), which is produced when silicon atoms react with fluorine atoms, is -90℃, whereas the boiling points of aluminum trifluoride (AlF3) and yttria (Y2O3), which are produced when aluminum atoms and yttrium atoms react with fluorine, are known to be very high at 1,297℃ and 1,387℃, respectively.

[0070] Therefore, it cannot be denied that the type of compound and its atomic molar ratio, which are the characteristics of the compound itself that constitutes the coating film, are the primary factors affecting plasma resistance.

[0071] Even when compounds share the same chemical formula or atomic ratio, secondary factors such as coating film density and crystallinity can also affect plasma resistance. These secondary factors are influenced by the coating film's deposition method and conditions, and efforts to find optimal process conditions and properties have been among the primary efforts to improve plasma resistance.

[0072] The inventors of the present invention, based on the principle of etching or corrosion in the plasma environment, have tried to find the cause of accelerated etching of a coating film in a plasma in which hydrogen is added to a halogen compound, and have investigated factors related thereto.

[0073] One of the characteristics of hydrogen reactive species, i.e. hydrogen ions or hydrogen radicals, existing within plasma is that their atomic size is extremely small. It is thought that the etching or corrosion process of the coating film by plasma is not a phenomenon that occurs when the reaction products evaporate at low pressure, but rather a phenomenon in which some of the areas near the surface where the reaction products or intermediate products exist exist, and the area near the surface where the plasma ion bombardment is applied, causing some of the areas near the surface of the coating film to collapse and escape to the outside of the surface. In addition, for this collapse and detachment of the coating film to occur effectively, the interatomic bonds of the coating film or reaction products must be partially weakened. It is thought that hydrogen that has penetrated from the surface of the coating film to a certain depth due to the plasma ion bombardment will effectively perform this role.

[0074] In order to prevent etching or corrosion by the above-mentioned hydrogen-active species, it is necessary to suppress the penetration of the hydrogen-active species in the thickness direction of the coating film, and to suppress the weakening of the interatomic bonding force of the coating film by the penetrated hydrogen-active species.

[0075] Based on this reasoning, the inventors of the present invention were able to develop a coating film that significantly improved resistance to plasma of a halogen compound containing hydrogen or a hydrogen plasma and halogen compound plasma process.

[0076] The plasma resistant coating film of the present invention is characterized by injecting hydrogen during or after the film formation process and controlling the concentration within a certain range.

[0077] Several reasons are thought to be responsible for the high etching or corrosion resistance of the hydrogen contained in the coating film to hydrogen-added plasma.

[0078] The first is that hydrogen atoms bond to defects on the surface or within the coating film, thereby enhancing the chemical and physical stability of the film. Yttrium compound coatings formed through physical or chemical vapor deposition inevitably have defects on the surface or within the film that are not stably bonded. These defects may contain dangling bonds, which are pairs of electrons that cannot bond to surrounding atoms. These defects are highly reactive and therefore highly susceptible to reaction with etching-active species. Furthermore, the defects themselves can weaken the physical strength of the coating film.

[0079] Hydrogen injected during or after the formation of the coating film can react with electrons that did not participate in the interatomic bonding at these defective sites, thereby weakening the reactivity of the defective sites and improving the physical properties. However, the function of this hydrogen can vary depending on the concentration of hydrogen atoms within the compound of the coating film. That is, an appropriate concentration of hydrogen atoms can function to stabilize the defective sites of the coating film, but a concentration of hydrogen atoms exceeding a certain amount can have the negative effect of destroying the stable interatomic bonding of the compounds that make up the coating film, and can impart brittle properties to the coating film, causing more particles to be generated during the plasma etching process. Furthermore, this negative effect caused by hydrogen atoms can mean the destruction of crystallinity. The present invention discloses a plasma-resistant coating film in which the concentration of hydrogen atoms is controlled within a predetermined range in order to maximize the positive function of the added hydrogen.

[0080] The second effect is the inhibition of plasma hydrogen-active species penetration by the hydrogen contained in the coating film. From this perspective, it is crucial that the concentration of hydrogen atoms contained in the coating film does not exceed a certain depth-wise deviation. To this end, the present invention controls the depth-wise deviation of the hydrogen atom concentration of the coating film, which is resistant to hydrogen-containing plasma, within a predetermined range.

[0081] In addition, one of the factors for maintaining the concentration of hydrogen atoms constant within a predetermined range in the depth direction of the coating film is to maintain the atomic molar ratio of yttrium atoms, which is one of the elements constituting the yttrium compound coating film, constant in the horizontal and vertical directions of the coating film.

[0082] Embodiments of the present invention are described below.

[0083] In the plasma-resistant coating film of the present invention, the term "plasma resistance" means etching resistance against plasma or resistance to corrosion caused by collective detachment of particles. In addition, the plasma defining plasma resistance refers to various plasmas used in semiconductor or display processes, and may specifically refer to plasma used in an etching process, and may particularly refer to plasma using a halogen compound and hydrogen gas or both sequentially.

[0084] The plasma-resistant coating film of the present invention may be an inorganic oxide, an inorganic nitride, or an inorganic fluoride, and specifically may be a compound containing yttrium, zirconium, titanium, or aluminum, and is not particularly limited as long as it is any other material having plasma resistance. Specifically, the coating film may be composed of yttrium oxide (yttria), yttrium aluminum oxide, zirconium oxide, aluminum oxide, titanium oxide, titanium nitride, aluminum oxynitride, yttrium fluoride, yttrium oxyfluoride, or a mixture thereof, and in the case of yttrium aluminum oxide, the atomic ratio of yttrium, oxygen, and aluminum may be variously changed. In addition, the plasma-resistant coating film may be composed in the form of a mixture in which a plurality of such compounds are blended. The coating film may be crystalline, amorphous, or nanocrystalline, and may also be a composite phase in which crystalline and amorphous phases are mixed in a predetermined range.

[0085] The hydrogen atoms included in the plasma-resistant coating film of the present invention may be chemically bonded to some of the atoms constituting the coating film or exist in a physically trapped state inside, and the concentration of the hydrogen atoms may be quantified as an atomic molar ratio with respect to the compound constituting the coating film. Secondary ion mass spectrometry (SIMS), elastic recoil detection (or energy recoil detection analysis, ERDA) may be used to quantify the concentration of the hydrogen atoms, and other known analysis methods capable of quantitatively detecting hydrogen may be used.

[0086] The substrate of the plasma-resistant coating film of the present invention may be made of a material such as metal, ceramic, or semiconductor material, and the chamber components constituting the substrate may be a chamber wall, a chamber upper and lower surface, a substrate support, a gas shower head, a window, or the like, and as long as it constitutes a component inside the plasma process chamber, the use and material thereof are not limited.

[0087] The concentration of hydrogen atoms included in the plasma-resistant coating film of the present invention may increase or decrease in the depth direction of the coating film, and preferably, uniformity may be maintained within a certain range in the depth direction of the coating film.

[0088] The concentration of hydrogen atoms included in the plasma-resistant coating film of the present invention may exist at different concentrations in the grains and grain boundaries of the coating film, and preferably, uniformity may be maintained within a certain range in the depth or horizontal direction of the coating film.

[0089] The plasma-resistant coating film of the present invention can be formed by a physical deposition method, a chemical deposition method, an electroplating method, etc., and the physical deposition method can be any one of a sputtering deposition method, a reactive sputtering deposition method, a laser ablation deposition method, an electron beam deposition method, or a combination thereof, and the chemical deposition method can be any one of a chemical vapor deposition method, a plasma deposition method, an ion-induced deposition method, an atomic layer deposition method, an atmospheric pressure plasma deposition method, or a combination thereof, and the physical deposition method, the chemical deposition method, the electroplating method, etc. can be sequentially performed to form a film.

[0090] The hydrogen included in the plasma-resistant coating film of the present invention can be injected during the deposition process of the coating film, or can be injected through a post-treatment process such as an annealing process in a hydrogen atmosphere or hydrogen plasma treatment.

[0091] The plasma resistance of the coating film of the present invention may be etching resistance or corrosion resistance against halogen radicals or halogen ions, etching resistance or corrosion resistance against hydrogen radicals or hydrogen ions, or etching resistance or corrosion resistance against halogen radicals or halogen ions accelerated by hydrogen radicals or hydrogen ions.

[0092] The plasma resistance of the coating film of the present invention may be etching resistance or corrosion resistance in a process gas containing both a halogen compound and hydrogen, and may be etching resistance or corrosion resistance for a process in which a halogen compound plasma process and a hydrogen plasma process are sequentially performed.

[0093] The amount of hydrogen atoms included in the plasma-resistant coating film of the present invention can be controlled during the deposition process or post-treatment process of the coating film, and specifically, can be controlled by controlling the amount of hydrogen injected during the deposition process or by controlling the hydrogen partial pressure inside the deposition chamber, and can be controlled by controlling the amount of hydrogen injected during the post-treatment process, the hydrogen partial pressure of the post-treatment atmosphere, the heat treatment temperature, and the conditions of the hydrogen plasma.

[0094] The hydrogen injected into the plasma-resistant coating film of the present invention may be injected in the form of hydrogen molecules or a compound containing hydrogen. Specifically, the compound containing hydrogen may be water, alcohol, hydrocarbon, or another compound containing hydrogen. The other compound containing hydrogen may be a compound in which some halogen atoms in a halogenated carbon are replaced with hydrogen.

[0095] The concentration of hydrogen atoms contained in the coating film 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 improving the etching or corrosion resistance against hydrogen-mixed plasma by adding hydrogen atoms is excessively low, and if it exceeds 9 mol%, the bond between yttrium and oxygen in the yttrium compound is excessively destroyed, so that the etching or corrosion rate increases, and the brittle nature may cause excessive particle generation. The concentration of hydrogen atoms contained in the coating film is more preferably 0.2 to 8 mol%, and even more preferably 0.3 to 6 mol%.

[0096] The average grain diameter of the coating film of the present invention is preferably 70 nanometers or less. This is because if the average grain diameter exceeds 70 nanometers, the relative volume of the grain boundary region becomes excessively large, which may result in an excessively fast etching or corrosion rate for a mixed plasma of a halogen compound and hydrogen. The average grain diameter can be measured by X-ray diffraction (XRD).

[0097] The porosity of the coating film of the present invention is preferably 5% or less. If the porosity exceeds 5%, the density of defective sites in the pore region increases, and the penetration of plasma active species is facilitated, resulting in an excessively fast etching or corrosion rate for the mixed plasma of halogen compounds and hydrogen. The porosity of the coating film is more preferably 3% or less, and even more preferably 1% or less.

[0098] The hardness of the coating film of the present invention is preferably 8 GPa or higher. The hardness of the coating film refers to the resistance to the physical impact of ions in a plasma environment. Therefore, if the hardness of the coating film is less than 8 GPa, the etching or corrosion rate against the mixed plasma of halogen compounds and hydrogen is excessively fast.

[0099] When the coating film of the present invention is yttrium oxide, the atomic ratio of yttrium and oxygen is preferably in the range of 1:0.6 to 1:2.5. This is because when the atomic ratio is less than 1:0.6 or exceeds 1:2.5, the oxygen atomic ratio becomes excessively low or high, increasing the possibility of occurrence of defective sites.

[0100] When the coating film of the present invention is yttrium aluminum oxide, the atomic ratio of yttrium and aluminum is preferably in the range of 1:0.1 to 1:7.0. This is because when the atomic ratio of yttrium and aluminum is less than 1:0.1 or more than 1:7.0, the etching or corrosion rate for the mixed plasma of halogen compounds and hydrogen is excessively fast. The atomic ratio of yttrium and aluminum is more preferably 1:0.1 to 1:2.5, and even more preferably 1:0.3 to 1:2.0.

[0101] When the coating film of the present invention is yttrium oxide, it is preferable that the atomic ratio of yttrium measured by transmission electron microscope energy dispersive spectroscopy under the conditions below is in the standard deviation range of 0.1 to 1.8 under the analysis conditions below. If the standard deviation of the atomic ratio of yttrium is too large, the atomic ratio uniformity of yttrium oxide or yttrium aluminum oxide is low, resulting in an excessively fast etching or corrosion rate for a mixed plasma of a halogen compound and hydrogen. It is more preferable that the standard deviation of the atomic ratio of yttrium measured in the coating film at the measuring portion and by the measuring method below is in the range of 0.3 to 1.4.

[0102] (1) Analysis method: Transmission electron microscope energy dispersive spectroscopy

[0103] (2) Measurement area: 9 areas spaced 0.2 micrometers apart in the horizontal and vertical directions on a plane parallel to the surface of the coating film.

[0104] (3) Calculation of standard deviation: Standard deviation of the yttrium atomic ratios (molar concentration or atomic concentration) measured at the above measurement site

[0105] When the coating film of the present invention is yttrium oxide, it is preferable that the atomic ratio of yttrium measured by scanning electron microscope energy dispersive spectroscopy is in the standard deviation range of 0.3 to 1.0 under the analysis conditions below. If the standard deviation of the atomic ratio of yttrium is too large, the uniformity of the atomic ratio of yttrium oxide or yttrium aluminum oxide is low, resulting in an excessively fast etching or corrosion rate for a mixed plasma of a halogen compound and hydrogen. It is more preferable that the standard deviation of the atomic ratio of yttrium measured in the coating film by the measuring portion and measuring method below is in the range of 0.4 to 0.9.

[0106] (1) Analysis method: Scanning electron microscope energy dispersive spectroscopy

[0107] (2) Measurement area: 9 areas spaced 20 micrometers apart in the horizontal and vertical directions on a plane parallel to the surface of the coating film.

[0108] (3) Calculation of standard deviation: Standard deviation of the yttrium atomic ratio (molar concentration or atomic concentration) measured at the above measurement site

[0109] For the coating film of the present invention, it is preferable that the standard deviation of the standardized yield of hydrogen measured by the Elastic Recoil Detection Analysis (ERDA) under the following measurement conditions be in the range of 0.07 to 1.6.

[0110] (1) Rutherford backscattering spectroscopy (RBS)

[0111] - Incident ion particles: 4 He 2+

[0112] - Incident ion energy: 2.0 MeV

[0113] - Incident ion beam charge: 10μC

[0114] - Ion incidence angle (angle between the normal direction of the coating film and the incident ion beam): 5°

[0115] - Angle of the coating film sample (angle between the vertical direction of the coating film and the incident ion beam): 5°

[0116] - Exit angle (the angle at which the reflected particle enters the sensor from the vertical line of the coating surface): 5°

[0117] - Rutherford backscattering spectroscopy (RBS) detector angle (angle formed by the incident beam with the extension line penetrating the sample): 170°

[0118] - Rutherford backscattering spectroscopy (RBS) detector scattering solid angle: 3.1 mSr

[0119] - Standard deviation measurement energy range: 30~700 keV

[0120] - Method for deriving standard deviation: Applying a linear regression model

[0121] - Measurement sensor: PIPS (Passivated Implanted Planar Silicon Detector) or SSD (Silicon Surface Detector), bias V is additionally weighted and can be determined according to sensor specifications.

[0122] (2) Elastic Resonance Analysis (ERDA)

[0123] - Incident ion particles: 4 He 2+

[0124] - Incident ion energy: 2.0 MeV

[0125] - Incident ion beam charge: 10μC

[0126] - Angle of the coating film sample (angle between the ion beam traveling perpendicular to the coating film): 75°

[0127] - Ion incidence angle (angle between the normal direction of the coating film and the incident ion beam): 75°

[0128] - Detector angle of elastic refractive index (ERDA) (angle formed by the incident beam with the extension line penetrating the sample): 30°

[0129] - Detector scattering solid angle of elastic spectroscopy (ERDA): 2.55 mSr

[0130] - Standard deviation measurement energy range: 30~700 keV

[0131] - Method for deriving standard deviation: Applying a linear regression model

[0132] - Install and apply a 10 um Mylar foil filter in front of the sensor.

[0133] - Measurement sensor: PIPS (Passivated Implanted Planar Silicon Detector) or SSD (Silicon Surface Detector), bias V is additionally weighted and can be determined according to sensor specifications.

[0134] If the difference in the concentration of hydrogen atoms in the depth direction is too large, the penetration of hydrogen ions or radicals present in the plasma is easy, so the etching or corrosion speed is too fast.

[0135] The present invention is described in more detail below using examples.

[0136]

[0137] Example 1

[0138] A hydrogen-containing yttrium oxide (Y2O3) coating was formed on a substrate using reactive sputtering. The substrate was ceramic, and the process pressure and internal chamber temperature were controlled to ensure a uniform hydrogen concentration. The base pressure of the vacuum chamber was 2 mTorr, and the internal chamber temperature was maintained at a constant level below ~200°C.

[0139] The target used yttrium, and RF+DC sputtering was applied. The substrate was attached to a ceramic substrate under conditions of 15,000 W DC power and 800 W RF power. To ensure uniformity of the specimen, the drum on which the specimen was mounted rotated at high speed at 100 rpm during deposition.

[0140] The oxygen flow rate during the deposition process was 120 sccm, and the hydrogen flow rate was 5 sccm. The deposition thickness of yttrium oxide (Y2O3) containing minority atoms was 10 micrometers.

[0141]

[0142] Example 2

[0143] An yttrium oxide (Y2O3) coating film containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 10 sccm.

[0144]

[0145] Example 3

[0146] An yttrium oxide (Y2O3) coating film containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 30 sccm.

[0147]

[0148] Example 4

[0149] An yttrium oxide (Y2O3) coating film containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 60 sccm.

[0150]

[0151] Example 5

[0152] An yttrium oxide (Y2O3) coating film containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 80 sccm.

[0153]

[0154] Example 6

[0155] An yttrium oxide (Y2O3) coating film containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 100 sccm.

[0156]

[0157] Example 7

[0158] An yttrium oxide (Y2O3) coating film containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 120 sccm.

[0159]

[0160] Example 8

[0161] An yttrium oxide (Y2O3) coating film containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 150 sccm.

[0162]

[0163] Example 9

[0164] An yttrium oxide (Y2O3) coating film containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 200 sccm.

[0165]

[0166] Comparative Example 1

[0167] An yttrium oxide (Y2O3) coating film 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.

[0168]

[0169] Comparative Example 2

[0170] An yttrium oxide (Y2O3) coating film containing hydrogen atoms was formed in the same manner as in Example 1, except that the hydrogen flow rate was changed to 0 sccm.

[0171]

[0172] Comparative Example 3

[0173] An yttrium oxide (Y2O3) coating film 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.

[0174]

[0175] Comparative Example 4

[0176] An yttrium oxide (Y2O3) coating film 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.

[0177]

[0178] Comparative Example 5

[0179] An yttrium oxide (Y2O3) coating film 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.

[0180]

[0181] Comparative Example 6

[0182] An yttrium oxide (Y2O3) coating film 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.

[0183]

[0184] Comparative Example 7

[0185] An yttrium oxide (Y2O3) coating film containing hydrogen atoms was formed in the same manner as in Example 4, except that the rotation speed of the drum equipped with the sample was changed to 5 rpm.

[0186]

[0187] Comparative Example 8

[0188] An yttrium oxide (Y2O3) coating film containing hydrogen atoms was formed in the same manner as in Example 2, except that the rotation speed of the drum equipped with the sample was changed to 5 rpm.

[0189]

[0190] Table 1 below summarizes the coating film deposition conditions according to Examples 1 to 9 and Comparative Examples 1 to 8.

[0191]

[0192] Oxygen flow rate (sccm) Hydrogen flow rate (sccm) Drum rotation speed (rpm) Example 1 1 2 0 5 1 0 0 Example 2 1 2 0 1 0 1 0 Example 3 1 2 0 3 0 1 0 0 Example 4 1 2 0 6 0 1 0 0 Example 5 1 2 0 8 0 1 0 0 Example 6 1 2 0 1 0 1 0 0 Example 7 1 2 0 1 2 0 1 0 0 Example 8 1 2 0 1 5 0 1 0 0 Example 9 1 2 0 2 0 0 1 0 Comparative Example 1 1 5 0 0 1 0 Comparative Example 2 1 2 0 0 1 0 Comparative Example 3 1 0 0 1 0 Comparative Example 4 8 0 6 0 1 0 0 Comparative Example 5 8 0 8 0 1 0 0 Comparative Example 6 8 0 1 0 1 0 Comparative Example 7 1 2 0 6 0 5 Comparative Example 8 1 2 0 1 0 5

[0193] Experimental Example 1 (Confirmation of the presence of hydrogen in the coating film)

[0194] Secondary ion mass spectrometry (SIMS) was performed on the yttrium oxide coating film manufactured according to Example 4. TOF. SIMS 5 (ION-TOF, Germany) was used as the measuring equipment, and negative mode and depth profiling were applied. A primary source (Bi+, acceleration voltage 30 keV, current 1 pA), an etching source (Cs+, acceleration voltage 2 keV, current 100 nA), an analysis area of ​​100 μm X 100 μm, and an etching area of ​​400 μm X 400 μm were applied, and a plasma flood gun was used.

[0195] The results of secondary ion mass spectrometry are presented in Fig. 1. Referring to Fig. 1, hydrogen atoms were detected in the yttrium oxide coating film manufactured in Example 4. However, due to the limitations of secondary ion mass spectrometry, the atomic ratio of yttrium oxide with other atoms could not be calculated.

[0196]

[0197] Experimental Example 2 (Scanning Electron Microscope Energy Dispersive Spectroscopy)

[0198] The yttrium atomic ratio of the coating films manufactured according to Example 4, Example 9, Comparative Example 1, Comparative Examples 6 to 8 was measured using scanning electron microscope energy dispersive spectroscopy (SEM EDS).

[0199] The measurement areas of energy dispersive spectroscopy were nine areas spaced 20 micrometers apart in the horizontal and vertical directions on a plane parallel to the surface of the coating film, and the analysis areas are indicated in the scanning electron microscope image in Fig. 2. Subsequently, the yttrium atomic ratio and standard deviation in the nine analysis areas were calculated.

[0200] The analysis results of Experimental Example 2 are summarized in Table 2 below.

[0201] Referring to Table 2, it can be confirmed that the deviation of the yttrium atomic ratio decreases rapidly as the rotation speed of the drum equipped with the sample increases. However, it was difficult to determine the tendency of the deviation of the yttrium atomic ratio according to the change in hydrogen flow rate. This is likely because the analysis area of ​​SEM energy-dispersive spectroscopy is relatively larger than that of TEM energy-dispersive spectroscopy, making it difficult to significantly distinguish the deviation of the yttrium atomic ratio in a fine region. In addition, the fact that the standard deviation of the yttrium atomic ratio using SEM energy-dispersive spectroscopy is generally smaller than that of the yttrium atomic ratio using TEM energy-dispersive spectroscopy is also thought to be due to the relatively large area of ​​the analysis area.

[0202]

[0203] Yttrium Atomic Ratio (At %) Standard Deviation Site 1 Site 2 Site 3 Site 4 Site 5 Site 6 Site 7 Site 8 Site 9 Example 4 42.36 43.47 42.34 43.52 42.13 42.88 43.11 43.97 43.21 0.62 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 657.4658.9856.6557.6956.9158.7958.3359.1254.541.45Comparative example 751.6750.4549.8846.6751.5950.2349.4545.2546.162.40Comparative example 841.1643.9641.3443.6242.1143.1842.9243.9744.631.22

[0204] Experimental Example 3 (Transmission Electron Microscope Energy Dispersive Spectroscopy)

[0205] The yttrium and oxygen atomic ratios of the coating films manufactured according to Examples 4, 9, Comparative Examples 1, and Comparative Examples 6 to 8 were measured using transmission electron microscope energy dispersive spectroscopy (TEM EDS). Specimens for transmission electron microscope analysis were polished using a polishing cloth and then prepared using a focused ion beam to obtain specimens of a thickness that allowed electron transmission.

[0206] The measurement areas of energy dispersive spectroscopy were nine areas spaced 0.2 micrometers apart in the horizontal and vertical directions on a plane parallel to the surface of the coating film, and the analysis areas are indicated in the transmission electron microscope image in Figure 3. Next, the standard deviation of the atomic ratio of yttrium or oxygen in the nine analysis areas was calculated.

[0207] The analysis results of Experimental Example 3 are summarized in Table 3 below.

[0208] Referring to Table 3, it can be confirmed that as the amount of hydrogen injected increases, the deviation in the yttrium atomic ratio increases, and as the rotation speed of the drum on which the sample is mounted increases, the deviation in the yttrium atomic ratio decreases rapidly.

[0209] These results include some trends that were not confirmed in scanning electron microscope energy-dispersive spectroscopy, which means that the hydrogen flow rate and specimen rotation speed of the reactive sputtering process that forms the coating film affect the atomic ratio homogeneity of the coating film, and in particular, this trend can be confirmed in an analysis method with a small analysis area and high resolution, such as transmission electron microscopy. In the present invention, it was discovered that the atomic ratio homogeneity in the micro-area of ​​the coating film affects the etching resistance or corrosion resistance against plasma, and from this point of view, it was confirmed that transmission electron microscope energy-dispersive spectroscopy is an effective analysis method that can prove this.

[0210]

[0211] Yttrium Atomic Ratio (At %) Standard Deviation Site 1 Site 2 Site 3 Site 4 Site 5 Site 6 Site 7 Site 8 Site 9 Example 4 44.87 44.56 41.68 42.02 41.45 41.05 42.29 43.56 42.01 1.38 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 41.139.68 39.76 41.97 42.02 43.5 11.33 Comparative Example 653.155.358.258.5652.3456.5660.1360.4556.112.87Comparative example 756.7851.3246.8945.2246.8950.9943.0453.7757.565.12Comparative example 845.7943.4739.8841.0538.8640.7644.8747.0246.713.10

[0212] Experimental Example 4 (Porosity Measurement)

[0213] As a result of measuring the gas adsorption specific surface area (BET) for the coating films manufactured by the examples and comparative examples, the porosity was measured to be 0 for all the coating films.

[0214]

[0215] Experimental Example 5 (Grain Diameter Measurement)

[0216] The grain diameter of the coating films manufactured by the examples and comparative examples was measured through XRD analysis.

[0217] The measured results are shown in Table 4 below.

[0218] Referring to Table 4, it can be seen that the grain diameter changes as the rotation speed of the drum on which the sample is mounted changes, and as the rotation speed increases, the uniformity of the grain diameter relatively increases.

[0219]

[0220] Grain average diameter (nanometers) 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 5.55 312.99 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 62.54 3.51 40.13 75.44 80.73 102.56 185.23 52.31

[0221] Experimental Example 6 (Hardness Measurement)

[0222] To determine the hardness of the coating, a nanoindenter (NHT3, Anton Paar) was used. Under specific conditions, the pressure was 20 mN, and the coating surface was measured approximately five times.

[0223] The hardness of the measured coating film was measured to be 8 GPa or more in the examples, and the measurement results are shown in Fig. 18.

[0224]

[0225] Experimental Example 7 (Measurement of Hydrogen Concentration, Elastic Semiconductivity Measurement)

[0226] The hydrogen concentration of the coating films 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 using secondary ion mass spectrometry used in Experimental Example 1.

[0227] The process of measuring the hydrogen concentration of the coating film using the elastic semiconductivity measurement method first derives the flux of incident ions and the atomic % of yttrium and / or oxygen atoms in the coating film using Rutherford Backscattering Spectrometry (RBS) on the coating film sample, and then uses this as correction information for the measurement data of the subsequent elastic semiconductivity measurement method to ultimately derive the atomic % of hydrogen in the coating film.

[0228] The equipment used for the analysis is ion species 4 He 2+ (2 protons + 2 neutrons, alpha particles), and a tandem ion accelerator (Pelletron Linear Accelerator, NEC (national electrostatics corp) model 6SDH-2) was used as the ion accelerator. The energy of the incident ions 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, and an area of ​​1 mm X 4 mm was scanned. The ion beam current incident on the coating film was set to 10 uC.

[0229] The ion beam, sample, and detector angle settings for elastic recombination spectroscopy (ERDA) and Rutherford backscattering spectroscopy (RBS) are illustrated in detail in Figs. 5a and 5b. The specific analytical equipment operation process is as follows: alpha particles accelerated to an energy of 2 MeV by a tandem ion accelerator 4 He 2+), the alpha particles backscattered close to the normal angle to the sample surface (normal angle to the sample surface) were measured in Rutherford backscattering spectroscopy, and this is shown in Fig. 5a.

[0230] Figure 5b shows a diagram for an elastic semiconductivity measurement method, in which alpha particles are incident at an angle to the sample surface of the coating film (grazing angle to the sample surface) and recoil hydrogen atoms are measured.

[0231] The specific measurement conditions for Rutherford backscattering spectroscopy and elastic semiconductivity measurement are as follows.

[0232] (1) Rutherford backscattering spectroscopy (RBS)

[0233] - Incident ion particles: 4 He 2+

[0234] - Incident ion energy: 2.0 MeV

[0235] - Incident ion beam charge: 10μC

[0236] - Ion incidence angle (angle between the normal direction of the coating film and the incident ion beam): 5°

[0237] - Angle of the coating film sample (angle between the vertical direction of the coating film and the incident ion beam): 5°

[0238] - Exit angle (the angle at which the reflected particle enters the sensor from the vertical line of the coating surface): 5°

[0239] - Rutherford backscattering spectroscopy (RBS) detector angle (angle formed by the incident beam with the extension line penetrating the sample): 170°

[0240] - Rutherford backscattering spectroscopy (RBS) detector scattering solid angle: 3.1 mSr

[0241] - Standard deviation measurement energy range: 30~700 keV

[0242] - Method for deriving standard deviation: Applying a linear regression model

[0243] - Measurement sensor: PIPS (Passivated Implanted Planar Silicon Detector) or SSD (Silicon Surface Detector), bias V is additionally weighted and can be determined according to sensor specifications.

[0244] (2) Elastic Resonance Analysis (ERDA)

[0245] - Incident ion particles: 4 He 2+

[0246] - Incident ion energy: 2.0 MeV

[0247] - Incident ion beam charge: 10μC

[0248] - Angle of the coating film sample (angle between the ion beam traveling perpendicular to the coating film): 75°

[0249] - Ion incidence angle (angle between the normal direction of the coating film and the incident ion beam): 75°

[0250] - Detector angle of elastic refractive index (ERDA) (angle formed by the incident beam with the extension line penetrating the sample): 30°

[0251] - Detector scattering solid angle of elastic spectroscopy (ERDA): 2.55 mSr

[0252] - Standard deviation measurement energy range: 30~700 keV

[0253] - Method for deriving standard deviation: Applying a linear regression model

[0254] - Install and apply a 10 um Mylar foil filter in front of the sensor.

[0255] - Measurement sensor: PIPS (Passivated Implanted Planar Silicon Detector) or SSD (Silicon Surface Detector), bias V is additionally weighted and can be determined according to sensor specifications.

[0256] Coating film sample treatment: A 5-micrometer-thick coating film was formed on a silicon substrate, the surface was cleaned with ethanol, and heat-treated in a dry furnace at 50 degrees for 24 hours. Since the measurement results may be affected by contamination such as additional oxide films formed on the surface, the surface of the coating film was etched twice by argon sputtering to a thickness of up to 600 nanometers before measurement. In the next step, Rutherford backscattering spectroscopy was performed first, and then the same sample was coated with 1-2 nanometers of gold in a vacuum chamber and stored in a vacuum chamber at 10-6 mbar, and elastic semiconductivity measurement and spectroscopy were performed consecutively.

[0257] This process is schematically illustrated in Fig. 6. Fig. 6 (a) is a cross-section before argon sputtering, where t1 represents the thickness of the coating film contaminated during storage, and t2 represents the thickness that can be measured by the elastic semiconductivity measurement method excluding the contaminated area. Fig. 6 (b) is a cross-section after argon sputtering, where a contaminated layer with a thickness of t3 may be generated again during the process of transferring to the elastic semiconductivity measurement chamber after sputtering, and t4 represents the thickness that can be measured by the elastic semiconductivity measurement method. In order to ensure the reproducibility of the elastic semiconductivity measurement method, the thickness of the argon sputtering may be 100 to 700 nanometers.

[0258] Figures 7 to 10 show the results of measuring the amount of hydrogen atoms contained in a coating film using an elastic semiconductivity measurement method. Each figure shows the results of the elastic semiconductivity measurement method for measuring the hydrogen atom concentration of coating films manufactured by Example 2 (Figure 7), Example 3 (Figure 8), Example 4 (Figure 9), and Comparative Example 6 (Figure 10).

[0259] Referring to the drawing, the horizontal axis represents the energy of ions or atoms (recoil particles) existing in the measurement coating film, and the hydrogen atoms existing inside the coating film 4 He 2+ This represents the energy of hydrogen atoms or hydrogen ions emitted toward the detector after colliding with ions (alpha particles). The peak observed in the region of approximately 700–900 keV is due to hydrogen atoms that existed relatively close to the surface of the coating film, and the intensity is caused by water molecules that contaminate the surface of the coating film and bind to it. The signal observed in the region of approximately 30–700 keV is due to hydrogen atoms that exist deeper than the surface contamination area of ​​the coating film. At this time, 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 due to energy loss that occurs as hydrogen atoms are emitted from the inside to the outside of the coating film. Therefore, the normalized yield observed in the region of approximately 30–700 keV reflects the depth information of the hydrogen atoms contained in the coating film. The normalized yield value here means the relative amount of hydrogen atoms or hydrogen ions emitted per incident helium ion, and the normalized yield value derived by energy intensity is corrected from the measurement results of Rutherford backscattering spectroscopy.

[0260] From the results of elasticity measurement of the examples and comparative examples, the concentration of hydrogen atoms existing inside the coating film can be quantified, and the value range of the standardized yield used at this time is the data of the standardized yield in the range of 30 to 700 keV excluding the information on the contaminated surface of the coating film.

[0261] The hydrogen atom concentrations of the examples and comparative examples calculated from the measurement results of the elastic semiconductivity measurement method are summarized in Table 5 below.

[0262] Referring to Table 5, it can be confirmed that the flow rate of hydrogen injected during the manufacturing process of the coating film and the amount of hydrogen contained in the coating film are proportional.

[0263]

[0264] 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 10.11 5.5 20.8 14.0 3 1.01

[0265] Experimental Example 8 (Deriving the standard deviation of hydrogen concentration, using the results of elastic semiconductivity measurement)

[0266] Using the Elastic Recoil Detection Analysis (ERDA) measurement results from Experimental Example 7, the standard deviation of hydrogen concentration reflecting information about the thickness direction of the coating film was derived. Although the hydrogen energy measured in Experimental Example 7 is not linearly inversely proportional to the depth of the coating film, the magnitude of the hydrogen energy provides information reflecting the thickness direction position of the coating film.

[0267] In the measurement results of the elastic semiconductivity measurement method, the hydrogen energy range of 30 to 700 keV is the range excluding the surface contamination information of the coating film. The standard deviation of the hydrogen concentration refers to the degree to which the data in the 30 to 700 keV range deviates by +σ, -σ (standard deviation: sigma) in the Y-axis direction based on the value of the linear regression line, and refers to the standard deviation of the concentration of hydrogen atoms distributed in the depth direction of the coating film.

[0268]

[0269] The procedure for obtaining the range of the standardized yield value is described in detail below.

[0270] First (Process A), from the original full energy (0 keV - 2000 keV region) data, data with energies between 30 keV and 700 keV are extracted based on the X-axis data. At this time, the theoretical model of the linear regression model is used, specifically, n X in the form of Y = β0 + β1X1 + β2X2 + ... n It is given in the form of independent variables and dependent variable Y. The linear independent variables of the given data are specified as n=1, so Odinary Least Square (OLS) = , that is, Y= + β1X1+ β2X2+ ...+ β that minimizes the sum of squares for the entire data n X n Each β of n To obtain the value, the following gradient descent process is used for calculation.

[0271]

[0272] Here, each variable is as follows:

[0273] α: learning rate

[0274] J (cost function) is defined as follows:

[0275]

[0276] Through the equation that has the minimum value of the previous process Ordinary Least Square (OLS), If you find the interval where the values ​​converge, you get a straight line graph (a straight line graph Y with slope m, Y-axis intercept b, linear-regression = mx +b ) can be obtained.

[0277] Next, in process A, the sampling standard deviation, σ (standard deviation: sigma), is calculated based on the Y-axis value based on the data in the 30 keV-700 keV region.

[0278] Next, based on the linear regression line of the central part with slope m and Y-axis intercept, Y linear-regression The upper boundary defined as + 2σ (standard deviation: sigma) (see Figs. 11 to 17) and Y linear-regression - Two additional straight lines can be obtained, which are the lower boundary lines defined by 2σ (see Figs. 11 to 17) (standard deviation: sigma).

[0279] At this time, the range of standardized yield values ​​is Y linear-regression + 2σ (standard deviation: σ sigma) and Y linear-regression - 2σ (standard deviation: σ sigma) can be specified as the area between two additional straight lines.

[0280] Figures 11 to 17 show the range of the standardized yield in the energy region of 30 to 700 KeV of hydrogen atoms measured by the elastic semiconductometry method. Each figure is a result reflecting the standard deviation of the standardized yield for the coating films manufactured by Figure 11, Example 2, Figure 12, Example 3, Figure 13, Example 6, Figure 14, Comparative Example 2, Figure 15, Comparative Example 6, Figure 16, Comparative Example 7, and Figure 17, Comparative Example 8.

[0281] Table 6 below summarizes the results reflecting the standard deviation of the standardized yield of the coating films manufactured by the examples and comparative examples.

[0282] Referring to Table 6, it can be seen that as the amount of hydrogen injected increases, the standard deviation of the reflected results tends to increase, and as the rotation speed of the drum equipped with the sample increases, the standard deviation decreases rapidly.

[0283]

[0284] Standardized Yield Standard DeviationExample 1Example 2Example 3Example 4Example 5Example 6Example 7Example 8 90.080.0950.1890.5880.7641.1211.2431.3761.511Comparative Example 1Comparative Example 2Comparative Example 3Comparative Example 4Comparative Example 5Comparative Example 6Comparative Example 7Comparative Example 80.0510.0540.0521.7411.9182.7673.3650.352

[0285] Experimental Example 9 (Analysis of plasma characteristics, CF4+O2 etching gas)

[0286] Plasma resistance experiments were performed on the coating films manufactured by the examples and comparative examples using CF4+O2 gas. The plasma etching device used was a capacitively coupled plasma (CCP) device, and the plasma etching conditions were as follows: power output of 300 W for CCP output, process gas mixed with CF4 gas and O2 gas at a ratio of 2:1, process pressure of 30 mtorr, and plasma etching time of 3 hours.

[0287] To measure the etching amount, a portion of the coating film was masked with Kapton tape before the plasma etching experiment, and the step difference between the masked area and the non-masked area irradiated with plasma after the etching experiment was measured using Alphastep. Specifically, 20mmX 20mmX2t, Al2O3 were commonly used as the base material, and the step difference of the specimen for each condition was recorded as the etching amount.

[0288] The results of Experimental Example 9 are summarized in Table 7 below.

[0289] Referring to Table 7, the coating film with the hydrogen concentration controlled within a certain range exhibited excellent plasma resistance characteristics, and in the case of coating films with similar hydrogen concentration ranges, the coating film with less depth-direction deviation in hydrogen concentration exhibited significantly superior plasma resistance characteristics.

[0290]

[0291] Etching amount (nm) Relative etching ratio (based on Comparative Example 2) Example 1 320.7 0.78 Example 2 310.3 0.76 Example 3 298.4 0.73 Example 4 279.10.68 Example 5 265.4 0.65 Example 6 263.5 0.64 Example 7 276.8 0.67 Example 8 294.10.72 Example 9 312.2 0.76 Comparative Example 1 422.11.03 Comparative Example 2 410.51 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 7542.11.32 Comparative Example 8424.31.03

[0292] Experimental Example 10 (Analysis of plasma characteristics, CF4+O2+H2 etching gas)

[0293] Plasma resistance experiments were performed on the coating films manufactured by the examples and comparative examples. The plasma etching device used a capacitively coupled plasma (CCP) device, and the plasma etching conditions were as follows: a CCP output of 300 W as the power output, CF4+O2 as the process gas at a ratio of 2:1, for 30 minutes, and then sequentially H2+Ar 3:1 for 2 hours and 30 minutes, with each process pressure set to 20 mtorr and the total plasma etching time set to 3 hours.

[0294] To measure the etching amount, a portion of the coating film was masked with Kapton tape before the plasma etching experiment, and the step difference between the masked and unmasked areas irradiated with plasma after the etching experiment was measured using AlphaStep. Specifically, the base material was commonly 20mmx20mmx2t, Al2O3, and the step difference of the specimen for each condition was recorded as the etching amount.

[0295] The results of Experimental Example 10 are summarized in Table 8 below.

[0296] Referring to Table 8, the tendency of the plasma resistance characteristics of the coating film is similar to that of Experimental Example 9, but it was confirmed that the plasma resistance characteristic improvement effect of the example in which the drum equipped with the sample was rotated showed a tendency to be more excellent than that of the halogen-based etching gas.

[0297]

[0298] Etching amount (nm) Relative etching ratio (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 2 220.71 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 7491.32.23 Comparative Example 8224.21.02

Claims

1. A coating film formed on the surface of a vacuum chamber wall or internal components used in the manufacture of semiconductors or display devices. The coating film is characterized in that the coating film contains an yttrium compound, has resistance to plasma, and contains hydrogen atoms in a predetermined concentration.

2. In paragraph 1, A coating film characterized in that the above yttrium compound is yttrium oxide or yttrium aluminum oxide.

3. In paragraph 2, The above yttrium oxide is a coating film characterized in that the atomic ratio of yttrium and oxygen is in the range of 1:0.6 to 1:2.

5.

4. In paragraph 2, The above yttrium aluminum oxide is a coating film characterized in that the atomic ratio of yttrium and aluminum is in the range of 1:0.1 to 1:7.

0.

5. In paragraph 1, A coating film characterized in that the concentration of hydrogen atoms contained in the coating film is 0.2 to 9 atomic%.

6. In paragraph 5, A coating film characterized in that the concentration of the hydrogen atoms is measured by elastic recoil detection.

7. In paragraph 1, A coating film characterized in that the porosity of the coating film is 5% or less.

8. In paragraph 1, A coating film characterized in that the coating film includes a crystalline substance.

9. In paragraph 1, A coating film characterized in that the average grain diameter of the coating film is 70 nanometers or less.

10. In paragraph 1, A coating film characterized in that the hardness of the coating film is 8 GPa or more.

11. In paragraph 1, A coating film characterized in that the standard deviation of the standardized yield of hydrogen measured by the energy elastic recoil detection method under the following measurement conditions for the above coating film is in the range of 0.07 to 1.

6. (1) Rutherford backscattering spectroscopy (RBS) - Incident ion particles: 4 He 2+ - Incident ion energy: 2.0 MeV - Incident ion beam charge: 10μC - Ion incidence angle (angle between the normal direction of the coating film and the incident ion beam): 5° - Rutherford backscattering spectroscopy (RBS) detector angle (angle formed by the incident beam with the extension line penetrating the sample): 170° - Rutherford backscattering spectroscopy (RBS) detector scattering solid angle: 3.1 mSr - Standard deviation measurement energy range: 30~700 keV (2) Elastic Resonance Analysis (ERDA) - Incident ion particles: 4 He 2+ - Incident ion energy: 2.0 MeV - Incident ion beam charge: 10μC - Ion incidence angle (angle between the normal direction of the coating film and the incident ion beam): 75° - Detector angle of elastic refractive index (ERDA) (angle formed by the incident beam with the extension line penetrating the sample): 30° - Detector scattering solid angle of elastic spectroscopy (ERDA): 2.55 mSr - Standard deviation measurement energy range: 30~700 keV - Method for deriving standard deviation: Applying a linear regression model 12. In paragraph 11, The above elastic recoil detection method is characterized in that the coating film is performed after removing 100 to 700 nanometers from the surface of the coating film by argon ion sputtering.

13. In paragraph 3, A coating film characterized in that the yttrium atomic ratio of the above yttrium oxide is in the range of a standard deviation of 0.1 to 1.8 under the analysis conditions below. - Analysis method: Transmission electron microscope energy dispersive spectroscopy - Measurement area: 9 areas spaced 0.2 micrometers apart in the horizontal and vertical directions on a plane parallel to the surface of the coating film - Standard deviation calculation: Standard deviation of the yttrium atomic ratio measured at the above measurement site 14. Containing any one of the coating films of clauses 1 to 13, Vacuum chamber walls or internal components used in the manufacture of semiconductor or display devices.

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